JPH0559394A - Detergent composition - Google Patents

Abstract

PURPOSE: To provide a detergent compsn. which possesses increased detergency for removing stains of fats and oils deposited on the surface of fiber products, tableware, furniture and the like by comprising a micellar phase surfactant and a lamellar phase surfactant, at least one of the surfactants being a glycolipid biosurfactant.

CONSTITUTION: This detergent compsn. comprises: (A) a micellar phase surfactant; and (B) a lamellar phase surfactant, wherein the wt. ratio of the component A to the component B is pref. (20:1) to (1:20) and the component A and/or the component B contain a glycolipid biosurfactant contg. a rhamnolipid represented by formula I [wherein a and b represent 1 or 2; n is 4 to 10; R¹ represents H or a cation; and R² represents H or formula II (wherein m is 4 to 10)].

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions, especially compositions used for cleaning surfaces such as textiles, tableware and furniture. The compositions of the present invention are particularly, but not exclusively, suitable for laundering textiles and comprise one or more glycolipid biosurfactants.

[0002]

BACKGROUND OF THE INVENTION Detergent compositions usually contain one or more cleaning actives in addition to various ingredients such as detergency builders, bleaches, fluorescent agents, perfumes and the like. The main uses of detergent compositions are:
Washing of textiles, usually by washing portable textiles in a tub or washing machine, washing of crockery and utensils, also by washing in the tub (hand dish washing), and Cleaning of hard surfaces such as glass, glazing, plastic, metal and enamel.

A number of surfactants, some of them for some years, have been used as cleaning actives, including anionic and cationic substances.

Glycolipid biosurfactants, which will be described in detail later, include rhamnolipid, sophorose lipid, glucose lipid, cellobiose lipid and trehalose lipid.
There is. The glycolipid biosurfactant can be produced by bacterial or yeast fermentation. This is an inherent advantage in the sense that fermentation products can usually be derived from renewable raw materials and biodegradation after use can be expected.

Japanese Patent JP 63 077 535A
No. (Toyo Beauty) discloses an emulsion composition containing α-decene-bound rhamnolipid or a salt thereof as an emulsifier. This emulsion is cosmetic
It is stated to be useful in health care products, medicines, detergents and foods.

[0006] West German Patent DE 3 562 417 A (Wella) discloses a cosmetic product containing sophorose lipid lactone which is used for the prevention of dandruff and as a bacteriostatic agent in deodorants.

US Pat. No. 4,216,311 (K
ao) discloses the preparation of glycolipid methyl ester from sophorose lipids. These glycolipid methyl esters are useful as bases or additives for various cleansers and oil products, and as coating and printing processes, textile processing, metalworking, stationery, cosmetics, pharmaceuticals, agricultural chemicals, anti-glare. , Synthetic resin, papermaking,
It can be used for machinery, leather, etc.

Applicant's co-pending UK patent application No. 9102945.4, filed February 12, 1991, describes the use of rhamnolipid in combination with other surfactants in detergent compositions. Has been done.

[0009]

Applicants have found that when glycolipid biosurfactants are used in combination with each other or with another surfactant, the synergistic action of detergency of greasy soils. Have been found to increase. In this way, an increase in detergency was observed even when glycolipid, which had poor detergency alone, was used.

Therefore, the present invention comprises (i) a first surfactant which is a micellar phase surfactant and (ii) a second surfactant which is a lamellar phase surfactant. 1
And a second surfactant, wherein at least one of them is a glycolipid biosurfactant.

The present invention comprises contacting a textile or an inanimate surface to be washed with the composition described above or by adding the composition to water, in particular in an amount of 0.5 to 50 grams per liter of water. Also provided is a cleaning method comprising contacting with the resulting cleaning liquid.

[0012]

The detergent composition of the present invention comprises:
It comprises at least two surfactants with different properties, at least one of which must be a glycolipid biosurfactant.

In the present specification, the two kinds of surfactants are referred to as a micellar phase surfactant and a lamellar phase surfactant, respectively. These terms refer to the structure of the phases that the surfactant would have under typical washing conditions.

These two kinds of surfactants have a pH of 7.
This can be determined by the behavior of a 1% by weight aqueous solution of deionized water at 0 and a temperature of 25 ° C. The surfactant solution containing the dispersed lamellar phase has a birefringent structure when observed with a polarizing microscope, but the miscella solution does not show such a structure.

Generally, the miscella phase surfactant has a pH of
A clear solution is formed when present at a concentration of 1% by weight in deionized water at 7.0, 25 ° C. However, the transparency may be reduced if a small amount of impurities are present. Lamellar phase surfactants always form an opaque solution when present at a concentration of 1% by weight in deionized water at pH 7.0 and 25 ° C.

At least one of these surfactants has to be selected from a particular surfactant class, namely glycolipid biosurfactants, while the other may or may not be a glycolipid biosurfactant. May be. That is, some of the glycolipids are micellar phase surfactants and some are lamellar phase surfactants.

Glycolipid surfactants useful in the present invention include rhamnolipids, glucose lipids, sophorose lipids, trehalose lipids, cellobiose lipids and mixtures thereof. In any type of glycolipid, one substance may be a miscella and the other substance may be a lamella.

The miscellaneous phase glycolipid biological surfactants are rhamnolipid, glucose lipid, sophorose lipid,
It may be suitably selected from cellobiose lipids and mixtures thereof.

The lamellar phase glycolipid biosurfactant may be suitably selected from rhamnolipids, glucose lipids, trehalose lipids and mixtures thereof.

