JP2001524586A - Liquid dishwashing detergent containing foam stabilizer - Google Patents

Abstract

  (57) [Summary] The present invention relates to proteinaceous foam stabilizers which provide improved foam volume and foam retention, thereby signaling the lasting efficacy of the cleaning ingredients and which are suitable for liquid detergent compositions. The proteinaceous foam stabilizer can be a naturally occurring polypeptide polymer, such as an enzyme or a polymer containing synthetic amino acids. Proteinaceous foam stabilizers are further identified in that they have an isoelectric point of about 7 to about 11.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to a liquid detergent composition useful for hand dishwashing comprising a proteinaceous foam stabilizer that provides improved grease removal performance and improved foam duration. Useful proteinaceous foam stabilizers of the present invention have an isoelectric point of about 9 to about 11.5. The invention also relates to an amino acid or amino acid-like containing protein material forming a polymeric material having an isoelectric point of about 9 to about 11.5.

BACKGROUND OF THE INVENTION [0002] Liquid detergent compositions suitable for hand dishwashing must meet several criteria in order to be effective. These compositions must be effective in removing grease and fatty foods, and once they have fallen, the fatty materials must not re-adhere to the dishes.

[0003] The presence of foam in hand dishwashing operations has long been used as an indicator that detergents remain effective. However, depending on the situation, the presence or absence of foam has nothing to do with the efficacy of the liquid detergent. Therefore, customers have turned to something wrong, namely, whether or not soap bubbles are present, to indicate the need to add detergent. In many cases, customers have added additional detergent amounts that are far in excess of that required to completely clean the dishes. This waste of detergent is especially true in hand-washing. Dirty cooking items are usually cleaned in a "difficult to clean" queue. For example, glasses and cups that do not normally come in contact with fatty foods are washed first, followed by dishes and flats, and finally, the pots and pans that contain the most leftover ingredients and are therefore usually the “greatest”.

[0004] Normally, when cleaning pots and pans, there is no bubble in the dishwashing water and the amount of food left on the cooking utensil surface can be visually checked, typically from the dish surface or the cooking utensil surface. Even if a sufficient amount remains in the solution to effectively remove dirt and grease, the customer is forced to add additional detergent. However, an effective grease dissolving material does not always produce a sufficient amount of the corresponding foam.

Accordingly, there is a continuing need in the art for a liquid dishwashing detergent useful for dishwashing with sustained foam levels while maintaining effective grease dissolving properties.
The need exists for compositions in which the dishwashing composition is effective and can still maintain high foam levels. Indeed, there has long been a need to provide hand dishwashing compositions that can be used effectively by customers to use as much detergent as needed to adequately accomplish the cleaning task.

SUMMARY OF THE INVENTION The present invention was described above in that it was unexpectedly discovered that some proteinaceous compounds function as foam enhancers in liquid detergent compositions that are effective in dissolving fats and oils. Satisfy requirements. Effective proteinaceous foam stabilizers have an isoelectric point of about 9 to about 11.5 and are effective in liquid detergent compositions having a pH of about 7 to about 12 when measured as a 10% aqueous solution. It is.

[0007] The proteinaceous foam stabilizer of the present invention comprises one or more amino acid residues, preferably at least about 10% by weight of amino acid residues having a proton withdrawing or donating moiety. The proteinaceous foam stabilizer can comprise any other amino acid compatible unit that provides for increased foam formation and foam volume.

[0008] A first aspect of the present invention is to provide a) an effective amount of an isoelectric point of 9 to 11.5, provided that the pH of a 10% aqueous solution of the detergent composition is from about 7 to about 12. A detergent composition suitable for hand dish washing comprising a proteinaceous foam stabilizer, b) an effective amount of a detersive surfactant and (c) a balance of carriers and other auxiliary ingredients.

The present invention further relates to protein materials in the form of peptides, polypeptides, peptide copolymers and mixtures thereof suitable for detergents where the formulator wishes to increase the amount and duration of foam.

[0010] The present invention also provides a method for dissolving a composition according to the present invention in water to form a hand dishwashing solution,
Thereafter, manually washing the dishes in said solution, the method comprising hand washing the dishes while providing increased foam and improved foam duration. These and other aspects, features and advantages will become apparent to those skilled in the art from the following detailed description and knowledge of the appended claims.

[0011] All percentages, ratios and proportions herein are by weight unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to peptides, polypeptides, amino acid containing copolymers and the like that provide improved foam stability and foam during hand washing of dishes. The present invention also relates to a liquid detergent composition comprising said proteinaceous foam stabilizer providing the advantage of increased foam.

Proteinaceous Foam Stabilizer The proteinaceous foam stabilizer of the present invention can be a peptide, polypeptide, amino acid-containing copolymer, and mixtures thereof. The backbone of the peptide, polypeptide or amino acid-containing copolymer of the present invention may be modified so long as at least 10% to about 40% of the amino acids comprising the peptide can be protonated at a pH of 7 to about 11.5. Any suitable amino acids that form can be used.

For the purposes of the present invention, the terms “peptide” and “polypeptide”
A polymer comprising 100% amino acids and having a molecular weight of at least 1500 daltons is equally well described as described hereinafter. For the purpose of the present invention,
The term "amino acid-containing copolymer" refers to "polymeric material having at least about 150
Provided that it has a molecular weight of 0 Daltons, it is defined as a polymeric material comprising at least about 10% by weight of one or more amino acids as defined herein.

Preferred proteinaceous foam stabilizers according to the invention are from 7 to about 11.5, preferably about 8.
It has an isoelectric point of 5 to about 11.5, more preferably about 9.5 to about 11.

In general, amino acids having the following formula that are suitable for use in producing the proteinaceous foam stabilizers of the present invention have 2 to 22 carbon atoms.

[0017]

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Wherein each R and R¹Is independently hydrogen, C₁~ C₆Linear or branched alkyl, C₁~ C₆It is selected from the group consisting of substituted alkyls and mixtures thereof. C ₁ ~ C₆Non-limiting examples of suitable moieties for substitution on an alkyl unit include:
Mino, hydroxy, carboxy, amide, thio, thioalkyl, phenyl;
Phenyl substituted with roxy, halogen, amino, carboxy, amide and the like
These mixed groups are mentioned. R and R¹C₁~ C₆Further non-limiting examples of suitable moieties for substitution on an alkyl unit include 3-imidazolyl, 4-imidyl
Dazolyl, 2-imidazolinyl, 4-imidazolinyl, 2-piperidinyl, 3-
Piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyra
Zoyl, 5-pyrazolyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazoli
Nil, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl,
Piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino and
And mixed groups thereof. Preferably R¹Is hydrogen and at least 10% of the R units may have a positive or negative charge at a pH of about 7 to about 11.5.
It is a possible part. Each R^TwoIs independently hydrogen, hydroxy, amino, guanidino, C₁~ C_FourAlkyl or R, R¹And every R^TwoUse with units
Can be used to form an aromatic or non-aromatic ring having 5 to 10 carbon atoms
Wherein each ring is an aromatic ring, a non-aromatic ring or
It can be a single ring or two fused rings that are mixed rings. In the present invention
When the amino acid according to the invention comprises one or more rings incorporated into the amino acid backbone, R,
R¹And one or more R^TwoThe unit is the carbon-carbon required to effect the ring formation.
Form elementary bonds. When R is hydrogen, preferably R¹Is not hydrogen, and vice versa. Preferably, at least one R^TwoIs hydrogen. The subscripts x and y are each independently 0 or 2.

An example of an amino acid according to the present invention that contains a ring as part of the amino acid backbone is 2-aminobenzoic acid (anthranilic acid) having the formula:

[0020]

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Here, x is equal to 1, y is equal to 0, and R, R ¹ and two R ² units from the same carbon atom are utilized together to form a benzene ring.

A further example of an amino acid according to the invention comprising a ring as part of the amino acid backbone is 3-aminobenzoic acid having the formula:

[0023]

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Here, x and y are each equal to 1, R is hydrogen, and R ¹ and the four R ² units are used together to form a benzene ring.

Non-limiting examples of amino acids suitable for the proteinaceous foam stabilizer of the present invention wherein at least one of x or y is not equal to 0 include 2-aminobenzoic acid, 3-aminobenzoic acid,
4-aminobenzoic acid, β-alanine and β-hydroxyaminobutyric acid.

Preferred amino acids suitable for the proteinaceous foam stabilizer of the present invention have the formula:

[0027]

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Wherein R and R ¹ are independently hydrogen or a moiety as described above, preferably, R ¹ is hydrogen and at least about 10% to about 40% of the R units are about Comprising a moiety having a positive charge at a pH of 7 to about 11.5)

Further preferred amino acids constituting the proteinaceous foam stabilizer of the present invention have the following formula:

[0030]

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Wherein R is hydrogen, C ₁ -C ₆ straight or branched alkyl, C ₁ -C ₆ substituted alkyl, and mixtures thereof. R is preferably C ₁ -C ₆ substituted alkyl;
Here, preferred moieties substituted on the C ₁ -C ₆ alkyl unit include amino, hydroxy, carboxy, amide, thio, C ₁ -C ₄ thioalkyl, 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl, -Imidazolinyl, 2-
Piperidinyl, 3-piperidinyl, 4-piperidinyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-pyrazolinyl, 3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino, amidino, phenyl; phenyl substituted with hydroxy, halogen, amino, carboxy and amide.

An example of a further preferred amino acid according to the invention is the amino acid lysine having the formula:

[0033]

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Wherein R is a substituted C ₁ alkyl moiety wherein the substituent is 4-imidazolyl

Non-limiting examples of preferred amino acids include alanine, arginine, asparagine, aspartic acid, kristine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, Tryptophan, tyrosine, valine and mixtures thereof. The aforementioned amino acids are typically referred to as “first α-amino acids”, but the proteinaceous foam stabilizer of the present invention has an isoelectric point of about 7 to
It can comprise any amino acid having an R unit that works with the aforementioned amino acids to adjust to a range of about 11.5. For example, further non-limiting examples of amino acids include homoserine, hydroxyproline, norleucine, norvaline, ornithine, penicillamine and phenylglycine, preferably ornithine. The R units preferably comprise a moiety that can be cationic or anionic in the pH range from about 7 to about 11.5. Anion R
Non-limiting examples of preferred amino acids having units include glutamic acid, aspartic acid and γ-carboxyglutamic acid.

For the purposes of the present invention, both optical isomers of any amino acid having a chiral center will work equally well to enter the backbone of a peptide, polypeptide or amino acid copolymer. A racemic mixture of one amino acid can be suitably combined with a single optical isomer of one or more other amino acids depending on the required properties of the final proteinaceous foam stabilizer. The same applies to amino acids capable of forming diastereomeric pairs, such as threonine.

1. Polyamino acid protein foam stabilizer One type of suitable protein foam stabilizer according to the present invention consists entirely of the amino acids described above. Provided that the compound has an isoelectric point of about 7 to about 11.5 and a molecular weight of about 1500 daltons or more, the polyamino acid compound can be a naturally occurring peptide, polypeptide, enzyme, or the like. . Preferably, the proteinaceous foam stabilizer of the present invention consisting entirely of amino acids comprises from about 10% to about 40% by weight of the amino acids capable of being protonated at a pH of from about 7 to about 11.5. Become. An example of a suitable polyamino acid as a proteinaceous foam stabilizer according to the present invention is the enzyme lysozyme.

