JP2002535443A - Dishwashing composition comprising an alkylbenzene sulfonate surfactant - Google Patents

Abstract

(57) Summary i) from about 0.01% to about 99.99% by weight of the composition is a surfactant mixture, wherein the surfactant mixture is of the formula (a) wherein L is M is a cation or a mixture of cations, q is its valency, and a and b are that the surfactant mixture is an acyclic aliphatic hydrocarbyl of 6 to 18 carbon atoms in total. is a number which is chosen to be neutral; R 'is selected from H and C ₁ -C ₃ alkyl; R''is selected from H and C ₁ -C ₃ alkyl; R''' is is selected from H and C ₁ -C ₃ alkyl; R 'and R''are all non-terminal binds to L, at least one of R' and R '' is an C ₁ -C ₃ alkyl; a Is an aryl] alkyl aryl sulfonate surfactant comprising at least two isomers of The alkylsulfonate surfactant system comprises two or more isomers with respect to the R ', R ", and A-L attachment positions, and comprises at least 60% of the alkylsulfonate surfactant system. In the arylsulfonate surfactant system, A is attached to L at one of the two terminal carbon atoms at a position selected from the α-position and the β-position; Having. That is, when the quaternary carbon atoms are present, the alkylaryl sulfonate surfactant system has a weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in L of at least 10: 1, and Ii) 0.0001% to 99.99% by weight of the composition is a conventional hand-washing dishwashing aid; and iii) 0% by weight of the composition as measured by a hardness resistance test. A dishwashing composition for hand washing, comprising from 0.01% to 7% by weight of divalent ions selected from the group consisting of magnesium, calcium, and mixtures thereof. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to hand dishwashing compositions comprising a specific type of alkylaryl sulfonate surfactant. More specifically, these alkylaryl sulfonates are highly branched, non-biodegradable or still commercially available in certain countries.
Unlike any of the "hard type" alkylbenzene sulfonates, it has a different chemical composition than the so-called linear alkylbenzene sulfonates, which are substituted at most positions, including the recently introduced "high 2-phenyl" type.

BACKGROUND Typical commercial hand dishwashing cleaning composition of the invention is a divalent ion to ensure proper oil removal in soft water (Mg, Ca) is incorporated. However, due to the presence of divalent ions in formulations containing anionic, non-ionic, or additional surfactants (eg, amine oxides, alkyl ethoxylates, LAS, alkanoyl glucose amides, alkyl betaines), The mixing speed of water with water is slowed (so that it does not foam quickly), rinsing is poor and stability at low temperatures is low. In addition, Ca and Mg precipitate as the pH increases, so Ca / M
The preparation of stable dishwashing detergents containing g is very difficult. Therefore, it is stable in hard water and at low temperatures, typically at pH 9 or below (unstable with conventional Ca / Mg systems, which does not provide grease removal and strong food cleanability), There is also a need for detergent compositions suitable for hand dishwashing, which can provide grease removal and strong food cleaning.

BACKGROUND ART US Pat. Nos. 5,026,933, 4,990,718, and 4,30.
No. 1,316, No. 4,301,317, No. 4,855,527, No. 4
No. 4,870,038, No. 2,477,382, European Patent No. 466,558 (Jan. 15, 1992), No. 469,940 (Feb. 5, 1992), French Patent No. 2 No., 697,246 (April 29, 1994), SU 793,
No. 972 (January 7, 1981); U.S. Pat. Nos. 2,564,072;
196,174, 3,238,249, 3,355,484, 3,442,964, 3,492,364, 4,959,491, WO 88/07030 (September 25, 1990); U.S. Pat.
No. 256, No. 5,196,624, No. 5,196,625, European Patent No. 364,012B (February 15, 1990), U.S. Pat. No. 3,312,74.
No. 5, No. 3,341,614, No. 3,442,965, No. 3,674
No. 885, No. 4,447,664, No. 4,533,651, No. 4,
Nos. 587,374, 4,996,386, 5,210,060, 5,510,306, WO 95/17961 (July 6, 1995), W
O 95/18084, U.S. Patent Nos. 5,510,306 and 5,087,7.
No. 88, No. 4,310,316, No. 4,301,317, No. 4,85
No. 5,527, No. 4,870,038, No. 5,026,933, No. 5
No. 4,625,105 and No. 4,973,788. The preparation of alkylbenzene sulfonate surfactants has recently been reviewed. "Science of Surfactants" series, Marcel Dekker, New York, 1996, 5th
See Volume 6, in particular, Chapter 2, titled "Alkylaryl Sulfonates: History, Production, Analysis, and Environmental Properties," 39-108 (including references in 297). References herein are incorporated by reference in their entirety.

SUMMARY OF THE INVENTION The present invention has a number of advantages over one or more of the above aspects, including excellent solubility in cold water (eg, washing with cold water), excellent hard water Including, but not limited to, resistance and excellent cleaning power. Further, it is expected that the present invention will have improved removal of lipid or grease stains. According to the present invention, substantially anticipated improvements that facilitate the manufacture of relatively high 2-phenylsulfonate compositions, including ease of manufacture and quality of the resulting formulation, and an attractive economy Including the benefits).

[0005] The present invention is based on an unexpected finding that is intermediate between an old, highly branched, less biodegradable alkylbenzene sulfonate and some new linear alkylbenzene sulfonates. It performs much better than the latter and is more biodegradable than the former.

[0006] New alkylbenzene sulfonates are readily available by some of the hundreds of known methods for preparing alkylbenzene sulfonates. For example, with the use of certain dealuminated mordenites, conventional manufacturing methods can be used.