Both surfactants (i) and (ii) may be glycolipids. In that case, it is most preferred that the miscella phase glycolipid is rhamnolipid, sophorose lipid or cellobiose lipid, and the lamella phase glycolipid is trehalose lipid, glucose lipid or rhamnolipid.

Alternatively, the surfactants (i) and (ii)
One of them may be a non-glycolipid surfactant, preferably an anionic or non-ionic surfactant. Zwitterionic and cationic surfactants are not preferred and if used, for example 10% by weight of the total surfactant present.
The following low concentrations are desirable.

Preferred anionic and nonionic surfactants are listed below.

The weight ratio of the first surface-active agent (i) to the second surface-active agent (ii) is preferably in the range of 20: 1 to 1:20, a narrower range, eg 10: 1 to 1:10. , And more preferably 4: 1 to 1: 4.

Glycolipid Biosurfactants Specific biosurfactants include rhamnolipids, glucose lipids, sophorose lipids, trehalose lipids, cellobiose lipids and mixtures thereof. Here, these surfactants will be individually described in detail.

Rhamnolipids Biological surfactants of this type have the formula (I):

[0026]

[Chemical 7]

[In the formula, a is 1 or 2, b is 1 or 2, n is 4 to 10, and preferably 6,
R ¹ is H or a cation, preferably H or a monovalent solubilizing cation, and R ² is H or a group shown below.

[0028]

[Chemical 8]

And preferably H and m is 4 to 1
0, and the values of m and n need not all be the same].

Rhamnolipid can be produced by bacterial fermentation. This is an inherent advantage in the sense that bacterial fermentation products can usually be derived from renewable raw materials and biodegradation after use can be expected. Another advantage of the surfactant of formula (I) is that it is obtained as a by-product of enzyme production.

[0031] rhamnolipid can be prepared by Pseudomon as bacteria of the genus. This bacterial fermentation usually uses sugar, glycerol, alkanes or mixtures thereof as substrates.

Suitable fermentation methods are described in D. Haferbur
g, R. Homel, R.M. Claus and H.C. P. K
Lever, Adv. Biochem. Eng. / Bi
otechnol . (1986) 33 , 53-90, and F.M. Wagner, H .; Bock and A. Kret
schmar, Fermentation (ed.R.
M. Lafferty) (1981), 181-19.
2, Springer Verlag, Vienna.

Usually, any rhamnolipid sample contains a variety of individual compounds of general formula (I). The proportion of individual compounds will depend on the microbial species, the particular strain used for fermentation, the substrate material supplied for fermentation and other fermentation conditions.

This bacterial fermentation usually produces compounds in which R ^{1 in} the formula is hydrogen or a solubilizing cation. Compounds of this kind may give rise to conversion between salt and acid forms in aqueous solution, depending on the pH of the solution. Common solubilizing cations are alkali metal, ammonium and alkanolamine cations.

Glucose Lipid A second type of glycolipid biosurfactant for use in the present invention is the following formula (II):

[0036]

[Chemical 9]

[Wherein R ¹ is H or a cation, p 1
Is 1 to 4 and q is 4 to 10, preferably 6.]
It consists of glucose lipid represented by.

Glucose lipids are bacteria Alcalige
nes Sp. It can be manufactured by MM1 . A suitable fermentation method is M. Schmidt's PhD thesis (1990),
Technical University of B
raunschweig, and Schulz et al. (199
1) Z. Natureforsch 46C 197-
203. Glucose lipids are recovered from the fermentation broth by solvent extraction with ethyl ether or dichloromethane: methanol or chloroform: methanol mixtures.

Sophorose Lipid A third type of glycolipid biosurfactant for use in the present invention is the following formula (III):

[0040]

[Chemical 10]

[Wherein R ³ and R ⁴ individually represent H or an acetyl group, and R ⁵ is a saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon group having 1 to 9 carbon atoms, preferably a methyl group. And R ⁶ is a saturated or unsaturated hydroxylated or unhydroxylated hydrocarbon radical having 1 to 19 carbon atoms, provided that the total number of carbon atoms in the radicals R ⁵ and R ⁶ is 20.
Hereinafter, it is preferably 14 to 18].

This sophorose lipid may be in the open chain free acid form where R ⁷ is H and R ⁸ is OH, or is of formula (I
V):

[0043]

[Chemical 11]

[Wherein R ³ , R ⁴ and R ⁶ are as defined above, with the proviso that at least one of R ³ and R ⁴ is an acetyl group], and between R ⁷ and R ⁸ The lactone ring may be incorporated into the detergent composition of the present invention.

Sophorose lipids are used in yeast cells such as To
rulopsis apicola and Torulop
It can be produced by sis bombicola . Sugar and alkanes are usually used as substrates for this fermentation process. A suitable fermentation method is A. P. Tulloc
h, J. F. T. Spencer and P.M. A. J. Go
rin, Can. J. Chem (1962) 40 13
26, and U.V. Gobbert, S .; Lang and F.D. Wagner, BiotehcologyLet
ters (1984) 6 (4), 225. The product obtained is a mixture of various open-chain sophorose lipids and sophorose lipid lactones, which can be used in the form of a mixture or can be separated in the desired form. When the glycolipid biosurfactant comprises sophorose lipid, the weight ratio of sophorose lipid to other surfactants is preferably in the range of 4: 1 to 3: 2, more preferably 4: 1.