When choosing naturally occurring enzymes, proteins and peptides as proteinaceous foam stabilizers, exceptions can occur in each case. Without wishing to be limited by theory, the unique second, third or fourth structure of the naturally occurring polypeptide may have a pH between about 7 and about 11.5.
Even within the range of from about 10 to about 40% by weight of protonatable amino acids within the range allows use of the polypeptide. For example, about 7 to about 11. comprising only 5% by weight of amino acids having R units that are protonated at a pH of about 7 to about 11.5.
Enzymes having an isoelectric point in the range of 5 can suitably function as effective proteinaceous foam stabilizers according to the present invention.

Another class of suitable polyamino acid compounds comprises from about 10 to about 40% by weight of an amino acid having a molecular weight of at least about 1500 daltons and capable of being protonated at a pH of from about 7 to about 11.5. It is a synthetic peptide further comprising: further,
The polyamino acid peptide has a content of 7 to about 11.5, preferably about 8.5 to about 11.
5, and more preferably from about 9.5 to about 11 isoelectric points. Examples of suitable polyamino acid synthetic peptides for use as proteinaceous foam stabilizers according to the present invention are amino acids having an average molecular weight of 52,000 daltons and a lysine: alanine: glutamic acid: tyrosion ratio of about 5: 6: 2: 1. It is a copolymer of lysine, alanine, glutamic acid and tyrosine.

Without wishing to be limited by theory, the presence of one or more cationic amino acids, such as histidine, ornithine and lysine, is necessary to ensure improved foam stabilization and foam volume. However, the relative amount of cationic amino acids present and the resulting isoelectric point of the polyamino acids are key to the effectiveness of the resulting material. For example, poly L-lysine having a molecular weight of about 18,000 daltons comprises 100% amino acids with the ability to have a positive charge in the pH range of about 7 to about 11.5, such that the material has It is ineffective as a foam enhancer and grease remover.

[0041] 2. Peptide copolymers Another class of materials suitable for use as proteinaceous foam stabilizers according to the present invention are peptide copolymers. For purposes of the present invention, a "peptide copolymer" is defined as "at least about 10% by weight comprises one or more amino acids, has an isoelectric point of about 7 to about 11.5, and has a molecular weight of about 1500 daltons or more. Polymer material "

Peptide copolymers suitable for use as proteinaceous foam stabilizers are polyethylene oxide segments that are attached to peptide or polypeptide segments to form a material with improved foam retention and compoundability. Can be included.

Non-limiting examples of a class of amino acid copolymers include:

A. Polyalkylenimine Copolymers Polyalkylenimine copolymers comprise random segments of polyalkylenimines, preferably polyethyleneimines, in conjunction with segments of amino acid residues. For example, tetraethylenepentamine is reacted with polyglutamic acid and polyalanine to produce a copolymer having the formula:

[0045]

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Where m is equal to 3, n is equal to 0, i is equal to 3, j is equal to 5,
x is equal to 3, y is equal to 4, and z is equal to 7)

However, the formulator may provide other polyamines, such as polyvinylamine, in place of the polyalkylimine, or a cationic charge source at a pH of 7 to about 11.5, and a pH of about 7 to about 11.5, etc. Other suitable polyamines that result in a copolymer having an electrical point can be used.

[0048] Formulators can combine non-amine polymers with non-protonable and non-protonable amino acids. For example, a carboxylate-containing homopolymer can be reacted with one or more amino acids, such as histidine and glycine, to form an amino acid-containing amide copolymer having the formula:

[0049]

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Wherein the copolymer has a molecular weight of at least 1500 daltons and about 2
: X: y: z ratio of 3: 6.

The liquid detergent composition according to the present invention comprises at least an effective amount, preferably about 0.3 to about 5%, more preferably about 0.4% to about 4%, most preferably about the weight of the composition. Comprises from about 0.5% to about 3% of one or more proteinaceous foam stabilizers described herein. "An effective amount of a proteinaceous foam stabilizer" refers to a foam produced by the compositions just described that lasts for an increased amount of time as compared to a composition that does not include the proteinaceous foam stabilizer described herein. Is meant herein.

Detergent Surfactants The compositions of the present invention comprise at least an effective amount of one or more detersive surfactants. The term "effective amount" is used to refer to a "proteinaceous foam stabilizer" to properly clean surfaces, preferably tableware surfaces (ie, glass, silverware, dishes, pots and pans) while maintaining improved foam levels. Required Amount of Surfactant "is defined herein.
An effective amount is typically from about 0.5% to about 90%, preferably from about 5% to about 50%, more preferably from about 10 to about 30% by weight of the detersive surfactant.

Anionic surfactants The anionic surfactants useful in the present invention are preferably linear alkylbenzene sulfonates, α-olefin sulfonates, paraffin sulfonates, methyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates , Alkylsulfonates, alkylalkoxycarboxylates, alkylalkoxylated sulfates, sarcosinates, taurates and mixtures thereof.

One type of anionic surfactant that can be utilized includes an alkyl ester sulfonate. These are preferred because they can be produced from renewable non-petroleum resources. The preparation of the alkyl ester sulfonate surfactant component can be carried out by known methods disclosed in the technical literature. For example, a linear ester of C ₈ -C ₁₂ carboxylic acid is “The Journal of the Ame”.
rice Oil Chemistry Society ", 52 (1975)
Pp. It can be sulfonated with gaseous SO ₃ according to 323-329. Suitable starting materials include natural fatty substances derived from tallow oil, palm oil and coconut oil and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include:
It comprises an alkyl ester sulfonate surfactant of the following structural formula.

[0056]

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Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a mixture thereof, and R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a mixture thereof. Yes, M is a soluble salt forming cation. Suitable salts include metal salts such as sodium, potassium and lithium salts, methyl ammonium cation, dimethyl ammonium cation, trimethyl ammonium cation, quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium, and alkanolamines such as Substituted or unsubstituted ammonium salts such as cations derived from ethanolamine, diethanolamine, and triethanolamine are included. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates wherein R ³ is C ₁₄ -C ₁₆ alkyl are particularly preferred.

[0058] Alkyl sulfate surfactants are another type of anionic surfactant of interest for use herein. Polyhydroxy fatty acid amides (see below), including good grease / oil cleaning over a wide range of temperatures, wash concentrations and wash times
In addition to providing excellent overall cleaning capacity when used in conjunction with, dissolution of alkyl sulfates and improved compoundability in liquid detergent formulations can be obtained. These surfactants, wherein ROSO ₃ M (wherein, R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component, more preferably C ₁₂ -C _{18 is} alkyl or hydroxyalkyl, where M is H or a cation, such as an alkali or alkaline earth metal (Group 1A or Group 2A) cation (eg, sodium, potassium, lithium, magnesium, calcium), methyl Ammonium cation, dimethyl ammonium cation, trimethyl ammonium cation,
Substituted or unsubstituted ammonium cations, such as quaternary ammonium cations, such as cations derived from alkanolamines such as tetramethylammonium and dimethylpiperidinium, and ethanolamine, diethanolamine, triethanolamine, and mixtures thereof. A) a water-soluble salt or acid. Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for lower wash temperatures (eg, less than about 50 ° C.), and C ₁₆ -C ₁₈ alkyl chains are preferred for higher wash temperatures (eg, about 50 ° C.). Higher temperature).

[0059] Alkyl alkoxylated sulfate surfactants are another class of useful anionic surfactants. These surfactants typically have the formula RO (A) _m SO ₃ M
(Wherein, R is an unsubstituted C ₁₀ -C ₂₄ alkyl or C ₁₀ -C ₂₄ hydroxyalkyl group having an alkyl component, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl group, more preferably C ₁₂ ~ A C ₁₈ alkyl or hydroxyalkyl group, wherein A is an ethoxy or propoxy unit and m is greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3 And M is H or a water-soluble salt of, for example, a metal cation (eg, a cation that can be an ammonium cation or a substituted ammonium cation, such as sodium, potassium, lithium, calcium, magnesium, etc.). Or an acid. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are contemplated herein. Particular examples of substituted ammonium cations include methylammonium, dimethylammonium, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidinium, and alkanolamines such as monoethanolamine, diethanolamine, Examples include cations derived from triethanolamine, as well as mixed cations thereof. Examples of surfactants, C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) M is selected conveniently from sodium and potassium sulfates, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.2
5) sulfates, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate. The surfactants used herein can be manufactured from natural or synthetic alcohol raw materials. The chain length corresponds to the average hydrocarbon distribution including the branches.

[0060]Other anionic surfactants Other anionic surfactants useful for cleaning purposes are also included in the compositions herein.
Can be included. These include soap salts (eg, sodium, potassium).
Substituted ammonium salts such as ammonium, ammonium, mono-, di- and triethanolamine salts.
Ammonium salt), C₉~ C₂₀Linear alkylbenzene sulfonate, C₈~ C _{twenty four} Olefin sulphonates, for example as described in GB 1,082,179
The sulfonation of the pyrolysis products of alkaline earth metal citrates as described
Sulfonated polycarboxylic acid, alkyl glycerol sulfonate,
Aliphatic acyl glycerol sulfonate, aliphatic oleyl glycerol sulfate,
Alkyl phenol ethylene oxide ether sulfate, paraffin sulfo
, Alkyl phosphates, isothionates such as acyl isothionates,
N-acyl taurate, fatty acid amide of methyl tauride, alkyl succinate
Salts, alkyl sulfosuccinates, monoesters of sulfosuccinates (especially saturated
Sum and unsaturated C₁₂~ C₁₈Monoester), diester of sulfosuccinate (particularly
And saturated and unsaturated C₆~ C₁₄Diesters), sulfates of alkyl polysaccharides such as N-acyl sarcosine salts, sulfates of alkyl polyglycosides (hereinafter referred to as “sulfates”).
Nonionic nonsulfated compounds described), branched primary alkyl sulfates, of the formula RO (CH _Two CH_TwoO)_kCH_TwoCOO^-M⁺(Where R is C₈~ C_{twenty two}Alkyl, k is an integer from 0 to 10 and M is a soluble salt forming cation).
Nonoxycarboxylate, esterified with isethionic acid and neutralized with sodium hydroxide
Fatty acids. Present in rosin, hydrogenated rosin, and tall oil
Or resin acids such as or derived from tall oil and hydrogenated resin acids and
Hydrogenated resin acids are also suitable. A further example is “Surface Active Ag
ents and Detergents "(Vol. I and II by
 Schwartz, Perry and Berch). varied
Such surfactants are also commonly known as Rollin, published December 30, 1975.
(Laughlin) et al., US Pat. No. 3,929,678, column 23, line 58.
To column 29, line 23.

Second Surfactant The second detersive surfactant is from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. You can choose. By selecting the type and amount of detergent surfactant in addition to the other auxiliary ingredients disclosed herein for use in the case of laundry washing or in other different washing applications, particularly including dishwashing. A detergent composition can be included. Thus, the particular surfactant used can vary widely depending on the particular end use being considered. Suitable second surfactants are described below.