[0007] According to a first aspect of the present invention, there is provided a novel hand-washing dishwashing composition. The new hand-washing dishwashing composition contains: i) from about 0.01% to about 99.99% by weight of the composition is a surfactant mixture, wherein the surfactant mixture has the formula:

[0008]

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Wherein L is an acyclic aliphatic hydrocarbyl of a total of 6 to 18 carbon atoms; M is a cation or a mixture of cations, q is its valency; b is a number selected such that the surfactant mixture is electrically neutral;
R 'is selected from H and C ₁ -C ₃ alkyl; R''is selected from H and C ₁ -C ₃ alkyl; R''' is selected from H and C ₁ -C ₃ alkyl; R ' And R ″ are both non-terminally linked to L;
At least one of R ′ and R ″ is C ₁ -C ₃ alkyl; and A is aryl.] Wherein the alkyl aryl sulfonate surfactant system comprises at least two isomers of the alkyl aryl sulfonate surfactant. The alkylaryl sulfonate surfactant system comprises R ′, R ″, and A
-Containing two or more isomers with respect to the attachment position of -L; in at least about 60% of the above alkylaryl sulfonate surfactant systems, A is located at any of the two terminal carbon atoms from the alpha and beta positions. And the alkylarylsulfonate surfactant system further comprises, if a quaternary carbon atom is present, the alkylarylsulfonate surfactant system comprising: Weight ratio of quaternary carbon atoms to quaternary carbon atoms is at least 1
0: 1 and a loss of no more than 40% by weight as measured by a Hardness Tolerance Test; ii) about 0.0001% by weight of the composition % To about 99.99% by weight is a conventional hand dishwashing aid; iii) about 0.01% to about 7% by weight of the composition is selected from the group consisting of magnesium, calcium, and mixtures thereof. Divalent ion.

According to a second aspect of the present invention, a novel dishwashing composition for hand washing is provided. The new hand-washing dishwashing composition contains: i) from about 0.01% to about 99.99% by weight of the composition is a surfactant mixture, wherein the surfactant mixture has the formula:

[0011]

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Wherein M is a cation, q is the valency of the cation; a and b are numbers selected such that the mixture is electrically neutral; A is aryl R ′ ″ is selected from hydrogen and C ₁ -C ₃ alkyl; R ′ is hydrogen and C ₁
It is selected from -C ₃ alkyl; R '' is selected from hydrogen and C ₁ -C ₃ alkyl; R '''' is selected from hydrogen and C ₁ -C ₄ alkyl; v is an integer of 0 Is; x is an integer from 0 to 10; y is an integer from 0 to 10]. Wherein the total number of carbon atoms attached to A is less than about 20; wherein the alkylaryl sulfonate surfactant system comprises R ′ ″ which is part of the above formula. '-C (-) H (CH _{2
) V C (-) H (} CH 2) x C (-) to _{H (CH 2) y -CH 3} , R ', R'', and two with respect to the bonding position of A or more isomers At least one of R ′ and R ″ is C ₁ -C ₃ alkyl; when R ″ ″ is C ₁ , v
+ X + y is at least 1 and when R ″ ″ is H, v + x + y
Is at least 2; in at least about 60% of the alkylaryl sulfonate surfactant systems, A is part of the above formula, R ″ ″ — C (−)
_{H (CH 2) v C (} -) H (CH 2) x C (-) to _{H (CH 2) y -CH 3} , are selected from the position and β-position α to either of the two terminal carbon atoms In addition, the alkylaryl sulfonate-based surfactant, when a quaternary carbon atom is present, wherein the alkylaryl sulfonate-based surfactant is R ″ ″ that is part of the above formula _{-C (-) H (CH 2} ) v C (-) H (
_{CH 2) x C (-)} H (CH 2) weight ratio of the non-quaternary carbon atom and the quaternary carbon atom in the _y -CH ₃ of at least 10: 1, and by a hardness tolerance test Ii) from about 0.0001% to about 99.99% by weight of the composition is a conventional hand dishwashing aid with a measured loss of less than or equal to 40% by weight; Iii) from about 0.01% to about 7% by weight of the composition of magnesium, calcium,
And a divalent ion selected from the group consisting of:

According to a third aspect of the present invention, there is provided a novel hand-washing dishwashing composition. The new hand-washing dishwashing composition contains: i) about 0.01% to about 99.99% by weight of the composition is a surfactant mixture, the surfactant mixture comprising: a) about 0.01% to about 99% by weight of the surfactant mixture. .99% by weight is

[0014]

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Wherein L is an acyclic aliphatic hydrocarbyl of a total of 6 to 18 carbon atoms; M is a cation or a mixture of cations; q is its valency; Is a number selected such that the surfactant mixture is electrically neutral; R
'Is selected from H and C ₁ -C ₃ alkyl; R''is selected from H and C ₁ -C ₃ alkyl; R''' is selected from H and C ₁ -C ₃ alkyl; R 'and R ″ is non-terminally linked to L, and at least one of R ′ and R ′
'' Is C ₁ -C ₃ alkyl; A is aryl] wherein the alkyl aryl sulfonate surfactant comprises at least two isomers of the alkyl aryl sulfonate surfactant; The system comprises R ′, R ″, and A
-Containing two or more isomers with respect to the attachment position of -L; in at least about 60% of the above alkylaryl sulfonate surfactant systems, A is located at any of the two terminal carbon atoms from the alpha and beta positions. And wherein the alkylaryl sulfonate surfactant system further comprises, if a quaternary carbon atom is present, the alkylaryl sulfonate surfactant system comprises a non-quaternary The weight ratio of carbon atoms to quaternary carbon atoms is at least 1
0: 1 and a loss of less than or equal to 40% by weight as measured by a hardness resistance test; and b) from about 0.01% to about 0.01% by weight of the surfactant mixture. 99.99% by weight is at least one isomer of the linear analog of the alkylaryl sulfonate surfactant (a); ii) from about 0.0001% to about 99.99% by weight of the composition is conventional. And iii) from about 0.01% to about 7% by weight of the composition is a divalent ion selected from the group consisting of magnesium, calcium, and mixtures thereof.