Trehalose Lipid A fourth type of glycolipid biosurfactant for use in the present invention is represented by the following general formula (V):

[0047]

[Chemical formula 12]

[Wherein R ⁹ , R ¹⁰ and R ¹¹ each independently represent a saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon group having 5 to 13 carbon atoms].

Trehalose lipid is a marine bacterium Arthr
objecter sp. Ek 1 or freshwater bacterium Rhod
ococcus erythropolis . A suitable fermentation method is described by Ishigami et al.
87), J. Jpn. OilChem. Soc. 368
47-851, Schultz et al. (1991), Z. N
atturforsch 46C 197-203, and Passeri et al. (1991), Z. Nature
sch 46C 204-209.

Cellobiose Lipids A fifth type of glycolipid biosurfactant for use in the present invention is represented by the following general formula (VI):

[0051]

[Chemical 13]

[Wherein R ¹ is H or a cation, and R ¹ is
¹² is a saturated or unsaturated hydroxylated or unhydroxylated hydrocarbon group having 9 to 15 carbon atoms, preferably 13, R ¹³ is H or an acetyl group, and R ¹⁴ is a saturated group having 4 to 16 carbon atoms. Or an unsaturated hydroxylated or non-hydroxylated hydrocarbon group].

Cellobiose lipids can be produced by fungal cells from the genus ustilago . Suitable fermentation methods are described in Frautz, Lang and Wagner (198).
6) Biotech Letts 8 757-762.
It is described in.

When the glycolipid biosurfactant consists of cellobiose lipid, the weight ratio of cellobiose lipid to additional surfactant is preferably from 4: 1 to 2: 3.

Non-Glycolipid Surfactant As previously described, the detergent composition of the present invention comprises at least 1
Optionally at least one non-glycolipid interface, in addition to the above-mentioned glycolipid biosurfactant, provided that one micellar phase surfactant and at least one lamellar phase surfactant are blended. An active agent may be included.
The glycolipid biosurfactant is preferably in the micellar phase and the non-glycolipid surfactant is preferably in the lamellar phase.

The non-glycolipid surfactant may be selected from anionic surfactants, nonionic surfactants, zwitterionic surfactants, cationic surfactants. However, when incorporating amphoteric or cationic surfactants, it is desirable to incorporate them at low levels, such as 10 wt% or less of the total surfactant incorporated.

[0057] Examples of suitable anionic surfactants which may be used anionic surface active agents, alkylbenzene sulfonates, alkyl ether sulfates, olefin sulfonates, alkyl sulfonates,
Secondary alkyl sulfonates, fatty acid ester sulfonates, dialkyl sulfosuccinates, alkyl orthoxylene sulfonates and literature, especially "surfactants" [Vol.
1, Schwartz & Perry, Interscience 1949] and "Surfactants" [Vol.2, Shwartz, Perry & Berch, Intersc
ience 1958], “MuCutcheon's Emulsifiers & Deterg
ents ”[latest issue, MuCutcheon division of Manufacturi
ng Confectioners Company] or “Tensid-Taschenbu
ch ”[H.Stache, 2nd edition., Carl Hanser Verlag, Munche
n & Wien, 1981].

Particular examples of alkylbenzene sulphonates include the alkali metal, ammonium or alkanolamine salts of alkylbenzene sulphonic acids having 10 to 18 carbon atoms in the alkyl radical.

Suitable alkyl and alkyl ether sulphates include those having 10 to 24 carbon atoms in the alkyl group, the alkyl ether sulphates having 1 to 5 ethylene oxide groups.

Suitable olefin sulfonates include:
C ₁₀ -C ₂₄ alpha-olefins were sulfonated and subsequently neutralized sulfonation reaction products are those prepared by hydrolyzing.

Particular examples of alkylsulfates or sulfated fatty alcohol salts include mixtures of alkyl chain lengths in which the ratio of C ₁₂ alkyl chains to C ₁₈ alkyl chains is from 9: 4 to 1: 6. Be done. Suitable materials can be obtained from a mixture of synthetic lauryl alcohol and oleyl alcohol of suitable properties.

Specific examples of fatty acid ester sulfonates include the general formula: [Wherein R ¹ is derived from tallow, palm or coconut oil, and R ² is a short-chain alkyl group (eg, butyl)].

As a specific example of a dialkyl sulfosuccinate, both alkyl substituents have at least 4 carbon atoms.
And those containing 12 to 20 carbon atoms in total (for example, di-C ₈ alkylsulfosuccinate, etc.).

Specific examples of alkyl orthoxylene sulfonates include those where the alkyl group contains 12 to 24 carbon atoms.

Other anionic surfactants which can be used include alkali metal soaps of fatty acids, preferably fatty acids containing 12 to 18 carbon atoms. Typical examples of such acids include oleic acid, ricinoleic acid and castor oil,
There are fatty acids derived from rapeseed oil, peanut oil, coconut oil, palm kernel oil or mixtures thereof. Sodium or potassium soaps of these acids may be used. In addition to acting as a surfactant, soap can also act as a detergency builder or textile conditioner.

Dialkyl sulfosuccinates are of particular importance as lamellar phase anionic surfactants for use in the present invention.

Nonionic Surfactants Nonionic detergent compounds that can be used include alkyl (C
₆ -C ₂₂₎ phenols - generation by condensation of ethylenediamine reaction product - ethylene oxide condensates, condensates and ethylene oxide and propylene oxide with linear or branched aliphatic C ₈ -C ₂₀ 1 primary or secondary alcohols with ethylene oxide Things can be mentioned. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, alkyl sulfoxide, C ₁₀ -C ₁₄ alkyl pyrrolidone and tertiary phosphine oxides.