Nonionic Detergent Surfactants Suitable nonionic detergent surfactants are generally described in US Pat. No. 3,929,678, column 13, by Laughlin et al., Issued Dec. 30, 1975.
It is disclosed from line 14 to column 16 line 6. This patent is hereby incorporated by reference. Non-limiting examples of useful nonionic surfactants include alkyldialkylamine oxides, alkyl ethoxylates, alkanoyl glucose amides, alkyl betaines and mixtures thereof.

Other nonionic surfactants for use herein include the following.

Polyethylene oxide condensates, polypropylene oxide condensates and polybutylene oxide condensates of alkylphenols. Generally, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols with alkyl phenols having alkyl groups containing from about 6 to about 12 carbon atoms in either a linear or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal, sold by GAF Corporation. Triton sold by CO-630 and Rohm & Hass Company X-45, X-114, X-100 and X-102. These compounds are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation product of an aliphatic alcohol with about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be straight or branched, either primary or secondary, and generally contains from about 8 to about 22 carbon atoms. About 10
Particularly preferred is the condensation product of an alcohol having an alkyl group containing about 20 carbon atoms with about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Union Carbide (U.S.A.).
Negion Carbide Corporation sells both Tergitol _{15-S-9 (C 11} ~C 15 condensation product of a linear secondary alcohol with 9 moles ethylene oxide), Tergitol (Tergit
ol) _{24-L-6NMW (C 12} ~C 14 narrow molecular weight distribution condensation products of primary alcohol and 6 moles of Echiren'o Kishido), Shell Chemical (Shell Ch
Neodol sold by the Electronic Company 45-9 (C ₁₄ ~C ₁₅ condensation product of linear alcohol with 9 moles of ethylene oxide), Neodol (Neodol) 23-6.5 (C ₁₂ ~C ₁₃ condensation product of linear alcohol with 6.5 moles of ethylene oxide), Neodol (Neodol
) 45-7 (C ₁₄ ~C ₁₅ condensation product of linear alcohol with 7 moles of ethylene oxide), Neodol (Neodol) 45-4 (C ₁₄ -C ₁₅ condensation product of linear alcohol with 4 moles of ethylene oxide), Procter & Gamble (
The kilos sold by The Procter & Gamble Company EOB (C ₁₃ ~C ₁₅ condensation products of alcohols with 9 moles of ethylene oxide) and the like. Other commercially available nonionic surfactants include Dovanol 91-8, sold by Shell Chemical Company. And Genapol UD-080 sold by Hoechst Are mentioned. Nonionic surfactants of this type are commonly referred to as "alkyl ethoxylates".
Called.

A condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds is about 15
It has a molecular weight of 00 to about 1800 and is water-insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole,
The liquid properties of the product are retained to a point where the polyoxyethylene content is about 50% of the total weight of the condensation product corresponding to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include commercially available Pluronic sold by BASF. Some of them are.

A condensation product of ethylene oxide with a product resulting from the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally comprises from about 2500 to about 30
It has a molecular weight of 00. The hydrophobic portion may comprise from about 40% to about 80% by weight of the condensation product.
And is condensed with ethylene oxide to an extent that it has a molecular weight of about 5,000 to about 11,000. Examples of this type of nonionic surfactant include commercially available Tetronic sold by BASF.
) Some of them are.

Semipolar nonionic surfactants are a special type of nonionic surfactants, which include one alkyl moiety having about 10 to about 18 carbon atoms and about 1 to about 3 carbon atoms. A water-soluble amine oxide comprising two moieties selected from the group consisting of an alkyl group containing carbon atoms and a hydroxyalkyl group, one alkyl moiety having about 10 to about 18 carbon atoms, and about 1 to about 3 carbon atoms. A water-soluble phosphine oxide comprising two moieties selected from the group consisting of an alkyl group comprising carbon atoms and a hydroxyalkyl group; and one alkyl moiety having from about 10 to about 18 carbon atoms; A water-soluble sulfoxide comprising about 3 moieties selected from the group consisting of alkyl and hydroxyalkyl moieties.

[0069] Semipolar nonionic detergent surfactants include amine oxide surfactants having the formula:

[0070]

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Wherein R ³ is an alkyl, hydroxyalkyl or alkylphenyl group containing from about 8 to about 22 carbon atoms or a mixture thereof, and R ⁴ is from about 2 to about 3 Wherein x is 0 to about 3 and each R ⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms. Or a polyethylene oxide group comprising about 1 to about 3 ethylene oxide groups. The R ⁵ groups can be linked to each other through, for example, an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxide and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxide.

[0073] US Patent No. 4 to Llenado, issued January 21, 1986.
No. 6,565,467, from about 6 to about 30 carbon atoms, preferably from about 1 to about 30 carbon atoms.
Alkyl polysaccharides and polysaccharides having hydrophobic groups containing from 0 to about 16 carbon atoms, such as from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 1.3. Any reduced saccharide containing 5 or 6 carbon atoms with a polyglycoside having a hydrophilic group containing 2.7 saccharide units can be used,
For example, the glucosyl moiety can be replaced with a glucose, galactose and galactosyl moiety (optionally, the hydrophobic group is attached at a 2-, 3-, 4-etc. Position, resulting in a glucose and galactosyl different from the glucoside or galactoside. ). The inter-saccharide linkage can be, for example, between a position of the additional saccharide unit and the 2-, 3-, 4- and / or 6-position on said saccharide unit.

Optionally, but less preferably, it is possible for a polyalkylene oxide chain to be present connecting the hydrophobic moiety and the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, branched or unbranched alkyl groups containing about 8 to about 18, preferably about 10 to about 16 carbon atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can include no more than about 3 hydroxy groups, and / or
Alternatively, the polyalkylene oxide chain can include up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, di-, tri-, tetra-, penta- and hexaglucoside, galactoside, lactoside, glucose, fructoside , Fructose and / or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.

Preferred alkyl polyglycosides have the formula R ² O (C _n H _2n O) _t (glycosyl) _{x where} R ² is an alkyl group of from about 10 to about 18 carbon atoms, preferably about 12 Alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof containing up to about 14 carbon atoms, where n is 2 or 3
, Preferably 2, t is 0 to about 10, preferably 0, and x is about 1.3 to
About 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7, and the glycosyl is preferably derived from glucose. To make these compounds, an alcohol, an alkyl polyethoxy alcohol, is first formed and then reacted with glucose or a glucose source to form a glucoside (attached at position 1). Thereafter, an additional glucosyl unit can be linked between its 1-position and the 2-, 3-, 4- and / or 6-position, preferably predominantly 2, of said glucosyl unit.

The fatty acid amide surfactant has the following formula:

[0077]

Embedded image

Wherein R ⁶ is an alkyl group containing about 7 to about 21 (preferably about 9 to about 17) carbon atoms, and each R ⁷ is hydrogen, C ₁ -C ₄ alkyl, It is selected from the group consisting of C ₁ -C ₄ hydroxyalkyl and — (C ₂ H ₄ O) _x H, where x varies from about 1 to about 3.

Preferred amides are C ₈ -C ₂₀ ammonia amide, monoethanolamide, diethanolamide and isopropanolamide.

[0080]Cationic surfactant Cationic detergent surfactants can also be included in the detergent compositions of the present invention. Katio
Surfactants such as alkyldimethylammonium halides
And surfactants having the following formula: [R^Two(OR^Three)_y[R^Four(OR^Three)_y]_TwoR^FiveN⁺X^- Where R^TwoIs an alkyl or alkylbenzyl group having about 8 to about 18 carbon atoms in the alkyl chain, and each R^ThreeIs -CH_TwoCH_Two-, -CH_TwoCH (CH _Three )-, -CH_TwoCH (CH_TwoOH)-, -CH_TwoCH_TwoCH_Two-And their mixtures
Selected from the group consisting of^FourIs C₁~ C_FourAlkyl, C₁~ C_FourHydroxyalkyl, benzyl, two R^FourA ring structure formed by bonding groups, -CH_TwoCHOHCHOHCOR⁶CHOH-CH_TwoOH (where R⁶Is about 1000
Any hexose or hexose polymer having a molecular weight of less than
And y is non-zero when selected from the group consisting of hydrogen;^FiveIs R^FourIs the same as
Or R^Two+ R^FiveIs an alkyl chain having a total number of carbon atoms of about 18 or less,
y is from 0 to about 10, the sum of y values is from 0 to about 15, and X is
It is Zion.

Other cationic surfactants useful herein are described on Oct. 1, 1980.
It is also described in U.S. Pat. No. 4,228,044 issued to Campbell on the 4th. This patent is hereby incorporated by reference.

Other Surfactants Amphoteric surfactants can be included in the detergent compositions herein. These surfactants are widely described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines where the aliphatic group can be linear or branched. can do. One of the aliphatic substituents has at least about 8
Carbon atoms, typically from about 8 to about 18 carbon atoms, at least one containing an anionic water solubilizing group, for example, carboxy, sulfonate, sulfate. For examples of amphoteric surfactants, see Rollin (L) published December 30, 1975.
U.S. Pat. No. 3,929,678, column 19, lines 18-3.
See No. 5. Preferred amphoteric surfactants include C ₁₂ -C ₁₈ alkyl ethoxylates (“AE”), including so-called narrow peak alkyl ethoxylates, C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ( "sultaines"), C ₁₀ ~C ₁₈ amine oxides and mixtures thereof.

[0083] Zwitterionic surfactants can also be incorporated into the detergent compositions herein. These surfactants can be broadly described as secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives or quaternary ammonium derivatives, quaternary phosphonium compounds or tertiary sulfonium compounds. it can. For examples of zwitterionic surfactants, see Laughl, published December 30, 1975.
in) et al., U.S. Pat. No. 3,929,678, column 19, lines 38-35 to column 2.
See line 48. Amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Polyhydroxy Fatty Acid Amide Surfactant The detergent compositions herein can also contain an effective amount of a polyhydroxy fatty acid amide surfactant. By "effective amount" is meant that the formulator of the composition can select the amount of polyhydroxy fatty acid amide that improves the cleaning performance of the detergent composition to be incorporated into the composition. In general, at conventional levels, the incorporation of about 1% by weight of polyhydroxy fatty acid amide improves purification performance.

The detergent compositions herein typically comprise about 1%, preferably about 3% to about 30%, by weight of a polyhydroxy fatty acid amide surfactant. The polyhydroxy fatty acid amide surfactant component comprises a compound of the following structural formula:

[0086]

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Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e., methyl), R ² is, C ₅ -C ₃₁ hydrocarbyl, preferably straight chain C ₇ -C ₁₉ alkyl le or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₅ alkyl or alkenyl, or a mixture thereof, wherein Z is a straight chain hydrocarbyl chain having at least three hydroxyls directly attached to the chain. Having polyhydroxyhydrocarbyl, or an alkoxylated derivative of polyhydroxyhydrocarbyl (preferably ethoxylated or Propoxy is a derivative). Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. High dextrose corn syrup, high fructose corn syrup and high maltost corn syrup
It can be used as a raw material in the same manner as the individual sugars described above. These corn syrups can yield a mixture of sugar components for Z. It is to be understood that no other suitable ingredients are to be excluded. Z _{preferably, -CH 2 - (CHOH) n} -CH 2 OH, -CH (CH 2 OH) - (CHOH) n-1 -CH 2 OH, -CH 2 - (CHOH) 2 (CH OR ' ) (CHOH) —CH ₂ OH, where n is an integer from 3 to 5, and R ′ is H or a cyclic or aliphatic monosaccharide and their alkoxylated derivatives. Is done. n is 4 glycityls, particularly _{-CH 2 - (CHOH) 4 -CH} 2 OH are most preferred.