According to a fourth aspect of the present invention, there is provided a novel dishwashing composition for hand washing. The new hand-washing dishwashing composition contains: i) about 0.01% to about 9.99% by weight of the composition is a surfactant mixture, the surfactant mixture comprising: a) about 0.01% to about 99% by weight of the surfactant mixture. .99% by weight is

[0017]

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Wherein M is a cation, q is the valency of the cation, and a and b are numbers selected so that the mixture is electrically neutral; A is aryl Is;
R ′ ″ is selected from H and C ₁ -C ₃ alkyl; R ′ is selected from hydrogen and C ₁ -C ₃ alkyl; R ″ is selected from hydrogen and C ₁ -C ₃ alkyl;
'' Is selected from hydrogen and C ₁ -C ₄ alkyl; v is an integer from 0 to 10; x is an integer from 0 to 10; y is an integer from 0 to 10] An alkylarylsulfonate surfactant system comprising at least two isomers calculated excluding the ortho, meta, para and stereoisomers of the sulfonate surfactant; the total number of carbon atoms attached to A is about 20 in there below; it said alkylarylsulfonate surfactant system, is a part of the formula R '''' - C ( -) H (CH 2
_{) V C (-) H (} CH 2) x C (-) H (CH 2) R to _{y -CH 3 ', R''} , and two or more isomers with respect to the bonding position of A and Including; R 'and R
'' Is at least one C ₁ -C ₃ alkyl, and when R ″ ″ is C ₁ , v
The sum of + x + y is at least 1; if R ″ ″ is H, then v + x + y
Is at least 2; in at least 60% of the alkylaryl sulfonate surfactant systems, A is part of the above formula and R ″ ″ — C (−) H
(CH ₂ ) _v C (−) H (CH ₂ ) _x C (−) H (CH ₂ ) _y —CH ₃ at one of its two terminal carbon atoms selected from α-position and β-position Further, the alkylarylsulfonate system may further comprise, if a quaternary carbon atom is present, the alkylarylsulfonate surfactant system may comprise R ″ ″-C (− _{) H (CH 2) v C} (-) H (
_{CH 2) x C (-)} H (CH 2) weight ratio of the non-quaternary carbon atom and the quaternary carbon atom in the _y -CH ₃ of at least 10: 1, and by a hardness tolerance test Has at least one of the following properties: a loss of less than or equal to 40% by weight; b) from about 0.01% to about 99.99% by weight of the surfactant mixture of the alkylaryl sulfonate surfactant. At least one isomer of the linear analog of (a); ii) from about 0.0001% to about 99.99% by weight of the composition is a conventional hand dishwashing aid; and iii) the composition. About 0.01% to about 7% by weight of the product is a divalent ion selected from the group consisting of magnesium, calcium, and mixtures thereof.

In all four of these aspects of the invention, the surfactant system comprises at least two, preferably four, more preferably at least eight, more preferably twelve, even more preferably at least sixteen, Most preferably, it comprises 20 isomers and / or homologs of the alkylarylsulfonate surfactant of formula (I). “Isomers” described herein in detail below include, among others, R ′ to L moieties.
And / or compounds having different bonding positions of the R ″ group. “Homologs” vary according to the number of carbon atoms included in the sum of L, R ′, and R ″.

The hand dishwashing composition preferably comprises at least about 0.1%, more preferably at least 0.5%, even more preferably at least 1% by weight of the above composition of a surfactant mixture. . The cleaning composition also preferably comprises no more than about 80%, more preferably no more than 60%, even more preferably 4% by weight of the composition.
Contains 0% by weight or less of the surfactant mixture.

Accordingly, an aspect of the present invention is to provide a novel cleaning composition. These and other aspects, features, and advantages will be apparent from the following detailed description, and from the claims.

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

[0023] DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel hand dishwashing cleaning composition. The surfactant system has the following formula

[0024]

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Wherein M is a cation or a mixture of cations comprising at least two alkylaryl sulfonate surfactants. Preferably, M is an alkali metal,
It is an alkaline earth metal, ammonium, substituted ammonium, or a mixture thereof, and more preferably, sodium, potassium, magnesium, calcium, or a mixture thereof. The valence q of the cation is preferably 1 or 2. The number of a and b is chosen such that the composition is electrically neutral, preferably a and b are 1 or 2, and 1 respectively.

A is selected from aryl. Preferably, Ar is benzene, toluene, xylene, naphthalene, and mixtures thereof, more preferably Ar is benzene or toluene, most preferably benzene.

R ′ is selected from H and C ₁ -C ₃ alkyl. Preferably R 'is, H, and C ₁ -C ₂ alkyl, more preferably R' is methyl or ethyl, most preferably R 'is methyl. R ″ is selected from H and C ₁ -C ₃ alkyl. Preferably R ″ is H or C ₁ -C ₂ alkyl, more preferably R ′ is H
Or methyl. R ′ ″ is selected from H or C ₁ -C ₃ alkyl.
Preferably R ′ ″ is H and C ₁ -C ₂ alkyl, more preferably R ′ ″ is H
Or methyl, most preferably R ′ ″ is H. R ′ and R ″ are both
Non-terminally bound to L. That is, R ′ and R ″ are groups that do not combine throughout the length of L, but rather are branched from L. Also, at least one of R ′ and R ″ is C ₁ -C ₃ alkyl. This limits L to be a hydrocarbyl molecule having at least one alkyl branch.

L is an acyclic aliphatic hydrocarbyl of a total of 6 to 18, preferably 9 to 14 (when only one methyl is branched) carbon atoms. Preferred L is
The following formula (II)

[0029]

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Wherein R ′, R ″, R ′ ″, A, M, q, a and b are defined above, including R ″ ″ , R ″, R ″ ″-C (−) H (CH ₂ ) _v C (−) H (CH ₂ ) _× C (−) H (C
H ₂₎ is a _y -CH _3. R ″ ″ is selected from H and C ₁ -C ₄ alkyl. Preferably, R ″ ″ is hydrogen and C ₁ -C ₃ , more preferably R ′
“″ Is hydrogen and C ₁ -C ₂ , most preferably R ″ ″ is methyl or ethyl. The number of subunits v, x, and y of the methylene group is each independently an integer from 0 to 10 when the total number of carbon atoms bonded to A is less than about 20. This number includes R ′, R ″, R ′ ″, and R ″ ″. Furthermore, R '
If '''is C ₁ then the sum of v + x + y is at least 1 and R''''is H
Where the sum of v + x + y is at least 2. Part R ''''-C (-
_{) H (CH 2) v C} (-) H (CH 2) x C (-) in the portion of the _{H (CH 2) y -CH 3} , 3 one C (-) is, A, R ', and R''Indicates three carbon atoms attached to the above moiety.