Suitable lamellar phase nonionic surfactants include those having an HLB value of 10.5 or less, preferably 10 or less, more preferably 8.5 to 9.5. In the case of ethoxylated nonionic surfactants, the HLB value is defined to be 1/5 (mol%) of ethylene oxide in the molecule.

Suitable nonionic surfactants may be ethoxylated substances, especially ethoxylated fatty alcohols with a relatively low ethoxylation rate such that the HLB value is below 10.5.

However, the ethylene oxide content of the nonionic surfactant is preferably <5% by weight of the surfactant system or 0, and various non-ethoxylated nonionic surfactants are also suitable for use in the present invention. It is suitable.

Examples of these include the general formula: R ¹⁵ O (R ¹⁶ O) _t (G) _y or R ¹⁵ CO (═O).
(R ¹⁶ O) _t (G) _y [wherein, R ¹⁵ is an organic hydrophobic residue containing 10 to 20 carbon atoms, R ¹⁶ contains 2 to 4 carbon atoms, and G is Is a sugar residue containing 5 to 6 carbon atoms, t is 0 to 25, and y is 1 to 10].

The hydrophobic group R ¹⁵ is preferably alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl. However, aryl groups (eg, alkyl-aryl, alkenyl-aryl and hydroxyalkyl-
Aryl etc.). R is 10 to 16 carbon atoms
Preferably, it is an alkyl or alkenyl, especially of 12 to 14 carbon atoms.

The value of t in the above general formula is preferably 0, so there is no-(R ¹⁶ O) _t -unit in the general formula.

When t is not 0, R ¹⁶ O is preferably an ethylene oxide residue. Others may be propylene oxide and glycerol residues. When the parameter t is not 0 and R ¹⁶ O is present, the value of t (which may be an average value) is preferably 0.5 to 10.

The G group is generally fructose, glucose, mannose, galactose, talose, gulose,
It is derived from allose, altrose, idose, arabinose, xylose, lyxose and / or ribose.

Preferably G is provided essentially exclusively by the glucose unit. The bond between sugars may be from 1-position to 2, 3, 4 or 6-position of adjacent sugars.
The hydroxyl group on the sugar residue may be esterified with a short alkyl chain of, for example, 1 to 4 carbon atoms.

The value (average) of y is preferably 1 to 4 and 1
~ 2 is particularly desirable.

Alkyl polyglycosides of the formula: R ¹⁵ O (G) _y , ie, those in which t is 0 in the above formula are Horizon Chemical
Commercially available from Co.

The O-alkanoyl glucoside is an Internat
ional Patent Application WO 88/10147 (Novo Indus
tri A / S). In particular, the surfactants described in this specification include glucose esters having an acyl group at the 3-position or the 6-position (eg, 3-O-acyl-D-glucose or 6-O-acyl-D-glucose). Etc.).
In the present invention, Applicants have found that 6-O-alkanoyl glycosides, especially of the formula:

[0080]

[Chemical 14]

[Wherein R ¹⁷ is an alkyl or alkenyl group having 7 to 19 carbon atoms, preferably 11 to 19 carbon atoms, and R ¹⁸ is hydrogen or an alkyl group having 1 to 4 carbon atoms. Is used.

Most preferred are such compounds where R ¹⁸ is an alkyl group such as ethyl or isopropyl. Alkylation at the 1-position by regioselective enzymatic synthesis as described by Bjokling et al. (J. Chem. Soc., Chem. Commun. 1989 p934, the disclosure of which is incorporated herein by reference). Such compounds can be prepared.

Particularly preferred are esters of glucose, but corresponding substances based on other reduced sugars (eg galactose and mannose).
Is also preferable.

Further possible nonionic surfactants are the monoglyceryl ethers of the respective formulas: R ¹⁹ OCH ₂ CH (OH) CH ₂ OH and R ¹⁹ C (═O) OCH ₂ CH (OH) CH ₂ OH. Or there is an ester.

R ¹⁹ is preferably a saturated or unsaturated aliphatic residue. In particular R ¹⁹ may be linear or branched alkyl or alkenyl. More preferably, R ¹⁹ is a linear alkyl or alkenyl moiety having substantially 9 to 16 carbon atoms, especially a C _{8 to} C ₁₂ alkyl moiety. Most preferably R ¹⁹ is decyl, undecyl or dodecyl.

Monoglyceryl ethers of alkanols are known substances and can be prepared, for example, by condensation of higher alkanols with glycidol. Glycerol monoester is, of course, a known substance and Alkyril Chemicals I
Commercially available from many suppliers, including nc.

Another important nonionic surfactant for use in the present invention has the general formula: R-CH (OH) -CH ₂ OH, where R is saturated or contains 8 to 16 carbon atoms. It is an unsaturated hydrocarbon group].

Amount and Ratio of Surfactant The composition of the present invention usually comprises a mixture of the surfactants consisting of the micellar phase surfactant (i) and the lamellar phase surfactant (ii) in the composition. In an amount of -60% by weight, preferably 2-45% by weight, more preferably 5-40% by weight, most preferably 5-
Contains 35% by weight.

The amount of glycolipid biosurfactant incorporated is preferably at least 2% by weight of the total composition, more preferably at least 5% by weight.

The detergency enhancing weight ratio depends on the particular surfactant used, but can be determined empirically. Generally, the proportion of glycolipid biosurfactant is low when the alkyl chain is short and high when the alkyl group is long.