R ′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl. .

R ² —CO—N <can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, and the like.

Z is 1-deoxyglucityl, 2-deoxyfrucchityl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotrio It can be Chityl or the like.

[0091] Methods for producing polyhydroxy fatty acid amides are known in the art. Generally, polyhydroxy fatty acid amides react an alkylamine with a reducing sugar in a reductive amination reaction to produce the corresponding N-alkyl polyhydroxyamine, which is then converted to a N-alkyl polyhydroxyamine in a condensation / amidation step. Reacting with a fatty aliphatic ester, ie, a triglyceride, to give N
-Alkyl-N-polyhydroxy fatty acid amide products. Methods for producing compositions containing polyhydroxyfatty acid amides are described, for example, in Thomas Hedley on February 18, 1959.
edley & Co. G., published by G., Ltd.). B. Patent specification No. 80
No. 9,060, Wilson, U.S. Pat. No. 2,965,576 issued Dec. 20, 1960, and Schwartz (S) issued Mar. 8, 1955.
Chwartz), US Pat. No. 2,703,798 and Dec. 1934.
U.S. Pat. No. 1,985,42 to Piggott, issued on May 25.
No. 4 discloses it. Each patent is hereby incorporated by reference.

Diamines Preferred liquid detergent compositions of the present invention comprise one or more diamines, preferably in an amount such that the ratio of anionic surfactant to diamine present is from about 40: 1 to about 2: 1. . The diamine provides for improved removal of fats and oils while maintaining suitable levels of foam.

Suitable diamines for use in the compositions of the present invention have the formula:

[0094]

Embedded image

Wherein each R is independently hydrogen, C₁~ C_FourLinear or branched alkyl, of the formula-(R^TwoO)_y R^Three(Where R^TwoIs C_Two~ C_FourStraight or branched alkylene and their mixed groups
Yes, R^ThreeIs hydrogen, C₁~ C_FourAlkyl and mixed groups thereof, wherein y is 1 to 10), and is preferably selected from the group consisting of
At least two R units are hydrogen, more preferably each R unit is hydrogen
, X is i) C_Three~ C_TenLinear alkylene, C_Three~ C_TenBranched alkylene, C_Three~ C_Ten Cyclic alkylene, C_Three~ C_TenBranched cyclic alkylene, formula-(R^TwoO)_yR^Two-(Where
R^TwoAnd y are the same as defined above), ii) C_Three~ C_TenStraight chain, C_Three~ C_TenBranched straight chain, C_Three~ C_TenCyclic, C_Three~ C _Ten Branched cyclic alkylene, C₆~ C_TenArylene, and iii) a main chain unit selected from the mixed group of (i) and (ii), wherein the diamine has a pK greater than 8.
a main chain unit comprising one or more electron donating or electron withdrawing moieties providing a
It is.

[0096] Preferred diamines of the present invention each have a p in the range of about 8 to about 11.5, preferably in the range of about 8.4 to about 11, and more preferably in the range of about 8.6 to about 10.75.
Having K ₁ and pK _2. For the purposes of the present invention, the term "pKa" refers equally well separately or term collectively "pK _1" and "pK _2".
The term "pKa" as used herein is used throughout the specification as it is used by those skilled in the art. pKa values are based on standard sources, eg, "Cri
physical Stability Constants: Volume 2, A
mines "by Smith and Martel, Plenum Pr
ess, N.M. Y. and London, (1975).

As defined herein, the pKa value is defined to be measured in an aqueous solution at 25 ° C. having an ionic strength of about 0.1 to about 0.5M. As used herein, pKa is an equilibrium constant that depends on temperature and ionic strength, and thus the values reported by reference rather than measured in the above-described method are those that constitute the present invention. And may not exactly match the range. To eliminate ambiguity, the relevant conditions and / or criteria used for pKa values of the present invention may be found herein or in “Critical Stability”.
Constants: Volume 2, Amines ". One typical measurement method is to potentiometrically titrate the acid with sodium hydroxide and use the method described in "The Chemist's Ready Reference H".
andbook "by Shugar and Dean, McGraw Hi
11, N. Y. , (1990) by a suitable method.
Ka is determined.

A preferred diamine in consideration of performance and supply is 1,3-diaminopropane (
pK ₁ = 10.5, pK ₂ = 8.8), 1,6-diaminohexane (pK ₁ = 11, pK ₂ = 10), 1,3-diaminopentane (Dytek EP) (pK ₁ = 10.5, pK ₂ = 8.9) and 2-methyl-1,5-diaminopentane (Dytek A) (pK ₁ = 11.2, pK ₂ = 10.0). Other preferred materials are the primary / primary diamines having alkylene spacers ranging from C ₄ -C _8. Generally, primary diamines are preferred over secondary and tertiary diamines.

The following are non-limiting examples of diamines suitable for use in the present invention.
1-N, N-dimethylamino-3-aminopropane having the formula

[0100]

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1,6-diaminohexane having the formula:

[0102]

Embedded image

1,3-diaminopropane having the formula:

[0104]

Embedded image

2-methyl-1,5-diaminopentane having the formula:

[0106]

Embedded image

1,3-Diaminopentane having the following formula and available under the trade name Dytek EP

[0108]

Embedded image

1,3-diaminobutane having the formula:

[0110]

Embedded image

Jeffamine, which is a diamine having the following formula and having an alkyleneoxy main chain (
Jeffamine) EDR148

[0112]

Embedded image

3-Methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophoronediamine) having the formula:

[0114]

Embedded image

A 1,3-bis (methylamino) cyclohexane having the formula:

[0116]

Embedded image

Auxiliary component builder The composition according to the invention can further comprise a builder system. Any conventional builders including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediaminetetraacetate, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid The system is suitable for use herein. Although less preferred for obvious environmental reasons, phosphate builders can also be used herein.

Suitable polycarboxylate builders for use herein include citric acid, preferably in the form of a water-soluble salt, of the formula R—CH (COOH) CH ₂ (COOH), where R is , C _10-20 , preferably C _12-16 alkyl or alkenyl, or R can be substituted with a hydroxy, sulfosulfoxyl or sulfone substituent). Particular examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate. The succinate builder is preferably used in the form of a water-soluble salt, including sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of tartarate monosuccinic and tartarate disuccinic acids such as those described in US Pat. No. 4,663,071.

Particularly for the liquid embodiments herein, fatty acid builders suitable for use herein are saturated or unsaturated C _10-18 fatty acids and their corresponding soaps. Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. A preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are based on dodecenyl succinic and citric acid.

The washing builder salts usually comprise 3% to 50%, preferably 5%, by weight of the composition.
% To 30%, most commonly from 5% to 25%.

Optional Detergent Components Enzymes The detergent compositions of the present invention can further comprise one or more enzymes that provide cleaning performance benefits. The enzymes include cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, lipase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase,
Examples include enzymes selected from pentosanase, malanases, β-glucanases, arabinosinases, or mixtures thereof. A preferred combination is a detergent composition having a mixture of available conventional enzymes such as proteases, amylases, lipases, cutinases and / or cellulases.

[0123] The cellulase usable in the cellulase present invention include both bacterial or fungal cellulases. Suitable cellulases are disclosed in US Pat. No. 4,435,307 to Barbesgoard et al., Which discloses a fungal cellulase produced from Humicola insolens. Suitable cellulases are GB-
A-2,075,028, GB-A-2,095,275 and DE-OS-2
, 247, 832.

Examples of such cellulases include Humicola insolens (Humicola grisea var. Ther
moidea), in particular, a cellulase produced by Humicola strain DSM1800. Other suitable cellulases are those from Humicola insolens having a molecular weight of about 50 KDA, an isoelectric point of 5.5 and containing 415 amino acids. Particularly suitable cellulases are those that have the advantage of color considerations. Examples of such cellulases are described in European Patent Application 9120287 filed on November 6, 1991.
9.2 (Novo).

The peroxidase enzyme is a source of oxygen such as percarbonate, perborate, persulfate,
Used together with hydrogen peroxide. They are used for "solution bleaching", i.e. to prevent the transfer of colors or dyes removed from the substrate during the washing operation to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89 /
No. 099813 and European Patent Application EP 912028 filed Nov. 6, 1991
82.6.

The cellulases and / or peroxidases are usually incorporated into detergent compositions at a level of 0.0001% to 2% active enzyme based on the weight of the detergent composition.

[0127] Proteolytic enzymes proteolytic enzymes, animal, may be of vegetable or microbial origin (preferred). Proteases for the detergent compositions herein include, but are not limited to, trypsin, subtilisin, chymotrypsin and elastase type proteases. Subtilisin-type protease enzymes are preferred for use herein. Bacterial serine proteases obtained from Bacillus subtilis and / or Bacillus licheniformis are particularly preferred.

Suitable proteolytic enzymes include commercially available Novo Industries
i A / S) Alcalase (Preferred), Esperase , Savi
nase Maxatase from Gist-Brocades (Copenhagen, Denmark) , Maxacal And Maxape
n15 (Protein Engineering Maxacal ) (Delft, The Netherlands) and subtilisins BPN and BPN '(preferred). EP 251 446 B, issued December 28, 1994 (especially pages 17, 24 and 98)
) And modified serine proteases derived from bacteria, such as those manufactured by Genencor International, Inc. (San Francisco, CA), also referred to herein as "Protease B". It is an enzyme. U.S. Pat. No. 5,030,378 issued to Venegas on Jul. 9, 1991 includes a modified serine protease from a bacterium, referred to herein as "Protease A" (Genencor International). ) (BNP '
The same is described). See, inter alia, columns 2 and 3 of US Pat. No. 5,030,378 for a complete description, including the amino sequences of Protease A and its variants. Other proteases are trade names, Primase, D
It is sold in Urazym, Opticlean and Optimase.
Here, a preferred protease is Alcalase. (Novo Indus tri A / S), BNP ', Protease A, Protease B (Genencor) and mixtures thereof. Protease B is most preferred.

The proteases described in US Pat. No. 5,470,733 are of particular interest for use herein.

The proteases described in our co-pending application USSN 08 / 136,797 can also be included in the detergent compositions of the present invention.

[0131] Another protease, referred to as "Protease D", is a carbonyl hydrolase variant having an unnatural amino acid sequence. This is Genencor (G
a patent application by A. Baeck et al., WO 95/10615, filed on April 20, 1995 (US patent application Ser. No. 08 / 322,676, filed Oct. 13, 1994) issued by Enencor International;
The title of the invention, "Protease-Containing Cleaning"
According to the numbering of Bacillus amyloliquefaciens subtilisin described in "Compositions", at the position of the carbonyl hydrolase corresponding to position +76, preferably +99, +101, +103, +104, +1
07, +123, +27, +105, +109, +126, +128, +135
, +156, +166, +195, +197, +204, +206, +210,
Replace multiple amino acid residues with different amino acids in combination with one or more amino acid residue positions corresponding to positions selected from the group consisting of +216, +217, +218, +222, +260, +265, and / or +274 It is derived from the precursor carbonyl hydrolase.