The alkylaryl sulfonate surfactant system comprises R ′, R ″, and AL
Contains two or more isomers for the binding site of At least 60%
, Preferably about 80%, more preferably 100% of the surfactant composition,
A binds to L at a position selected from the α and β positions of any of the two terminal carbon atoms of L. The terms “α-position and β-position” are each 1 remote from the terminal carbon atom.
Means the first and second carbon atoms. To better illustrate this, the structure below shows two possible α-positions and two
Two possible β positions are shown.

[0032]

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Further, in a first aspect of the present invention, the alkylaryl sulfonate surfactant system comprises a non-quaternary carbon atom and a quaternary carbon atom in L, if a quaternary carbon atom is present. Is at least about 10: 1. Preferably, the weight ratio of non-quaternary to quaternary carbon atoms in L is at least about 20: 1, most preferably about 100: 1.

Further, as described below, the loss is less than 40% by weight, preferably less than 20% by weight, more preferably less than 10% by weight as tested by a hardness test.

In another aspect of the present invention, a second embodiment of the surfactant mixture comprises a surfactant system comprising at least one isomer of a linear analog of the above alkylaryl sulfonate surfactant. it can. A linear analog is an alkylaryl sulfonate surfactant having the following formula:

[0036]

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Wherein A, R ′ ″, M, q, a and b are defined above, and Q is
Linear hydrocarbyl containing 20 carbon atoms]. Preferably, the total carbon number in Q is equal to the total carbon number of R ', L and R "of the surfactant of formula (I) above.

In a second aspect of the present invention, the surfactant mixture has the formula:

[0039]

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Wherein A, R ′, R ″, R ′ ″, R ″ ″, M, q, a, b, v, x,
And y are as defined above], wherein the alkylaryl sulfonate surfactant comprises at least two isomers calculated excluding the ortho, meta, para, and stereoisomers. .

The alkylarylsulfonate surfactant system comprises an L moiety, R ″ ″ ″-C
(-) H (CH_Two)_vC (-) H (CH_Two)_xC (-) H (CH_Two)_y-CH_ThreeR to
, R '', and two or more isomers with respect to the point of attachment of A.
No. At least about 60%, preferably about 80%, more preferably about 100%
In the surfactant composition, A is R '' "-C (-) H (CH_Two)_vC (-) H (C
H_Two)_xC (-) H (CH_Two)_y-CH_ThreeThe α-position to any of the two terminal carbon atoms of
And L-position R '' ''-C (-) H (CH _Two )_vC (-) H (CH_Two)_xC (-) H (CH_Two)_y-CH_ThreeTo join.

Further, in the first embodiment of the present invention, when a quaternary carbon atom is present,
The alkylarylsulfonate surfactant system comprises an L moiety, R ""-C (
_{-) H (CH 2) v} C (-) H (CH 2) x C (-) H (CH 2) weight ratio of the non-quaternary carbon atom and the quaternary carbon atom in the _y -CH ₃ is It is at least about 10: 1. Preferably, L moiety R '''' - C ( -) H (CH 2) v C (-) H (CH 2) x C (-
) H (CH _{2) y} weight ratio of the non-quaternary carbon atom and the quaternary carbon atom in the -CH ₃ of at least about 20: 1, and most preferably 100: 1.

Furthermore, the loss is 40% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less as measured by a hardness resistance test.

In another aspect of the present invention, a second embodiment of the surfactant mixture can include a surfactant system that includes at least one isomer of a linear analog of an alkylaryl sulfonate surfactant. . A linear analog is an alkylaryl sulfonate surfactant having the following formula:

[0045]

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[Wherein R ″ ″ is n-alkyl, A, R ′ ″, R ″ ″, M
, Q, a, and b are defined above]. In other words, R ′ and R ″ are both hydrogen. This linear analog does not have all the properties of an alkylaryl sulfonate surfactant system. That is, at a position selected from the α-position and the β-position of any of the two terminal carbon atoms, A is R ″
'' -C (-) H ( CH 2) v CH 2 (CH 2) x CH 2 (CH 2) may be less than about 60% of the analog to bind to a portion of the _y -CH _3. Similarly, as a surfactant system, the loss can be over 40% by weight for the analogs, as tested by the hardness tolerance test.

Alkyl Aryl Sulfonate Surfactant System The present invention relates to a hand dishwashing composition comprising a surfactant mixture. This surfactant mixture has the formula

[0048]

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Wherein L, M, R ′, R ″, R ′ ″, q, a, b, and A are as defined above, including at least two surfactants Includes alkylaryl sulfonate surfactant systems.

The present invention also relates to a hand dishwashing composition comprising a surfactant mixture. This surfactant mixture has the formula

[0051]

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[Wherein, R ″ ″, M, R ′, R ″, R ′ ″, q, a, b, A, v, x,
And y are as defined above], including alkylaryl sulfonate surfactant systems comprising at least two surfactants. Possible isomers present in both alkylarylsulfonate systems are:

[0053]

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[0054]

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[0055]

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Structures (a)-(m) are merely exemplary of some possible alkylaryl sulfonate surfactants and are not intended to limit the scope of the invention.

The alkylarylsulfonate surfactant may be selected from the following i) regioisomers based on the position of attachment of the substituents R 'and R "to L; ii) based on the chiral carbon atom in L or a substituent thereof. Stereoisomer, iii) when Ar is substituted or unsubstituted benzene, it may also include at least two “isomers” selected from ortho, meta, and para isomers based on the position of the substituent attached to Ar. Also preferred. This means that L is ortho, meta, or para to A, and L is ortho, meta, or to a substituent on A other than L (eg, R ′ ″) or any other substituent. Means that it can be para.

Examples of the two types of isomers of (i) are the structures of (a) and (c). The difference is that the methyl in (a) binds to position 5 while the methyl in (c) binds to position 7.

Examples of the two types of isomers of (ii) are the structures of (c) and (d). The difference is that these isomers are stereoisomers and the chiral carbon is the seventh carbon atom in the hydrocarbyl moiety.