The weight ratio of micellar phase surfactant to lamellar phase surfactant is usually 20: 1 to 1:20, but in a narrower range (eg 10: 1 to 1:10, more preferably 4: 1 :). (1 to 1: 4, etc.)
May be inside.

The ratio of the surfactant is such that the oily stain gives a cleaning power superior to the cleaning power provided by the glycolipid biological surfactant alone (assuming that the total amount of the surfactant is the same). It is preferable that the ratio is high.

When the non-glycolipid biosurfactant is added, the ratio of the non-glycolipid surfactant gives a detergency superior to the detergency provided by the non-glycolipid surfactant alone to the oily stain (surfactant It is preferable that the total amount be the same).

Detergency Builder When the composition of the present invention is intended for laundering textiles, the composition will usually comprise one or more detergency builders, suitably 5-80% by weight, preferably 7-. 70% by weight, more preferably
20 to 80% by weight is included. When solid, the composition comprises at least 10 or 15% by weight builder. The builder can be any substance that can reduce the level of free calcium ions in the wash liquor, the composition having a pH of alkaline and other convenient properties such as suspending soil removed from textiles. Is preferably provided.

Preferred builders include alkali metal aluminosilicate (preferably sodium) salts, crystalline or amorphous having the general formula: 0.8-1.5 Na ₂ O.Al ₂ O ₃ .0.8-6 SiO _2. Of the composition (anhydrous basis).
-60% by weight may be added.

These substances contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO / g. Aluminosilicate sodium salt is 1.5-3.5Si
It preferably contains O ₂ units (in the above formula). Both amorphous and crystalline materials can be readily prepared by reaction between sodium silicate and sodium aluminate, as well described in the literature.

Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in British Patent 1 429 143.
No. (Procter & Gamble). Preferred sodium aluminosilicates of this type are the commercially available known zeolites A and X, and mixtures thereof. Also of interest is the novel zeolite P described and claimed in EP 38070 (Unilever).

Phosphate-fortified detergent compositions are also within the scope of the invention. Examples of phosphorus-containing inorganic detergency builders include water-soluble salts of pyrophosphoric acid, orthophosphoric acid, polyphosphoric acid and phosphonic acid, especially alkali metal salts. Specific examples of inorganic phosphate builders include the sodium and potassium salts of tripolyphosphoric acid, orthophosphoric acid and hexametaphosphoric acid.

However, the preferred detergent compositions of the present invention preferably contain no more than 5% by weight of inorganic phosphate builders and are substantially free of phosphate builders.

If necessary or desired, the detergent composition of the present invention can contain builders other than those mentioned above, and a suitable organic or inorganic water-soluble or water-insoluble builder can be used by a detergent formulation expert. If you have one, come up with it easily. Inorganic builders that may be present in the compositions of the present invention include alkali metal salts of carbonic acid (usually sodium salts), while organic builders include polyacrylates, acrylic acid / maleic acid copolymers and polyphosphinates such as acrylic phosphinate. Carboxylate polymers and monomeric polymers such as citrate, gluconate, oxydisuccinate, glycerol mono-, di- and trisuccinate, carboxymethyl oxysuccinate, carboxymethyl oxymalonate, dipicolinate and hydroxyethyliminodiacetate. Included are carboxylates and organic precipitation builders such as alkyl and alkenyl malonates and succinates and sulfonated fatty acid salts.

A particularly preferred auxiliary builder is 0.5 to 1
Polycarboxylate polymers, preferably polyacrylates and acrylic acid / maleic acid copolymers, which are preferably used in amounts of 5% by weight, in particular 1 to 10% by weight, and 3 to
Monomeric polycarboxylates, preferably citric acid and its salts, which are preferably used in amounts of 20% by weight, in particular 5 to 15% by weight.

Other Ingredients It is desirable that the textile laundry composition according to the present invention be substantially neutral or at least slightly alkaline, ie the composition of the present invention in distilled water at 25 ° C. and a surfactant. The pH should desirably be 7.5 or higher when dissolved in an amount to give a concentration of 1 g / l. When the composition is a solid, the pH will typically be a relatively high value, such as 9 or higher. In order to achieve the required pH, the composition according to the invention may contain water-soluble alkali salts. This salt is
It may be a detergency builder (as described above) or an alkaline material that does not function as a builder.

The composition of the present invention includes, for example, 1% of the composition.
An amount of electrolyte may be included such that when added to water at a concentration of g / l, the concentration is at least 0.01M.
The electrolyte concentration is 0.0, especially when the composition is in a solid state.
It can be relatively high, such as 5 or 0.1 M or higher. Liquid compositions typically limit the electrolyte content so that stability is not compromised. The minimum use level when the detergent composition for washing textile products is used in the usual way is approximately 1 g / l. A relatively common usage level is 4-50 g / l. The amount of electrolyte can be determined such that the electrolyte concentration is 0.01 M or more, particularly preferably 0.1 M or more when the composition is added to water at a concentration of 4 g / l.

Other ingredients that may optionally be used in the detergent compositions of the present invention include sodium or potassium salts of carboxylic or sulfonic acid groups in the acid form or neutralized in whole or in part, It preferably includes a polymer contained in the form of a sodium salt.

Preferred polymers are homopolymers and copolymers of acrylic acid and / or maleic acid or maleic anhydride. Of particular interest are polyacrylates, polyalphahydroxyacrylates, acrylic acid / maleic acid copolymers, and acrylic phosphinates. Other polymers which are particularly preferably used in liquid detergent compositions include, for example, European Patent EP 3
There are deflocculating polymers such as those disclosed in 46995.