Useful proteases are also described in PCT Application, Procter & Gamble (Th
e Procter & Gamble Company) January 1995
WO 95/3010 issued on January 9, Procter & Gamble (Th
e Procter & Gamble Company) January 1995
WO 95/30011 issued on January 9, Procter & Gamble (Th
e Procter & Gamble Company) January 1995
It is described in WO 95/29979 issued on January 9th.

[0133] Protease enzymes can be incorporated into compositions according to the present invention at levels of about 0.0001% to 2% active enzyme, by weight of the composition.

Lipases Suitable lipase enzymes include, for example, those disclosed in British Patent 1,372,034.
And those produced by Pseudomonas microorganisms such as Pseudomonas stutzeri ATCC 19.154. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM1057, which exhibit a positive immunocross reaction with antibodies to the lipase. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano" and is hereinafter referred to as "Amano-P". Further suitable lipases are M1 Lipase And Lipomax (Gist-Brocades). Other suitable commercial lipases include Amano-CES, Lipase ex Chromobacter viscosu
m, for example, Chromobacter viscosum var. from Toyo Brewery in Tagata, Japan. lipoly
ticum NRRLB 3673, US Biochemical Corp. (US
. Biochemical Corp. ) And Dutch Disoins (Diss)
oynth Co. ) From Chromobacter viscosum lipase, and lipase e
x Pseudomonas gladioli. Lipolase derived from Humicola lanuginosa and commercially available from Novo Enzymes are preferred lipases for use herein. See also EP 341,947. Lipase and amylase variants stabilized against peroxidase enzymes
It is described in WO9414951A by Novo. WO9205
See also 249 and RD94359044.

A highly preferred lipase is the D96L lipolytic enzyme variant of natural lipase derived from Humicola lanuginosa as described in US patent application Ser. No. 08 / 341,826 (see also patent application WO 92/05249). See, ie, that the natural lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is replaced with leucine (L).
The substitution of aspartic acid for leucine at position 6 is shown as D96L). Preferably, Humicola lanuginosa strain DSM4106 is used.

Despite many publications on lipase enzymes, Humicola lanugin
Only lipases derived from osa and produced in aspergllus oryzae as hosts have so far gained widespread use as additives for cleaning products. It is, as mentioned above, the trade name Lipolase And Lipolase Ultra Available from Novo Nordisk. To optimize the stain removal performance of Lipolase, Novo Nordis
k) has produced a number of variants. As described in WO 92/05249, the D96L mutant of native Humicola lanuginosa lipase improves the efficiency of removing swine fat stain 4.4-fold over wild-type lipase (0.075-2.5 mg of enzyme / protein). In the range of liters). Novo Nordis
Research Disclosure No. 35944, published by K) on March 10, 1994, corresponds to 0.001 to 100 mg (5 to 500,000 LU / liter) of lipase variant (D96L) corresponding to lipase variant / liter of washing solution. It is disclosed that it can be added in an amount.

Also suitable are cutinases [EC 3.1.1.50], which can be considered a special type of lipase, ie lipases that do not require interfacial activation.

[0138] Lipases and / or cutinases are usually present in an amount of 0.
Formulated in detergent compositions at levels of 0001% to 2% active enzyme.

Amylase Amylases (α and / or β) can be included for the removal of carbohydrate-based stains. Suitable amylase is Termamyl (Novo Nordisk) Fungamyl And Ban (Novo Nordisk). The enzymes may be of any suitable origin, such as from plants, animals, bacteria and yeast. Amylase enzymes are usually
0.0001% to 2%, preferably about 0.0001% by weight of the detergent composition
To about 0.5%, more preferably from about 0.0005% to about 0.1%, even more preferably from about 0.001% to about 0.05% active enzyme level in the detergent composition. .

The amylase enzyme was obtained from Novo Nordisk using W
No. 95/26397 and co-pending application PCT / DK96 / 00056. Accordingly, other specific amylase enzymes for the detergent compositions of the present invention include: (a) Ter in a temperature range of 25 ° C to 55 ° C and a pH value in the range of 8 to 10.
mamyl An α-amylase characterized by having a specific activity at least 25% higher than the specific activity of α-amylase. Its specific activity is Phadebas It is measured by an α-amylase activity assay. Such a Phadebas The α-amylase activity assay is described in WO 95/26397, pages 9-10. (B) an α-amylase according to (a) comprising the amino acid sequence shown in the SEQ ID listing in the reference cited above, or an α which is at least 80% homologous to the amino acid sequence shown in the SEQ ID listing. −
amylase. (C) His-His-Asn-Gly-Thr-Asn-G at the N-terminus
ly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-T
An α-amylase according to (a) obtained from an alkalophilic Bacillus species comprising the amino acid sequence of yr-Leu-Pro-Asn-Asp. Science 22
7, 1985, p. If the comparison of the respective amino acid sequences performed via an algorithm such as those described by Lipman and Pearson at 1435 shows X% identity, the polypeptide is identified as having an X against the parent amylase. % Is considered to be a cognate string. (D) The α-amylase is an alkalophilic Bacillus spp.
9, α-amylase by (ac) which can be obtained from any of NCB12512, NCIB12513 and DSM935. In the context of the present invention, the term "obtainable from" refers not only to the amylase produced by the Bacillus sp., But also to the DNA sequence isolated from such a Bacillus sp. Amylase produced in the transformed host microorganism is also meant. (E) An α-amylase exhibiting positive immunocross reactivity with an antibody raised against an α-amylase having an amino acid sequence corresponding to each of the α-amylases in (ad). (F) (i) a parent α-amylase having one of the amino acid sequences shown in each correspondence to α-amylase in (ae), or (ii) at least 80% homologous sequence with one or more said amino acids And / or a parent α-amylase exhibiting immunocross reactivity with an antibody raised against an α-amylase having one of the above amino acid sequences. DNA sequences that encode a single α-amylase include variants of the parent α-amylase that are encoded by the same probe and hybridizing DNA sequence. In these mutants: At least one amino acid residue of the parent α-amylase is peripheral.
And / or 2. At least one amino acid residue of the parent α-amylase has been replaced with a different amino acid residue. And / or 3. At least one amino acid residue has been inserted into said parent α-amylase. The mutant has α-amylase activity and exhibits at least one of the following properties with respect to the parent α-amylase. Improved thermal stability, improved oxidative stability, reduced Ca ion dependence, improved stability at neutral to relatively high pH values and / or alpha starch degradation activity, enhanced alpha starch degradation at relatively high temperatures Increasing or decreasing the activity and the pI to better match the isoelectric point (pI) value for the α-amylase variant to the medium pH.

The variants are described in patent application PCT / DK96 / 00056.

Other amylases suitable herein include, for example, Novo
Α-amylase, described in GB 1,296,839 by International Bio-Synt.
hetics, Inc. ) By RAPIDASE And TERMAMYL by Novo Is mentioned. FUNGAMY L from Novo Is particularly useful. Enzyme engineering for improved stability, eg, oxidative stability, is known. For example, J. Biological Chem. , Vol.
260, no. 11, June 1985, pp. See 6518-6521. Some preferred embodiments of the composition are amylases having improved stability in detergents such as automatic dishwashing types, especially TERMAMYL in commercial use in 1993. Amylase with improved oxidative stability as measured against a reference point can be utilized. These preferred amylases herein are, for example, oxidative stability against hydrogen / peroxide / tetraacetylethylenediamine in a buffer solution at pH 9-10, as measured against the reference point amylase described above, for example, about 60. The property of being an "stability-improving" amylase characterized by at least a thermostability at normal wash temperatures such as <RTIgt; To share. Stability can be measured using any technical test for which the technology has been published. See, for example, the references disclosed in WO9402697. Stability improving amylase can be purchased from Novo and Genencor International. One class of highly preferred amylases herein is Bacillus amylase, especially Bacillus α-amylase, whether one amylase species, two amylase species or multiple amylase species are direct precursors. Of 1
It has common features derived using site-directed mutagenesis from one or more.
Amylases with improved oxidative stability relative to the reference amylases described above are preferred for use in oxygen bleaching detergent compositions, especially as different from the bleaching detergent compositions herein, more preferably chlorine bleaching detergent compositions. Such preferred amylases include (a) Termamyl B. known as licheniformis alanine or threonine at position 197 of α-amylase, preferably threonine, or B. amyloliquefaciens, B. subtilis or B.
Nov. 3, Nov. 1994 (Nov. 2007) as further described by variants that are substituted using a homologous variant of the parental amylase, such as .stearothemophilus.
amylase according to WO 9402597 described above by o), (b) by C. Mitchinson, March 13-17, 1994;
A paper “Oxidatively” presented at the 2007 American Chemical Society National Conference
"Resistant Alpha-Amylase"
(Enencor International). Among them, a bleach in an automatic dishwashing detergent inactivates α-amylase, but an amylase having improved oxidative stability is disclosed in B.A. licheniformis NCI
B8061 is described as being made by Genencor. Methionine (Met) has been identified as the residue most likely to be modified. Met
Substituted at one time at positions 8, 15, 197, 256, 304, 366 and 438, leading to particular mutants of particular interest being M197L and M197T;
The M197T mutant is the most stable expression mutant. Stability is CASCAD And SUNLIGHT It was measured in. (C) Particularly preferred amylases include amylase variants with additional modifications in the immediate parent as described in WO 9510603, including DURAMYL Available from the assignee Novo. Other particularly preferred oxidative stability improving amylases include those described in WO 9418314 by Genencor International and WO 9402597 by Novo. For example, any other oxidative stability improving amylase, such as that induced by site-directed mutagenesis from known chimeric hybrids or single mutant parent forms of available amylase can be used. Other preferred enzyme modifications are available. WO950 by Novo
See 9909A.

Enzyme Stabilizing System The enzyme-containing composition herein may also optionally comprise from about 0.001% to about 10%
, Preferably about 0.005% to about 8%, most preferably about 0.01% to about 6% by weight of the enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the cleaning enzyme. Such stabilizing systems can be provided essentially by other formulated active species, or can be added separately, for example, by the formulator or the manufacturer of the detergent enzyme. Such stabilizing systems can comprise, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acids, and mixtures thereof, depending on the type and physical form of the detergent composition. Designed to address stabilization issues.

One approach to stabilization is to use a water-soluble ion source that provides calcium and / or magnesium ions to the enzyme in the final composition.
Calcium ions are generally more effective than magnesium ions and are preferred herein when only one type of cation is used. Typical detergent composition,
In particular, the liquid detergent composition comprises about 1 to about 30, preferably about 2 to about 20, more preferably about 8 to about 12 mmol of calcium ion / liter of final detergent composition. However, it is possible to vary depending on factors including the variety, type and level of enzyme to be incorporated. Preferably, water-soluble calcium or magnesium salts including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate are used, and more generally calcium sulfate or e.g. Magnesium salts corresponding to the calcium salts mentioned can be used. For example, even increased levels of calcium and / or magnesium are useful, for example, to promote certain types of fat dissolving effects of surfactants.