Examples of the two types of isomers of (iii) are the structures of (l) and (m). The difference is that the sulfonate group of (l) is meta to the hydrocarbyl moiety,
In (m) the sulfonate group is ortho to the hydrocarbyl moiety.

[0061] Example 1: skeletal isomerization was improved alkylbenzenesulfonate surfactant system processes prepared by linear olefins (a): at least partially linear in reduced olefin (suitably washing of cleaning products A mixture of 1-decene, 1-undecene, 1-dodecene, and 1-tridecene in a weight ratio of 1: 2: 2: 1 for different chain lengths . (Eg, commercially available from Chevron) at 220 ° C. over a Pt-SAPO catalyst using any suitable LHSV (eg, 1.0
). The catalyst is prepared in the manner of the examples in US Pat. No. 5,082,956. See, for example, Example 1 of WO 95/21225 and its specification. The product is a skeletal isomerized, slightly branched olefin having a chain length range useful for making alkylbenzene sulfonate surfactant systems for incorporation into consumer cleaning compositions. More generally, the temperature of this step may be from about 200C to about 400C, preferably from about 230C to about 320C.
The pressure is typically from about 15 psig to about 2000 psig, preferably about 15 psig.
psig to about 1000 psig, more preferably about 15 psig to 600 psig.
g. Hydrogen is a useful pressurized gas. Space velocity (LHSV or WHSV
) Is suitably from about 0.05 to about 20. Low pressure and low space velocity improve selectivity, increase isomerization, and reduce pyrolysis. 40 ℃ / 10mmH
Distill off any volatiles by boiling up to g.

Step (b): An alkylated glass autoclave liner of the product of step (a) using an aromatic hydrocarbon , 1 molar equivalent of the slightly branched olefin mixture formed in step (a), 20 molar equivalents of benzene and 20% by weight, based on the olefin mixture, of a shape-selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ FM-8 / 25H) are added. Seal the glass liner in a stainless steel locking autoclave. Autoclave 25
Purged twice with N ₂ for 0 psig, then filled up to 1000 psig N _2.
While mixing, heat the mixture at 170-190 ° C. for 14-15 hours, cool,
Remove from autoclave. The reaction mixture is filtered to remove the catalyst and unreacted starting materials and / or impurities (e.g., benzene, olefins, paraffins,
The trace elements, but useful substances are recycled if desired) are concentrated by removal by distillation to give a clear, almost colorless liquid product. The product formed is the desired modified alkylbenzene, which can optionally be transported to a remote manufacturing facility where further sulfonation steps and incorporation into consumer cleaning compositions can be performed. .

Step (c): Sulfonation of the product of step (b) The product of step (b) was sulfonated with an equivalent amount of chlorosulfonic acid using methylene chloride as solvent. The methylene chloride is distilled off.

Step (d): Neutralization of the product of step (c) The product of step (c) is neutralized with a methanolic solution of sodium methoxide and the methanol is evaporated to improve the alkylbenzene sulfonate surfactant system. Get.

Example 2 Improved Alkylbenzene Sulfonate Surfactant System Prepared with Skeletal Isomerized Linear Olefins Except for using sulfur trioxide (without the use of a methylene chloride solvent) as the sulfonating agent in the sulfonation step (c). The procedure of the example was repeated. Details of sulfonation using a suitable air / sulfur trioxide mixture can be found in US Pat. No. 3,427,342 to Chemiton. Further, step (d) uses sodium hydroxide instead of sodium methoxide for neutralization.

Example 3 Modified alkylbenzene sulfonate surfactant system prepared with skeletal isomerized linear olefins Step (a): Linearity of at least partially reduced olefins The slightly branched olefin mixture comprises: C11 at a weight ratio of 3: 1 and C1
A mixture of 2 and a C13 monoolefin is prepared by passing over a H-ferrierite catalyst at 430 ° C. The methods and catalysts described in US Pat. No. 5,510,306 can be used for this step. Distill off any volatiles by boiling to 40 ° C./10 mmHg.

Step (b): An alkylated glass autoclave liner of the product of step (a) using an aromatic hydrocarbon , 1 mole equivalent of the slightly branched olefin mixture produced in step (a), 20 molar equivalents of benzene and 20% by weight, based on the olefin mixture, of a shape-selective zeolite catalyst (acidic mordenite catalyst Zeocat ^™ FM-8 / 25H) are added. Seal the glass liner in a stainless steel locking autoclave. Autoclave 25
It purged twice with N ₂ for 0 psig, to fill up 1000 psig N _2. With mixing, the mixture is heated at 170-190 ° C. overnight for 14-15 hours, cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. The benzene is distilled and reused to remove volatile impurities. A clear or almost colorless liquid product is obtained.

Step (c): Sulfonation of the product of step (b) The colorless, clear or almost colorless liquid of step (b) was sulfonated with an equivalent amount of chlorosulfonic acid using methylene chloride as solvent. The methylene chloride is distilled off.

Step (d): Neutralization of the product of step (c) The product of step (c) is neutralized with a solution of sodium methoxide in methanol and the methanol is evaporated to give an improved alkylbenzene sulfonate surfactant A sodium salt mixture, which is an agent system, is obtained.

Example 4 Modified Alkylbenzene Sulfonate Surfactant System Prepared by Skeletal Isomerized Paraffin Step (ai) 1: 3: 1 weight ratio of n-undecane, n-dodecane and n-tridecane At a temperature of about 300 ° C. and 1000 ps to convert 90% or more
ig hydrogen gas, weight hourly space velocity in the range of 2-3
y space velocity) and 30 mol H ₂ / mol hydrocarbon under the condition of Pt-SAPO-11. Further details of such isomerizations can be found in S.D. J. Miller, Microporous Material
s, 2, 1994, 439-449. As a further example, the starting linear paraffin mixture may be the same as that used in conventional LAB production.
Distill off any volatiles by boiling up to 40 ° C./10 mmHg.