The molecular weight of the above homopolymers and copolymers is usually 1,000 to 150,000, preferably 1,5.
00 to 100,000. The amount of any polymer can be 0.5 to 5% by weight of the composition. Other suitable polymeric materials are cellulose ethers such as carboxymethyl cellulose, methyl cellulose and hydroxyalkyl cellulose, and mixed cellulose ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of different cellulose ethers, especially mixtures of carboxymethylcellulose and methylcellulose, are suitable. Molecular weight 400-50,0
Polyethylene glycol of 00, preferably 1,000 to 10,000, and copolymers of polyethylene oxide and polypropylene oxide are suitable, as are copolymers of polyacrylates and polyethylene glycol. Polyvinylpyrrolidone having a molecular weight of 10,000 to 60,000, preferably 30,000 to 50,000,
And copolymers of polyvinylpyrrolidone with other polypyrrolidones are also suitable. Molecular weight 1,000-100,0
00, especially 3,000 to 30,000 polyacrylic phosphinates and related copolymers are also suitable.

It may be desirable to include in the detergent composition of the present invention an alkali metal salt of silicic acid, in particular sodium orthosilicate, sodium metasilicate, or preferably neutral or alkaline sodium silicate, in a given amount. .. When the alkali metal salt of silicic acid as described above is present at a level of 0.1 to 10% by weight, the washing power is improved to some extent and the treatment effect is enhanced, and the metal portion of the washing machine is corroded. It may be advantageous to protect against

Further examples of other ingredients that may be present in the compositions of the present invention further include textile softeners such as fatty amines and textile softening clay materials; alkanolamides, especially palm kernel fatty acids and coconut fatty acids. Foam enhancers such as monoethanolamide; foam suppressors;
Oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate; Peracid bleach precursors; Chlorine-releasing bleaching agents such as trichloroisocyanuric acid; Heavy metal ion sequestering agents such as EDTA; Fluorescent agents; Deodorants Fragrances including fragrances;
Enzymes such as cellulases, proteases, lipases and amylases; bactericides; pigments, colorants or colored spots; and inorganic salts such as sodium sulfate and magnesium sulfate. Sodium sulphate can be present as an extender substance in an amount up to 40% by weight of the composition, if desired, but may be present in a small amount, up to 10% by weight of the composition, or not at all. Good.

The detergent composition according to the invention comprises a powder, a bar,
It may be in any suitable form including liquids and pastes. For example, a suitable liquid composition may be non-aqueous or aqueous,
If it is aqueous, it may have an isotropic or lamellar structure. The composition of the invention may be manufactured in a number of different ways depending on its physical form. Granular products may be prepared by dry blending, co-agglomeration, spray drying from aqueous slurries, or any combination of these methods. One preferred physical form is that of particles containing a detergency builder salt. Such particles can be manufactured by conventional particle forming techniques or spray drying.

[0110]

The present invention is illustrated by the following non-limiting examples. Parts and percentages are by weight unless otherwise stated.

[0111] In rhamnolipid Example 1 This example used the rhamnolipid produced glucose and glycerol as a by-product of the fermentation, which is implemented using Pseudomonas glumae as substrate as micellar phase surfactant (i). Partial characterization of the dry matter obtained from the fermented product revealed that it contained one or more compounds of formula I above, where n is 10 !. An ethoxylated fatty alcohol was used as the lamellar phase surfactant (ii).

The following materials were added to deionized water to make an aqueous wash.

Rhamnolipid (as fermented product-derived dry matter) +
1 g / l Ethoxylated dodecyl alcohol (average of 3 ethylene oxide residues) Sodium metaborate 0.05M The above dose was obtained when a specific detergent product containing 16.7% by weight of a surfactant was used in an amount of 6 g / l. Equivalent to the typical amount.

The pH of the obtained washing liquid was about 10.7 due to the presence of the metaborate salt.

Wash solutions containing the above two surfactants in various ratios were prepared and used for washing radioactively labeled triolein-stained polyester test cloths. Cleaning
Performed for 20 minutes at 40 ° C. in a Tergotometer.

Triolein deficiency was determined using radiotracer technology. The results are shown in Table 1.

Table 1 Rhamnolipid (%; active C12EO3 (%; based on active triolein removal material weight) based on material weight) (%) 100 0 28 80 20 42 60 40 63 40 60 73 20 80 72 0 100 1 Clear In addition, all mixtures of rhamnolipid and ethoxylate nonionic surfactants provided superior detergency than either surfactant alone.

Example 2 The procedure of Example 1 was repeated, except that the ethoxylate nonionic surfactant as lamellar surfactant (ii) was replaced with the anionic surfactant di-C ₈ alkyl sulfosuccinate. The results are shown in Table 2.

(; Based on the active di -C ₈ sulfosuccinates triolein removal material weight%) [0119] Table 2 rhamnolipid (%; based rather on the active material weight) (%) 100 0 28 80 20 30 60 40 38 40 60 45 20 80 46 0 100 35 Example 3 The procedure of Example 1 was repeated, except that the micelle surfactant (i) was used as Petrogen Inc. , Ill
Rhamnolipid BioEm-L available from inois
KP (trademark) was used. This rhamnolipid has the above-mentioned formula I
[Wherein n = 6, b = 2, R ¹ = H, R ² = H], and the mixture was a mixture of compounds. The compound with a = 1 and the compound with a = 2 were present in approximately equal weight ratios.

The results are shown in Table 3. From this table, a very significant synergistic effect is observed.