Another approach to stabilization is through the use of borate species. Sevason (S
See U.S. Pat. No. 4,537,706 to Eberson. When using a borate stabilizer, it can be used at a level of up to 10% or more of the composition. However, more typically, up to about 3% by weight levels of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent applications. A substituted boric acid such as phenyl boric acid, butane boric acid or p-bromophenyl boric acid can be used in place of boric acid, and reduced levels of total boron in the detergent composition may be possible through the use of such substituted boron derivatives.

[0146] The stabilization system of certain cleaning compositions, for example, automatic dishwashing compositions, furthermore, the chlorine bleaching chemical species present in many feedwaters can attack or inactivate enzymes, especially under alkaline conditions. 0 to about 10%, preferably about 0.
It may comprise from 01 to about 6% by weight of a chlorine bleach scavenger.
Chlorine levels in the water are small, typically in the range of about 0.5 ppm to about 1.75 ppm, while, for example, in the total water volume that comes into contact with the enzyme during dishwashing or fabric washing. Available chlorine can be relatively high. Thus, the stability of the enzyme to chlorine during use is sometimes problematic. Since perborate or percarbonate capable of reacting with chlorine bleaches may be present in some of the compositions in amounts calculated separately from the stabilizing system, the use of additional stabilizers for chlorine is , Although it is possible to obtain improved results from its use, but is most generally not required. Suitable chlorine scavenger anions are widely known and readily available and, when used, can be salts containing the ammonium cation with sulfites, bisulfites, thiosulfites, thiosulfates, iodides, etc. It is. Antioxidants such as carbamates and ascorbates, organic amines such as ethylenediaminetetraacetic acid (EDTA),
Alternatively, alkali metal salts of EDTA, monoethanolamine (MEA) and mixtures thereof can be used as well. Similarly, special enzyme suppression systems can be formulated so that different enzymes have maximum compatibility. Sources of hydrogen peroxide such as bisulfite, nitrate, chloride, sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate; and phosphates, condensed phosphates, acetates, benzoates,
Other conventional scavengers such as citrate, formate, lactate, malate, tartrate, salicylate, and the like, and mixtures thereof, can be used if necessary. In general, the function of a chlorine scavenger can be performed by components listed separately (eg, a hydrogen peroxide source) under well-recognized functions, so that compounds that perform the required function to the extent necessary are described in the present invention. There is no absolute need to add another chlorine scavenger as long as it is present in the enzyme-containing embodiments of the present invention. Even so,
Scavengers are added only for optimal results. In addition, the formulator will exercise the chemist's usual skills in avoiding the use of any enzyme scavenger or enzyme stabilizer that is very incompatible with other reaction components when formulated. With respect to the use of ammonium salts, such salts can be easily incorporated into detergent compositions,
Tends to absorb water and / or liberate ammonia during storage. Accordingly, such salts, if present, are preferably Baginski (Baginski).
) Et al., U.S. Pat. No. 4,652,392.

[0147] Useful perfumes and perfume ingredients in the perfume present compositions and methods are aldehydes, but are not limited like ketones and esters, comprising a variety of natural and synthetic chemical components containing them. Various natural extracts and essences that can comprise a complex mixture of ingredients, such as orange oil, lemon oil, rose extract,
Also included are lavender, musk, patchouli oil, aromatic extracts, sandalwood oil, pine oil, and eelwood. The final fragrance can comprise an extremely complex mixture of these components. The final perfume typically comprises from about 0.01% to about 2% by weight of the detergent compositions herein, with the individual perfume ingredients comprising from about 0.0001% to about 2% of the final perfume composition. It is possible to make up 90%.

Non-limiting examples of perfume ingredients useful herein include 7-acetyl-1,2
, 3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, ionone methyl, ionone gamma methyl, methyl sedrone, methyl dihydrojasmonate, methyl 1,6,10 -Trimethyl-2,5,9-cyclododecatrien-1-yl ketone, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, 4-acetyl-6-t-butyl-1,1 -Dimethylindane, para-hydroxy-phenyl-butanone, benzophenone, methyl beta naphthyl ketone, 6-acetyl-1,1,2,3,3,5-hexamethylindane, 5-acetyl-3-isopropyl-1,1 , 2,6-tetramethylindane, 1-dodecanal, 4- (4-hydroxy-4-methylphenyl) -3-cyclohexene-1-ca Boxaldehyde, 7-hydroxy-3,7, -dimethyloctanal, 10-undecen-1-al, iso-hexenylcyclohexylcarboxaldehyde, formyltricyclodecane, condensation product of hydroxycitronellal and methylanthranilate, Condensation product of hydroxycitronellal and indole, condensation product of phenylacetaldehyde and indole, 2-methyl-3- (para-t-butylphenyl) -propionaldehyde, ethylvanillin, helitropin, hexylcinnamaldehyde, amylcinnamaldehyde ,
2-methyl-2- (para-iso-propylphenyl) -propionaldehyde,
Coumarin, decalactone gamma, cyclopentadecanolide, 16-hydroxy-
9-hexadecenoic acid lactone, 1,3,4,6,7,8-hexahydro-4,6
, 6,7,8,8-Hexamethylcyclopenta-gamma-2-benzo-pyran,
Beta-naphthol methyl ether, ambroxane, dodecahydro-3a, 6
, 6,9a-Tetramethyl-naphtho [2,1b] furan, cedrol, 5- (2,
2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopentene-1-
Yl) -2-buten-1-ol, caryophyllene alcohol, tricyclodecenyl propionate, tricyclodecenyl acetate, benzyl salicylate, ceryl acetate and cyclohexyl para- (t-butyl) acetate.

Particularly preferred perfume materials are those that provide the greatest fragrance improvement in the final product composition containing cellulase. These fragrances include hexylcinnamaldehyde, 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-. 1,1,6
, 7-Tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1,1,1
3,4,4,6-hexamethyltetralin, para-t-butyl-cyclohexyl acetate, methyl dihydrojasmonate, beta naphthol methyl ether, methyl beta naphthyl ketone, 2-methyl-2- (para-iso-propylphenyl )
-Propionaldehyde, 1,3,4,6,7,8-hexahydro-4,6,6
, 7,8,8-Hexamethylcyclopenta-gamma-2-benzo-pyran, dodecahydro-3a, 6,6,9a-tetramethyl-naphtho [2,1b] furan, anisaldehyde, coumarin, cedrol, vanillin, Cyclopentadecanolide, tricyclodecenyl acetate and tricyclodecenyl propionate,
Not limited to them.

Other perfume materials include essential oils, resinoids, and a variety of sources from but not limited to Peruvian balsam, frankincense, sogo aroma, Radanum resin, nutmeg, cassia oil, benzoin resin, Corianda and Lavandin. Resins. Still other perfume chemicals include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1,1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and eugenol. A carrier such as diethyl phthalate can be used in the final perfume composition.

Polymeric Dispersants Polymeric dispersants can be advantageously utilized in the compositions herein at levels from about 0.1% to about 7% by weight. Without wishing to be limited by theory, it is believed that the polymeric dispersant improves overall detergent performance by inhibiting crystal growth, deflocculating and deflocculating particulate soils, and preventing redeposition.

The polymeric polycarboxylate materials can be produced by polymerizing or copolymerizing a suitable unsaturated monomer, preferably in the form of an acid. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), formic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene Malonic acid. The presence of monomeric segments that do not contain carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., in the polymeric polycarboxylates herein are suitable as long as such segments do not constitute more than about 40% by weight.

[0153] Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid based polymers useful herein are water soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2,000 to 10,000, more preferably from about 4,000 to 7,000
, Most preferably in the range of about 4,000 to 5,000. Such water-soluble salts of acrylic acid polymers include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Suitable polymers of this type are known materials. The use of this type of polyacrylate in detergent compositions is described, for example, in 1967
No. 3,308,067 to Diehl, issued March 7, 2014.

Acrylic / maleic acid based copolymers can also be used as a preferred component of the dispersant / anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such polymers in acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, and most preferably from about 7,000 to 65,000.
Range. The ratio of acrylate to maleate segments in such copolymers is generally from about 30: 1 to about 1: 1, more preferably about 10: 1.
２2: 1. Such water-soluble salts of acrylic acid / maleic acid copolymer include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Soluble acrylic acid / maleic acid copolymers of this type are disclosed in European Patent Application No. 66915 published December 15, 1982 and published September 3, 1886 which also describe such polymers comprising hydroxypropyl acrylate. It is a known material described in EP 193,360. Still other useful dispersants include maleic / acrylic / vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, 45/45/10 terpolymers of acrylic acid / maleic acid / vinyl alcohol.

Other polymeric materials that can be included are polypropylene glycol (PP
G), propylene glycol (PG) and polyethylene glycol (PEG)
It is. PEG exhibits dispersant performance and acts as a clay soil removal-redeposition inhibitor. Typical molecular weight ranges for these purposes are from about 500 to about 10
000, preferably from about 1,000 to about 50,000, more preferably about 1,
It ranges from 500 to about 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (average) of about 10,000.

In addition, polymeric soil release agents, hereinafter referred to as “SRA” or “SRA's”, may optionally be used in the present detergent compositions. When utilized, SRA's generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the composition. .

Preferred SRA's typically adhere to hydrophilic segments and hydrophobic fibers that hydrophilize the surface of the hydrophobic fibers, such as polyester and nylon, and adhere to the hydrophobic fibers through the completion of a wash and rinse cycle. And thus has a hydrophobic segment that acts as a fixing medium for the hydrophilic segment. Thereby, SR
Stain generated after treatment with A can be more easily cleaned in a subsequent cleaning procedure.

SRA's can include a variety of charged, for example, anionic or rarely cationic (US Pat. No. 4,956,447) monomer units, and uncharged monomer units, and the structure is It can be linear, branched, or even star-shaped. SRA's can include capping moieties that are particularly effective in controlling molecular weight or in altering physical or surface active properties. The structure and charge distribution can be tailored for applications for different fiber or fabric types, and for various detergent or detergent additive products.

Preferred SRA's typically include oligomeric terephthalate esters produced by a process that often involves at least one transesterification / oligomerization with a metal catalyst such as a titanium (IV) alkoxide. These esters, of course, do not form a tightly crosslinked
It can be made with additional monomers that can be incorporated into the ester structure via two, three, four or more positions.

Suitable SRA's include US Pat. No. 4,968,451 and US Pat.
No. 11,730, US Pat. No. 4,721,580, US Pat. No. 4,702,8
No. 57, U.S. Pat. No. 4,877,896, U.S. Pat. No. 3,959,230,
U.S. Pat. No. 3,893,929, U.S. Pat. No. 4,000,093, EP Application 0219048, U.S. Pat. No. 5,415,807, U.S. Pat. No. 4,201,8
No. 24, U.S. Pat. No. 4,240,918, U.S. Pat. No. 4,525,524,
U.S. Pat. No. 4,201,824, U.S. Pat. No. 4,579,681, EP27
9,134A, EP 457,205, DE 2,335,044, U.S. Pat.
240,918, U.S. Pat. No. 4,787,989, U.S. Pat.
No. 524, U.S. Pat. No. 4,877,896, U.S. Pat. No. 4,968,451, U.S. Pat. No. 4,702,857, U.S. Pat. No. 08 / 545,351 and U.S. Pat. No. 355,938. Examples that are commercially available include SOKALA, available from BASF, Germany.
NHP-22, ZELCON5126 from DuPont and MILEASE T from ICI.