Step (a ii) The paraffin of step (a i) can be dehydrogenated using conventional methods. See, for example, U.S. Patent No. 5,012,021 (April 30, 1991) or U.S. Patent No. 3,562,797 (February 9, 1971). Suitable dehydrogenation catalysts are described in U.S. Patent Nos. 3,274,287, 3,315,007, 3,315,008, 3,745,112, and 4,430. , 5
No. 17 and 3,562,797.
Dehydrogenation for the purposes of this example is as described in US Pat. No. 3,562,797. The catalyst is zeolite A. The dehydrogenation is carried out in the gas phase (paraffin: dioxygen = 1: 1 molar ratio) in the presence of oxygen. Temperature is 450 ° C to 550 ° C
Range. The ratio of grams of catalyst to total moles fed per hour is 3: 9.

Step (b): An alkylated glass autoclave liner of the product of step (a) using an aromatic hydrocarbon , 1 mole equivalent of the slightly branched olefin mixture produced in step (a), 5 molar equivalents of benzene and 20% by weight, based on the olefin mixture, of a shape-selective zeolite catalyst (acidic mordenite catalyst Z
eocat ^™ FM-8 / 25H). Seal the glass liner in a stainless steel locking autoclave. Autoclave 250
twice purged with psig of N _2, to fill up 1000psig N _2. With mixing, the mixture is heated at 170-190 ° C. overnight for 14-15 hours, cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. The benzene and any unreacted paraffin are distilled and recycled. A clear or almost colorless liquid product is obtained.

Step (c): Sulfonation of the product of step (b) The colorless, clear or almost colorless liquid of step (b) is sulfonated with sulfur trioxide / air without solvent. See U.S. Patent No. 3,427,342. The molar ratio of sulfur trioxide to alkylbenzene is from about 1.05: 1 to about 1.15: 1. The reactant stream is cooled and separated from excess sulfur trioxide.

Step (d): Neutralization of the product of step (c) The product of step (c) is neutralized with a slight excess of sodium hydroxide to obtain an improved alkylbenzene sulfonate surfactant system.

EXAMPLE 5 An Improved Alkylbenzene Sulfonate Surfactant System Prepared with Specific Tertiary Alcohols from the Grignard Reaction 5-methyl-5-undecanol, 6-methyl-6-dodecanol
A mixture with methyl-7-tridecanol is prepared by the following Grignard reaction. 28 g of 2-hexanone, 28 g of 2-heptanone and 14 g of 2-hexanone
A mixture of octanone and 100 g of diethyl ether is added to another funnel. The ketone mixture is then added dropwise over 1.75 hours to a nitrogen-filled stirred three-necked round bottom flask equipped with a reflux condenser and containing 350 mL of a 2.0 M solution of hexylmagnesium bromide in diethyl ether and another 100 mL of diethyl ether. did. After the addition is complete, the reaction mixture is stirred at 20 ° C. for a further hour. The reaction mixture is then added to 600 g of a mixture of water and ice with stirring. 228.6 to this mixture
g of a 30% sulfuric acid solution are added. The two resulting liquid layers are added to a separating funnel.
The aqueous layer is poured, and the remaining ether layer is washed twice with 600 mL of water. The ether layer is then evaporated under reduced pressure to give 115.45 g of the desired alcohol mixture. A 100 g sample of the pale yellow alcohol mixture is added to a glass autoclave liner along with 300 mL of benzene and 20 g of a shape-selective zeolite catalyst (Zeocat ^™ FM-8 / 25H acidic mordenite catalyst). Seal the glass liner in a stainless steel locking autoclave. The autoclave was purged twice with N ₂ of 250psig, 1000ps
to fill up ig N _2. With mixing, the mixture is heated at 170 ° C. overnight for 14-15 hours, cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distillation of benzene (dried and reused). A colorless, transparent or almost colorless, slightly branched olefin mixture is obtained.

The 50 obtained by dehydrogenation of the Grignard alcohol mixture as described above
g of the slightly branched olefin mixture in 150 mL of benzene and 10 g
Zeolite catalyst (acid mordenite catalyst Zeocat ^™ FM-8)
/ 25H) together with the glass autoclave liner. Seal the glass liner in a stainless steel locking autoclave. The autoclave was purged twice with N ₂ of 250 psig, to fill up 1000 psig N _2. With mixing, the mixture is heated at 195 ° C. overnight for 14-15 hours, cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distillation of benzene (dried and reused). A clear or almost colorless liquid product is obtained. The product is evaporated under reduced pressure (1-5 mmHg), keeping the 95-135 ° C fraction.

The retained fraction (ie, a clear or almost colorless liquid) is sulfonated with a molar equivalent of SO ₃ , the resulting product is neutralized with a solution of sodium methoxide in methanol and the methanol is evaporated. An improved alkylbenzene sulfonate surfactant system is obtained.

[0078] Hardness Tolerance Test (Hardness Tolerance Test) alkyl aryl sulfonate surfactant system of the present invention was measured by Hardness Tolerance Test, 40 wt% or less, preferably 20 wt% or less, more preferably 10
Less than weight percent loss. Details are as follows. Hardness Test-All used glassware is washed and completely dried.
The sample concentrate used is based on the anhydrous form of the alkylarylsulfonate surfactant system of the present invention. Experiments are performed at 22 ± 1 ° C.

Sodium salt of 4500 ppm alkylarylsulfonate surfactant system for measuring hardness resistance, 5500 ppm sodium tripolyphosphate, 3250 p
A 20 g surfactant solution containing pm sodium carbonate and 5295 ppm sodium sulfate is prepared by dissolving each component in deionized water at the indicated concentrations. 20 g of the surfactant solution are added to 180 g of a 27.8 grain / gallon hardness solution (prepared from the corresponding sulphate) with a Ca ⁺⁺ : Mg ⁺⁺ molar ratio of 3: 1. 200 g of the test solution obtained are shaken vigorously for 30 seconds and allowed to stand. After 40 minutes, a 10 mL aliquot of the test solution was added to a 0.1 μM Gelman Acrodisk.
Syringe filter (VWR Scientific, Cat. No. 28143)
-309). Discard the first 2 mL of filtrate and collect the remaining 8 mL of filtrate for analysis. The surfactant concentration (ppm) of the collected filtrate, C _surf , can be determined using a suitable analytical technique (eg, Introduction to Surfactant).
Analysis, Cullum, D .; C edition, Blackie Academi
can and Professional, Glasgow, 1994, 59-64.
(Two-phase titration as described in International Standard Method ISO 2271).