Table 3 BioEm-LKP (%; active C12EO3 (%; based on active triolein removal material weight) based on material weight) (%) 100 0 4.59 80 20 4.20 60 40 36.51 40 60 55.78 20 80 43.01 0 100 1.55 Examples 4-10 Test Systems The detergency of the biosurfactant was investigated using the test textiles listed in Table 4 and the test conditions described below.

Table 4 Test cloth: EMPA 104 WFK20D Supplier: EMPA, St. Gallen W ■ schereiforschung, Krefeld Test cloth type: polyester / cotton polyester / cotton Composition of stain: ink 50 ml kaolin 1.72 g / l olive oil 100 ml carbon 0.16 g / l Water 850ml Iron oxide (black) 0.08g / l Iron oxide (yellow) 0.04g / l Sebum 14.00g / l CCl ₄ Sprayed onto the cloth as a solution Reflectivity of unwashed test cloth: 14.7 Reflectance unit 42.6 Reflectance Unit Wash Solution The following materials were added to deionized water to make an aqueous wash solution.

One or more Glycolipid Biological Surfactants (as dry matter from fermentation) + 0.5 g / l any non-glycolipid surfactant Sodium Metaborate 0.05M The pH of the wash solution is Therefore, it became about 10.

Test conditions In a polyethylene bottle with a capacity of 100 ml, 30 m per bottle
The test was carried out by adding 1 l of the washing liquid, one 6 × 6 cm test cloth, and one 6 × 6 cm white (clean) cotton cloth as a cloth for reattachment test. The cloth: liquid ratio per bottle was 1:30. Up to 50 polyethylene bottles prepared as described above were stirred for 30 minutes at 40 ° C in a Miele TMT washing machine. The washed test textile was then rinsed 3 times with cold water before drying.

Monitoring Method Detergency was evaluated by calculating the increase in reflectance (ΔR460 *) at 460 nm (incident light below 400 nm is filtered) [ΔR = reflectance of washed cloth (R _w ) -Reflectance of unwashed cloth (R _i )].

Example 4 Various rhamnolipid samples (micelle phase) were combined with the nonionic surfactant C12EO3 (ethoxylated dodecyl alcohol having an average of 3 ethylene oxide residues; lamellar phase) in the wash described above. Tested. Pseu
By the bacterium of the genus domo NASGLUMAE , the formula I
[In the formula, a = 2, b = 2, n = 10, R ¹ = H, R ² = H]
Rhamnolipid RL-BNS consisting of pure rhamnolipid
Was manufactured. BioEm-LKP (trademark; Petrog
en Inc. , Illinois) is a mixture of rhamnolipids from Ps Eudomonas as described in Example 3. The results are shown in Table 5.

[0127] Table 5 ΔR (460) * rhamnolipid BioEm-LKP RL-BN S wt% EMPA 104 WFK20D EMPA 104 WFK20D 100 5.8 10.7 4.2 12.8 80 17.2 14.4 10.8 14.9 60 17.7 19.8 14.7 16.5 40 14.1 20.9 10.2 19.5 20 of active mixture 10.4 16.8 5.7 17.7 0 6.2 14.2 6.8 15.3 Sophorose Lipid Example 5 Sophorose Lipid SOL-TUBS (micelle phase) was tested in combination with some lamellar phase surfactants in the aforementioned wash liquor. The co-surfactants tested were Synper
onic A3, C ₁₂ -1,2- diol and C ₁₀ - it was glycerol ether - mono. The results are shown in Table 6.

SOL-TUBS is a technical
University of Braunschwei
g, a sophorose lipid obtained from Germany, produced by the yeast strain Torulopsis bombicola . SOL-TUBS is a compound of formulas (III) and (IV) in which at least 80% is 1 ', 4 "-lactone-6', 6" -diacetate lipid [wherein formula (IV)
Wherein R ³ and R ⁴ are acetyl groups, R ⁵ is 1.
And R ⁶ is 15.] is a mixture of four sophorose lipids. Reference JAOCS 65 (9) (1990)
1460, the length of the fatty acid backbone in SOL-TUBS is C ₁₈ (ie R in formula (IV)
⁵ + R ⁶ = a C _16).

[0129]

[Table 1]

Example 6 Sophorose lipid SOL-CH (micelle phase) was used in Example 5.
Tested as described in. The results are shown in Table 7.

SOL-CH is a yeast strain Torulops.
A sophorose lipid produced by is bombicola, which is a mixture of at least eight sophorose lipids of formulas (III) and (IV).

[0132]

[Table 2]

[0133] Example 7 Sohorosuripido (SOL-COO ^-) was tested as described in Example 5 (micellar phase). The results are shown in Table 8.

SOL-COO ^- is a yeast strain Torulo.
a sophorose lipid produced by Psis bombicola, which is partially hydrolyzed, thus R ³ and R ⁴ are H, R ⁵ is 1, R ⁶ is 15, R ⁷ is H, and structural formula wherein R ⁸ is OH (II
I).

[0135]

[Table 3]

Cellobiose Lipid Example 8 Cellobiose lipid (CELL-TUBS) (micellar phase) produced by the strain Ustilago maydis was tested in combination with several lamellar phase surfactants in the above washing liquor. The cosurfactant tested was S
ynperonic A3, C ₁₂ -1,2- diol and C ₁₀ - was glycerol ether - mono. The results are shown in Table 9.

CBL-TUBS consists of about four cellobiose lipids of formula (IV). In the main component, R ¹
Is H, R ¹² is 15, R ¹³ is acetyl, and R ¹⁴ is 4.