[0162] Alkoxylated polycarboxylates, such as those made from polyacrylates, are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815, p. 4 and below. These patents are incorporated herein by reference. Chemically these materials comprise polyacrylates having one ethoxy side chain for each 7-8 acrylate unit. The side chains have the formula _{- (CH 2 CH 2 O)} m (CH 2) n CH 3 ( wherein, m is 2 to 3, n is 6 to 10) are of. The side chains are esterified to the polyacrylate "backbone" to form a "comb" polymer-type structure. The molecular weight can vary, but typically is about 20
In the range of from about 00 to about 50,000. Such alkoxylated polycarboxylates can make up from about 0.05% to about 10% by weight of the compositions herein.

[0163] Another polymeric dispersant for use herein includes polyethoxylated polyamine polymers (PPP). Preferred polyethoxylated polyamines useful herein are generally polyalkyleneamines (PAA), polyalkyleneimines (PAI), preferably polyethyleneamine (PEA), polyethyleneimine (PEI). General polyalkyleneamine (PAA)
Is terebutylenepentamine. PEA is obtained by a reaction involving ammonia and ethylene dichloride, followed by fractional distillation. The general PEA obtained is
Triethylenetetramine (TETA) and tetraethylenepentamine (TEP)
A). Above pentamine, ie, hexamine, heptamine, octamine, and possibly nonamine co-productive mixtures, are unlikely to separate by distillation and may contain other materials such as cyclic amines and especially piperazine. Cyclic amines having side chains in which the nitrogen atom appears may also be present. 195 describing the preparation of PEA
Dickinson, U.S. Pat. No. 2, issued May 4, 2007
792,372.

The polyamine can be produced, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, and acetic acid. Particular methods for preparing these polyamine backbones include:
U.S. Pat. No. 2, issued December 5, 1939 to Ulrich et al.
U.S. Pat. No. 3,033,746 issued to Mayle et al., Issued May 8, 1962, et al.
U.S. Patent No. 2,208,095 to Sselmann et al., U.S. Patent No. 2,806,8 to Crowther, issued September 17, 1957.
No. 39 and Wilson, U.S. Pat. No. 2,553,696 issued May 21, 1951. All are incorporated herein by reference.

In addition, some alkoxylated (especially ethoxylated) quaternary polyamine dispersants are useful herein as dispersants. The alkoxylated quaternary polyamine dispersant that can be used in the present invention is of the following formula:

[0166]

Embedded image

In the formula, R is a linear or branched C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, [(CH ₂ CH _{2 O) q CH 2 CH 2]} - and _{-CH 2 CH (OH) CH 2} O- (CH 2 CH 2 O) q CH 2 CH (OH) CH 2) - ( where q is from about 1 to about 100 Selected). When present, each R ¹ is independently selected from C ₁ -C ₄ alkyl, C ₇ -C ₁₂ alkylaryl or A. R ¹ may not be present on some nitrogens, but at least three nitrogens must be quaternized. A has the following formula:

[0168]

Embedded image

Wherein R ³ is selected from H or C ₁ -C ₃ alkyl, n is from about 5 to about 100, and B is selected from H, C ₁ -C ₄ alkyl, acetyl or benzoyl. , M is from about 0 to about 4, and X is a water-soluble anion.

In a preferred embodiment, R is C ₄ -C ₈ alkylene and R ¹ is a C ₁ -C ₈ alkylene.
A selected from C ₂ alkyl or C ₂ -C ₃ hydroxyalkyl, wherein A is

[0171]

Embedded image

Wherein R ³ is selected from H or methyl, n is from about 10 to about 50, and m is 1.

In another preferred embodiment, R is straight or branched C ₆ , R ¹ is methyl, R ³ is H, n is from about 20 to about 50, and m is 1 It is.

The level of these dispersants used can range from about 0.1% to about 10% by weight, typically from about 0.4% to about 5% by weight. These dispersants can be synthesized according to the method set forth in U.S. Pat. No. 4,664,848 or other methods known to those skilled in the art.

Brighteners Optical brighteners, other brighteners or whitening agents known in the art, typically at levels of from about 0.01% to about 1.2% by weight of the detergent compositions herein. Can be blended into the product. Commercial optical brighteners useful in the present invention include stilbenes, pyrazolines, coumarins, carboxylic acids, methine cyanines,
Dibenzothiophene-5,5-dioxide, azoles, 5-membered heterocycles, 6-membered heterocycles, and other agents are not necessarily limited, and can be classified into subgroups including them. An example of such a brightener is John Win
M. Ley & Sons, New York (1982). Z
"The Production and Appli by Ahradnik
Cation of Fluorescent Brightening Ag
ent ".

A specific example of an optical brightener useful in the present composition is December 1, 1988
No. 4,790,856 issued to Wixon on March 3. These brighteners include Verona
The brightener PHORWHITE series from a) is mentioned. Other brighteners disclosed in this document include Ciba-Geigy (Ciba-Ge
igno) available from Tinopal UNPA, Tinopal CBS,
Tinopal 5BN: Artic White CC and Artic W
white CWD, 2- (4-styryl-phenyl) -2H-naphtho [1,2-d] triazole, 4,4′-bis- (1,2,3-triazol-2-yl) -stilbene, 4, 4'-bis (styryl) bisphenyl and aminocoumarin. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenyl-pyrazoline, 2,5-bis (Benzoxazol-2-yl) thiophene, 2-styryl-naphtho [1,2-d] oxazole and 2- (
Stilben-4-yl) -2H-naphtho [1,2-d] triazole. See also U.S. Pat. No. 3,646,015 to Hamilton, issued Feb. 29, 1972.

Chelating Agents The detergent compositions herein may optionally also contain one or more iron and / or manganese chelating agents. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof, all of which are defined hereinafter. While not intending to be bound by theory, it is believed that the benefits of these materials are due in part to the remarkable ability to remove iron and manganese ions from the cleaning solution by the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraamine hexaacetate, Diethylene triamine pentaacetate, and their ethanol diglycine,
Alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in the detergent composition, and ethylenediaminetetrakis (DEQUEST) Methylene phosphonate). Those aminophosphonates which do not contain alkyl or alkenyl groups having more than about 6 carbon atoms are preferred.

[0180] Polyfunctionally substituted aromatic chelators are also useful in the compositions herein.
U.S. Pat. No. 3,8, issued May 21, 1974 to Conner et al.
See 12,044. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelators for use herein are ethylenediamine disuccinates ("EDDS"), particularly US Pat. No. 4 to Hartman et al., Issued Nov. 3, 1987. , 704, 233 [S, S] isomer.

The compositions herein can also contain water-soluble methylglycine diacetate (MGDA) salt (or acid form) as a chelating agent or co-builder. Similarly, so-called "weak" builders, such as citrate, can also be used as chelating agents.

When utilizing these chelating agents, they generally comprise from about 0.1% to about 15% of the detergent compositions herein. More preferably,
If a chelating agent is utilized, the chelating agent will comprise from about 0.1% to about 3.0% by weight of such compositions.

Composition pH The dishwashing compositions of the present invention, when used, ie, when used in diluted and soiled dishes, are exposed to the acid stress caused by food soil. If a composition with a pH greater than 7 is more effective, it is preferably in the composition and a dilute solution,
That is, it should contain a buffer capable of providing a generally more alkaline pH in an aqueous solution of about 0.1% to 0.4% by weight of the composition. The pKa value of this buffer should be about 0.5-1.0 pH units below the required pH of the composition (as determined above). Preferably, the pKa of the buffer is from about 7 to about 1
Should be 0. Under these conditions, the buffer most effectively controls pH while using its minimum amount.

The buffer can itself be an active detergent, or the buffer can be
It can be a low molecular weight organic or inorganic material used in this composition only to maintain an alkaline pH. Preferred buffers for the compositions of the present invention are nitrogen-containing materials. Some examples are amino acids such as lysine or lower alcohol amines such as mono-, di- and tri-ethanolamine. Other preferred nitrogen-containing buffering agents are tri (hydroxymethyl) aminomethane _{(HOCH 2) 3 CNH 3 (} TRIS), 2- amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl - Propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,
3-diamino-propanol, N.P. N'-tetra-methyl-1,3-diamino-
2-propanol, N, N-bis (2-hydroxyethyl) glycine (bicine)
And N-tris (hydroxymethyl) methylglycine (tricine). Any mixtures of the above are acceptable. Useful inorganic buffers / alkali sources include:
Alkali metal carbonates and phosphates, such as sodium carbonate, sodium phosphate. For other buffers, see McCutcheon's
s EMULSIFIERS AND DETERGENTS, North A
American Edition, 1997, McCutcheon Div
issue, MC Publishing Company Kirk and W
See O 95/07971. Both are incorporated herein by reference.

When a buffer is used, it is present in the compositions of the invention herein at a level of about 0.1% to 15%, preferably about 1% to about 10%, by weight of the composition. I do.

Other Ingredients Detergent compositions, including other active ingredients, carriers, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for rod compositions, etc. Various other ingredients useful therein can be included in the compositions herein. If severe foaming is required, a foam boosters such as C ₁₀ -C ₁₆ alkanolamides typically be incorporated into the composition at a level of from 1% to 10%. C ₁₀ -C ₁₄ monoethanol amine and diethanolamine are intended to illustrate typical class of such suds boosters. It is also advantageous to use such foam enhancers in combination with high foam co-surfactants such as amine oxides, betaines and sultaines.

[0188] Antioxidants can optionally be added to the detergent compositions of the present invention. They are found in detergent compositions such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamates, ascorbates, thiosulfates, monoethanolamine (MEA), diethanolamine, triethanolamine, and the like. It can be any conventional antioxidant used. When present, the antioxidant is preferably present in the composition at about 0.001% to about 5% by weight.

[0189] The various detergent components used in the present compositions are optionally further stabilized by absorbing the components onto a porous hydrophobic support and then coating the support with a hydrophobic coating. It is possible. Preferably, the detergent components are mixed with the surfactant before being absorbed on the porous support. In use, the detergent component is released from the support into the aqueous cleaning liquid as it performs its intended detergent function.

The technology will be described in more detail. Porous hydrophobic silica (trade name: SIPERNA)
T D10, Degussa (DeGussa)) is mixed with proteolytic enzymes containing 3% -5% of C _{13 to 15} ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme / detergent solution is 2.5 times the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities ranging from 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or added separately to the final detergent matrix.
By this, the enzyme, bleach, bleach activator, bleach catalyst, photoactivator,
Ingredients such as dyes, fluorescers, fabric conditioners, and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.

[0191] Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohol is
Preferred for solubilizing surfactants, polyols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol) can also be used. The composition may contain from 5% to 90%, typically 10% to 50% of such carriers.

An example of a procedure for producing the granules of the detergent composition herein is as follows. Via a crutcher, add linear alkylbenzene sulfonic acid, sodium tripolyphosphate, sodium silicate, sodium sulfate, fragrance, diamine and water, heat and mix. The obtained slurry is spray-dried into granules.

An example of a procedure for producing a liquid detergent composition herein is as follows. Free water, is then added dissolved in citrate and MgCl _2. Amine oxide, betaine, ethanol, hydrotrope and nonionic surfactant are added to this solution. If free water is not available, the addition of MgCl ₂ and citrate to the above mixture and stirred until then dissolve. At this point, the maleic acid is added, followed by the diamine. AExS is added last. For formulations without Mg ⁺⁺ , the procedure is the same.