The hardness resistance obtained in this test is expressed as the% loss of the surfactant system tested according to the following formula: % Loss = ([450 ppm−C _surf (ppm)] ÷ 450 ppm) × 100% For example, Solution A B Hardness % loss 49% 8% A = Commercially available C _11-8 linear alkylbenzene sulfonate prepared by HF method. B = alkylarylsulfonate surfactant system of the present invention, comprising at least the following isomers of a disordered crystallinity surfactant, for example, prepared as described in Example 5:

[0081]

Embedded image

Various variations of the hand dishwashing composition of the present invention are useful. Such modifications include the following. -At least about 0.1% or less, preferably about 10% or less, more preferably about 5%
% Or less, still more preferably hand dishwashing cleaning composition comprising up to about 1% commercial C ₁₀ -C ₁₄ linear alkyl benzene sulfonate surfactant; - at least about 0.1% or less, preferably about 10% , More preferably about 5
% Or less, even more preferably about 1% or less, a hand-washed dishwashing composition comprising a commercially available highly branched alkylbenzenesulfonate surfactant (eg, TPBS or tetrapropylbenzenesulfonate); includes a non-ionic surfactant at a level of about 0.5 wt% to about 25 wt%, the nonionic surfactant, a form not capped or capped, linear C ₁₀ -C ₁₆ alkyl, mid-chain A hydrophobic group selected from C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, Guerbet branched C ₁₀ -C ₁₆ alkyl, and mixtures thereof, and 1
-15 ethoxylate, 1-15 propoxylate, 1-15 butoxylate,
And a dishwashing composition for hand-washing, which is a polyalkoxylated alcohol in a capped or uncapped form having a hydrophilic group selected from a mixture thereof. (A terminal primary -OH group is also present for the uncapped form, and -OR for the capped form.
A terminal group of the form (R is also a C ₁ -C ₆ hydrocarbyl moiety optionally including a primary alcohol or, preferably, a secondary alcohol, if present) is also present.
;

The alkylsulfate at a level of from about 0.5% to about 25% by weight of the detergent composition;
A surfactant, wherein the alkyl sulphate surfactant comprises a linear C_Ten~ C ₁₈ Alkyl, medium chain C₁~ C_ThreeBranch C_Ten~ C₁₈Alkyl, Guerbet branch C_Ten~ C₁₈Al
And a hydrophobic group selected from a mixture thereof, and Na, K, and a mixture thereof.
Handwashing dishwashing compositions having a cation selected from the group consisting of: alkyl (Polya) at a level of from about 0.5% to about 25% by weight of the detergent composition;
Alkoxy) sulfate surfactants, wherein the alkyl (polyalkoxy)
If the sulfate surfactant is in a capped or uncapped form and the linear C_Ten~
C₁₆Alkyl, medium chain C₁~ C_ThreeBranch C_Ten~ C₁₆Alkyl, Guerbet branch C_Ten~ C₁₆A
And a hydrophobic group selected from the group consisting of
Fate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate
, 1 to 15 mixed poly (ethoxy / propoxy / butoxy) sulfate,
(Polyalkoxy) sulfate hydrophilic groups selected from and mixtures thereof,
Tableware having a cation selected from the group consisting of Na, K, and a mixture thereof
Cleaning composition.

The hand-washing dishwashing composition may be in a capped or uncapped form and comprise a linear C _Ten ~ C₁₆Alkyl, medium chain C₁~ C_ThreeBranch C_Ten~ C₁₆Alkyl, Guerbet branch C_Ten~ C ₁₆ A hydrophobic group selected from alkyl and mixtures thereof, and 1 to 15 polyethoxy.
Sulfate, 1-15 polypropoxy sulfate, 1-15 polybutoxys
Rufate, 1-15 mixed poly (ethoxy / propoxy / butoxy) sulfate
(Polyalkoxy) sulfate hydrophilic groups selected from the group consisting of
And an alkyl having a cation selected from Na, K, and mixtures thereof
It is preferable to include a (polyalkoxy) sulfate surfactant.

When the hand-washing dishwashing composition comprises a nonionic surfactant, it is in a capped or non-capped form and is a straight chain C ₁₀ -C ₁₆ alkyl, medium chain C ₁ -C ₃ branched C. ₁₀ -C ₁₆ alkyl, Guerbet branching C ₁₀ -C ₁₆ alkyl, and a hydrophobic group selected from mixtures thereof, 1-15 ethoxylates, 1-15 propoxylates, 1
It is preferably a capsulated or uncapped polyalkoxylated alcohol having a hydrophilic group selected from 15 butoxylates and mixtures thereof.
In the uncapped form, a terminal primary -OH group is also present, and in the capped form, a form of -OR, where R is optionally a primary alcohol or, preferably, a secondary alcohol when present. (C ₁ -C ₆ hydrocarbyl groups).

The hand-washing dishwashing composition is selected from linear C ₁₀ -C ₁₆ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₈ alkyl, Guerbet-branched C ₁₀ -C ₁₆ alkyl, and mixtures thereof. It is preferred to include an alkyl sulfate surfactant having a hydrophobic group and a cation selected from Na, K, and mixtures thereof.

The hand-washing dishwashing composition of the present invention can be used or applied for hand-washing and / or can be applied by a single or variable dosage or by automatic dispensing means. These can be used in aqueous or non-aqueous cleaning systems. The composition has a wide range of pH (e.g., about 2 to about 12 or more).
The composition can have a wide range of alkalinities, although in preferred embodiments the alkaline detergent has a pH of about 8 to about 11.
Both high and low foam types are included, as well as molds for use with all known aqueous and non-aqueous consumer product cleaning methods.

The hand-washing dishwashing composition can be in any conventional form, ie, liquid, powder, agglomerate, paste, tablet, bar, gel, liquid-gel microemulsion, liquid crystal, or particle.