[0138]

[Table 4]

Example 9 Cellobiose lipids as described in Example 8 were prepared according to formula (V
In I), R ¹ is H, R ¹³ is H, R ¹² is 15, R ¹³ is H, and the ester-bonded fatty acid group containing R ¹⁴ is partially absent so as to be absent. Disassembled.
Such cellobiose lipids (micellar phase) were investigated using various lamellar phase surfactants as described in Example 8. The results are shown in Table 10.

[0140]

[Table 5]

Example 10 Trehalose lipid (THL-4) (lamellar phase) was used as rhamnolipid BioEm-LKP as described in Example 2.
It was tested in combination with (micellar phase).

Trehalose lipid THL-4 is a bacterium A
rthrobacter sp. It is produced by Ek1 and consists of trehalose lipids of formula (V) in which R ⁹ , R ¹⁰ and R ¹¹ have an average of 7 to 9 carbon atoms.

The results are shown in Table 11.

[0144] Table 11 Trehalose Lipid rhamnose lipids [Delta] R (460) * wt% EMPA 104 weight% active mixture of active mixture WFK 20D 100 100 5.8 9.8 80 80 8.9 10.7 60 60 10.9 13.6 40 40 7.2 14.8 20 20 8.2 12.9 0 0 4.5 9.5 Examples 11 to 12 Test System Using the test cloth WFK 20D as shown in Table 4 and the following test conditions, the cleaning ability of the biological surfactant was investigated.

[0145] A washing liquid containing the following materials in the washing solution in deionized water was prepared:
Glycolipid biosurfactant (as dry material from fermentation system), any non-glycolipid surfactant, Table 12
Detergent base powder as shown in.

The total surfactant concentration was 0.5 g / liter. The detergent base powder was blended at 2.5 g / liter. The test conditions and monitoring method were as described in Examples 4-10.

Table 12-Detergent base powder part Zerolite 4A (anhydride base) 27.62 Maleic acid / acrylic acid copolymer 4.15 Sodium carbonate 10.15 Alkali silicate 0.46 Sodium carboxymethylcellulose 0.81 Fluorescent agent 0 .22 Moisture + salt 12.85 Example 11 Sophorose lipid SOL-TU as described in Example 5.
BS (micellar phase) was tested in combination with Synperonic A3 (lamellar phase). The results are shown in Table 13.

[0148] Example 12 Cellobiose Lipid CBL-T as described in Example 8.
UBS (micellar phase), Synperonic A3
It was tested in combination with (lamellar phase). The results are shown in Table 14.

[0149]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C11D 1:72) (C11D 1/83 1:28 1:68) (72) Inventor Cornelis Helhardt・ Juan Clarynchen, England, Cheshire, Chester, Weberton, Mountway 10 (72) Inventor Michael H. Schmiditz Netherlands, 3121 Ixar Scheedam, Bosland 13

Claims (8)

[Claims] 1. A first surfactant which is (i) a micellar phase surfactant, and a (ii) a second surfactant which is a lamellar phase surfactant. A detergent composition in which at least one of the two surfactants is a glycolipid biosurfactant. 2. A glycolipid biosurfactant represented by the following formula (I): [In the formula, a is 1 or 2, b is 1 or 2, and n is
Is 4 to 10, R ¹ is H or a cation, R ² is H or the following group: And m is 4 to 10, and the values of m and n need not all be the same]], The detergent composition according to claim 1 containing a rhamnolipid. 3. A glycolipid biosurfactant represented by the following formula (II): The detergent composition according to claim 1, comprising a glucose lipid represented by the formula: wherein R ¹ is H or a cation, p is 1 to 4, and q is 4 to 10. 4. A glycolipid biosurfactant represented by the following formula (III): [In the formula, R ³ and R ⁴ individually represent H or an acetyl group,
R ⁵ is a saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon group having 1 to 9 carbon atoms, and R ⁶ is a saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon group having 1 to 19 carbon atoms. With the proviso that the total number of carbon atoms of the groups R ⁵ and R ⁶ is 20 or less, R ⁷ is H or a lactone ring formed between R ⁸ and R ⁸ is OH or R It is a lactone ring formed with ⁷ ]
The detergent composition according to claim 1, comprising a sophorose lipid represented by the formula: 5. A glycolipid biosurfactant represented by the following formula (V): [In the formula, R ⁹ , R ¹⁰ and R ¹¹ are each independently a carbon atom number of 5 to 1;
Representing 3 saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon groups], the detergent composition of claim 1 comprising a trehalose lipid. 6. A glycolipid biosurfactant represented by the following formula (VI): [Wherein R ¹ is H or a cation, R ¹² is a saturated or unsaturated hydroxylated or non-hydroxylated hydrocarbon group having 9 to 15 carbon atoms, R ¹³ is H or an acetyl group, R ¹⁴ is a saturated or unsaturated hydroxylated or unhydroxylated hydrocarbon group having 4 to 16 carbon atoms]
The detergent composition according to claim 1, comprising a cellobiose lipid represented by: 7. The micellar phase surfactant (i) is a glycolipid biological surfactant, and the lamellar phase surfactant (ii).
The detergent composition of claim 1, wherein is selected from glycolipid biosurfactants, non-glycolipid anionic and nonionic surfactants, and combinations thereof. 8. The detergent composition according to claim 1, wherein the weight ratio of the micellar phase surfactant (i) to the lamellar phase surfactant (ii) is in the range of 20: 1 to 1:20.