Non- Aqueous Liquid Detergent A product of a liquid detergent composition comprising a non-aqueous carrier medium is disclosed in US Pat.
No. 570, No. 4,767,558, No. 4,772,413, No. 4,889,
No. 652, No. 4,892,673, GB-A-2,158,838, GB-A
-2,195,125; GB-A-2,195,649; U.S. Pat.
No. 462, U.S. Pat. No. 5,266,233, EP-A-225,654 (1).
June 16, 987), EP-A-510,762 (October 28, 1992)
, EP-A-540,089 (May 5, 1993), EP-A-540,09.
0 (May 5, 1993), U.S. Patent No. 4,615,820, EP-A-56.
5,017 (October 13, 1993), EP-A-030,096 (1981)
(June 10, 2010). These patents are incorporated herein by reference. Such compositions can contain various particulate cleaning ingredients (eg, bleaches as disclosed above) stably suspended therein. Accordingly, such non-aqueous compositions comprise a "liquid phase" and optionally, but preferably, a "solid phase", all of which are described in further detail hereinbelow and in the references cited. Have been.

The compositions of the present invention can be used to form aqueous washing solutions for hand dishes. Generally, an effective amount of such a composition is added to water to form such an aqueous cleaning or dipping solution. The aqueous solution thus formed is then brought into contact with dishes, dishes and utensils.

An effective amount of a detergent composition herein that is added to water to form an aqueous cleaning solution comprises an amount sufficient to form about 500-20,000 ppm of the composition in an aqueous solution. It is possible to be More preferably, about 800 to 5,000.
0 ppm of the composition herein is formed in an aqueous cleaning solution.

The present invention also relates to a means for preventing the re-adhesion of grease, grease and dirt, especially grease, from dishes for hand washing onto dishes. The method comprises contacting an aqueous solution of the composition of the present invention with soiled dishes and washing the dishes with the aqueous solution.

An effective amount of a detergent composition herein added to water to form an aqueous cleaning solution according to the method of the present invention is used to form about 500-20,000 ppm of the composition in an aqueous solution. Comprising a sufficient amount. More preferably, about 800 to 2.5.
00 ppm of the composition herein is formed in an aqueous cleaning solution.

The liquid detergent compositions of the present invention are effective to prevent the re-adhesion of grease from the cleaning solution onto dishes during cleaning. One measure of the effectiveness of the composition of the present invention involves a reattachment test. The following tests and other tests of similar content are used to assess the suitability of the formulations described herein.

An aqueous solution (water = 7 grains) comprising about 500 to about 20,000 ppm of the liquid detergent composition according to the invention is filled into a 2 liter graduated cylinder made of polyethylene up to the 1 liter scale. Then, the synthetic oil stain is added to the measuring cylinder and the solution is stirred. After a period of time, the solution is gently poured out of the graduated cylinder and the inner wall of the graduated cylinder is rinsed with a suitable solvent or mixture of solvents to collect any redeposited grease. The weight of greasy soil remaining in the solution is determined by removing the solvent and subtracting the amount of soil recovered from the amount of initial soil added to the aqueous solution.

Other re-adhesion tests include immersing tableware, flatware, etc., and collecting any re-adhered soil.

The tests described above can be further modified to determine increased amounts of foam volume and foam duration. The solution is first agitated, and between each subsequent soil addition, the solution is bubbled in a single dose of oily soil with agitation. Foam volume can be easily determined by using the empty volume of a 2 liter graduated cylinder as a guide.

The following are non-limiting examples of liquid detergent compositions comprising a polymeric foam enhancer according to the present invention.

[0204]

[Table 1]

1: E ₉ ethoxylated alcohol as sold by Shell Oil Co. 2: 1,3-diaminopentane sold as Dytek EP 3: Lys, Ala, Glu, Tyr (5 : 6: 2: 1), about 52
Polypeptide having a molecular weight of 2,000 daltons 4: including fragrances, dyes, ethanol and the like.

[0206]

[Table 2]

1: E as sold by Shell Oil Co.₉Ethoxylated alcohol 2: 1,3-bis (methylamino) cyclohexane 3: diethylenetriaminopentaacetate 4: Suitable protease enzymes include Savinase , Maxatase , M
axacal , Maxapem15 , Subtilisin BPN and BPN ', P
rotateB, ProteaseA, ProteaseD, Primase  , Durazym , Opticlean , Optimase And Alca
case Is mentioned. 5: Suitable amylase enzymes include Termamyl , Fungamyl , Du
ramyl , BAN , And Novo Nordisk
WO95 / 26397 and PCT / DK / 96/0005
Amylase described in No. 6 above. 6: Suitable hydrotropes include toluenesulfonic acid, naphthalenesulfonic acid,
Cumenesulfonic acid, sodium salt, potassium salt of xylenesulfonic acid, ammonia
Or a water-soluble substituted ammonium salt. 7: Lys, Ala, Glu, Tyr (5: 6: 2: 1), about 52
Polypeptide having a molecular weight of 2,000 daltons 8: including fragrances, dyes, ethanol and the like.

[0208]

[Table 3]

1: E ₉ ethoxylated alcohol as sold by Shell Oil Co. 2: 1,3-bis (methylamino) cyclohexane 3: Lys, Ala, Glu, Tyr (5: 6: 2: 1), about 52
Polypeptide having a molecular weight of 2,000 daltons 4: including fragrances, dyes, ethanol and the like.

[0210]

[Table 4]

1: E as sold by Shell Oil Co.₉Ethoxylated alcohol 2: 1,3-diaminopentane sold as Dytek EP 3: Suitable protease enzymes include Savinase , Maxatase , M
axacal , Maxapem15 , Subtilisin BPN and BPN ', P
rotateB, ProteaseA, ProteaseD, Primase  , Durazym , Opticlean , Optimase And Alca
case Is mentioned. 4: Suitable amylase enzymes include Termamyl , Fungamyl , Du
ramyl , BAN , And Novo Nordisk
WO95 / 26397 and PCT / DK / 96/0005
Amylase described in No. 6 above. 5: Suitable lipase enzymes include Amino-P, M1 Lipase , Lipo max , Lipolase No. 08 / 341,826.
Examples include D96L, a lipolytic enzyme variant of natural lipase derived from humicola lanuginosa, and humicola lanuginosa sp. DSM4106. 6: diethylenetriamine pentaacetate 7: lysozyme 8: including fragrance, dye, ethanol and the like.

[0212]

[Table 5]

1: E as sold by Shell Oil Co.₉Ethoxylated alcohol 2: 1,3-bis (methylamino) cyclohexane 3: Suitable protease enzymes include Savinase , Maxatase , M
axacal , Maxapem15 , Subtilisin BPN and BPN ', P
rotateB, ProteaseA, ProteaseD, Primase  , Durazym , Opticlean , Optimase And Alca
case Is mentioned. 4: Suitable amylase enzymes include Termamyl , Fungamyl , Du
ramyl , BAN , And Novo Nordisk
WO95 / 26397 and PCT / DK / 96/0005
Amylase described in No. 6 above. 5: Suitable lipase enzymes include Amino-P, M1 Lipase , Lipo max , Lipolase No. 08 / 341,826.
Examples include D96L, a lipolytic enzyme variant of natural lipase derived from humicola lanuginosa, and humicola lanuginosa sp. DSM4106. 6: diethylenetriamine pentaacetate 7: comprising Lys, Ala, Glu, Tyr (5: 6: 2: 1), about 52
Polypeptide having a molecular weight of 2,000 daltons 8: including fragrances, dyes, ethanol and the like.

[0214]

[Table 6]

1: E ₉ ethoxylated alcohol as sold by Shell Oil Co. 2: Lys, Ala, Glu, Tyr (5: 6: 2: 1), comprising about 52
Polypeptide having a molecular weight of 2,000 daltons 3: including fragrances, dyes, ethanol and the like.

──────────────────────────────────────────────────の Continuation of the front page (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Shafer, Michael Gail Alexandria, South, Kramer, Drive 6032, Kentucky, USA F term (reference) 4H003 AB27 AB31 AC05 AC08 AC15 AD04 BA12 DA17 EA19 EB04 EB08 EB13 EB38 EC01 EC02 EC03 ED02 FA17 FA28

Claims (10)

[Claims] 1. An effective amount of a proteinaceous foam stabilizer having an isoelectric point of 9 to 11.5, provided that a 10% aqueous solution of the detergent composition has a pH of 7 to 12; A detergent composition suitable for hand dish washing comprising an amount of a washing surfactant and (c) a carrier as a balance and other auxiliary ingredients. 2. The composition according to claim 1, comprising 0.5% to 5% by weight of said proteinaceous foam stabilizer. 3. The composition according to claim 1, wherein the proteinaceous foam stabilizer is a peptide comprising 10% to 40% of one or more amino acids protonated at a pH of less than 11. . 4. The composition according to claim 1, wherein the proteinaceous foam stabilizer comprises at least 10% by weight of one or more amino acids. 5. The method of claim 1, wherein the proteinaceous foam stabilizer comprises at least 10% by weight of one or more amino acids protonated at a pH of less than 11. Composition. 6. The method according to claim 1, further comprising 0.25% to 15% of a diamine having the following formula, provided that the diamine has a pKa of at least 8. A composition as described. Embedded image (Wherein, each R is independently hydrogen, C ₁ -C ₄ straight or branched alkyl, wherein _{^{- (R 2 O) y R}} 3 - ( where R ² is, C ₂ -C ₄ linear or branched Alkyleneoxy and mixtures thereof; R ³ is selected from the group consisting of alkyleneoxy having hydrogen, C ₁ -C ₄ alkyl and mixtures thereof, and y is 1-10); Is
i) C ₃ ~C ₁₀ linear alkylene, C ₃ -C ₁₀ branched alkylene, C ₃ -C ₁₀ cyclic Al Killen, C ₃ -C ₁₀ branched cyclic alkylene, wherein _{^{- (R 2 O) y R}} 2 - Alkyleneoxyalkylene having (where R ² and y are the same as defined above), ii) C ₃ -C ₁₀ straight chain, C ₃ -C ₁₀ branched straight chain, C ₃ -C _{10 10} cyclic, a C ₃ -C ₁₀ units selected from mixed Gomoto branch cyclic alkylene, C ₆ -C ₁₀ arylene, and iii) and (i) (ii), from 8 to said diamine A unit comprising one or more electron donating or electron withdrawing moieties that impart a high pKa) 7. The method of claim 1, further comprising an enzyme selected from the group consisting of a protease, an amylase, a lipase, a cellulase, and a mixture thereof.
A composition according to any one of the preceding claims. 8. A proteinaceous foam stabilizer having an isoelectric point of 9.5 to 11.5 and a molecular weight of at least 1500 daltons and comprising at least 10% by weight of amino acid residues. 9. A composition comprising at least 10% by weight of a unit having the formula:
A compound according to claim 8. Embedded image Wherein R and R ¹ are each independently hydrogen, a moiety having a positive or negative charge at a pH of 9.5 to 11.5, and x and y are each independently 0 or 1. 10. A compound according to claim 8 or 9 comprising more than 95% by weight of amino acids.