Conventional Handwashing Dishwashing Aids and Methods : The exact nature of these additional ingredients and their level of incorporation will depend on the physical form of the composition and the nature of the washing operation in which I am used.

The level of conventional hand dishwashing aids is about 0.00001% by weight of the composition
~ 99.9% by weight. The level of use of the entire composition can vary widely depending on the intended application (for example, in the range of a few ppm in solution to the undiluted cleaning component to the cleaning surface, the so-called "raw solution application").

Preferably, conventional cleaning aids include builders, detergent enzymes, surfactants other than alkylaryl surfactant systems (typically anionic, cationic, amphoteric,
Zwitterionic, nonionic, and mixtures thereof), at least partially water-soluble or water-dispersible polymers, abrasives, germicides, discoloration inhibitors, dyes, solubilizers, pidotropes,
Selected from the group consisting of fragrances, thickeners, antioxidants, processing aids, foaming agents, defoamers, buffers, antifungals, fungicides, insect repellents, anticorrosion aids, chelating agents, and mixtures thereof Is done. More preferably, conventional cleaning aids include one or more of the above.

[0092] Consumer product cleaning compositions are described in Surfactant Science S
eries ", Marcel Dekker, New York, Vols. 1-67. Liquid compositions are described, inter alia, in Volume 67, "Liquid Dete".
rgents ", edited by Kuo-Yann Lai, 1997, ISBN 0-82.
47-9391-9 (incorporated herein by reference). More classical formulations (particularly in particulate form) are described in Detergent Man
ufactory included Zeolite Builders
and Other New Materials, "M. Sittig, N
Oyes Data Corporation, 1979, which is incorporated herein by reference. Kirk Othmer's Encyc
See also, loopedia of Chemical Technology.

Detergents including persistent fragrances (eg, US Pat. No. 5,500,154, WO 9
6/02490), and is envisioned for use in combination with the surfactants of the present invention.

In general, conventional hand dishwashing aids are used to convert compositions containing only a minimum of essential ingredients (herein a mixture of essential surfactants) into compositions useful for hand dishwashing. Any substance needed for change. In a preferred embodiment, those skilled in the art will readily recognize that conventional hand dishwashing aids are a definitive feature of a cleaning product.

The exact nature of these additional components and their level of incorporation will depend on the physical form of the composition and the nature of the washing operation used.

[0096] Common adjuvants include builders, surfactants, enzymes, polymers, and the like. As used herein, other adjuvants include various active ingredients or specific substances, such as foaming agents, antifoaming agents (antifoaming agents), for example, dispersion polymers (eg, BASF C
orp. Or Rohm & Haas), colored speckles (color sp
eckle), silverware protectants, anti-tarnishing agents, and / or anticorrosives, dyes, fillers, bactericides, alkali sources, hydrotropes, antioxidants, enzyme stabilizers, fragrances (p
ro-perfumes, perfumes, stabilizers, carriers, processing aids, pigments, and solvents for liquid formulations (described in more detail below).

[0097] Although some easily formulated products require only one adjuvant, very typically the compositions herein require several adjuvants Nevertheless, a comprehensive list of suitable laundry or cleaning aids and methods was filed on July 21, 1997 and published by Procter & Gamble.
No. 60 / 053,318, assigned to U.S. Pat.

The surfactant mixtures of the present invention can be used in a wide variety of hand dishwashing formulations. This new surfactant mixture can be used to replace all or part of the conventional LAS in existing hand dishwashing compositions. Formulations in which the surfactant mixture of the present invention can be used as a replacement for all or part of an existing surfactant-based adjuvant or LAS include, but are not limited to: WO 98 / 12290, U.S. Patent No. 5,728,668, WO
98/05745, U.S. Patent Nos. 5,756,441 and 5,714,45.
No. 4, No. 5,712,241, No. 5,707,955, No. 4,133
U.S. Pat. No. 5,779,779, WO 97/47717, U.S. Pat. Nos. 5,688,754 and 5,665,689, WO 97/38073, U.S. Pat. No. 5,696,07.
No. 3, WO 97/38071, WO 97/00930 A, British Patent No. 2,
No. 292,562 A, US Pat. Nos. 5,736,310 and 5,269,9.
No. 74, No. 5,230,823, No. 4,923,635, No. 4,68
No. 1,704, No. 4,316,824, No. 4,133,779, No. 5
No. 5,700,773, WO 97/35947, WO 97/34976, US Pat. No. 5,629,279, WO 97/15650, US Pat. No. 5,616.
No. 5,548, No. 5,610,127, No. 5,565,421, WO 9
6/31586, U.S. Pat. Nos. 5,561,106 and 5,552,089, WO 96/22347, U.S. Pat. Nos. 5,503,779 and 5,480.
No. 5,586, EP 573,329, U.S. Pat. No. 5,382,386,
European Patent No. 487,169, US Patent No. 5,096,622, European Patent No. 4
No. 31,050, U.S. Pat. Nos. 5,102,573, 4,772,425, 4,725,337, EP 228,797, and U.S. Pat.
No. 56,509, No. 4,454,060, No. 4,454,098, No. 4,430,237, No. 4,877,546, No. 4,064,076, No. 4,101,456, No. 3,944,663, No. 4,040,9
Nos. 89, 4,102,826, 5,767,051 and 5,78
0,417, WO 97/26315, U.S. Patent Nos. 5,290,482, 3,954,679, 5,700,331, and 5,679,877.
No. 5,565,419, WO 98/22569, U.S. Pat.
No. 6,496, No. 5,733,560, No. 574,169, No. 5,7
Nos. 33,860, 5,741,770, 5,719,114, 5,604,195, European Patents 848,749, 839,177,
U.S. Pat. Nos. 5,646,104 and 5,580,848; European Patent 78
1,324, U.S. Patent Nos. 5,415,812, 5,435,936,
Nos. 5,082,584 and 5,393,468.

Detergent Surfactants The compositions of the present invention may be used with a co-surfactant (co-surfactant) with an essential surfactant mixture.
It is desirable to include a detersive surfactant used as an actant. Since the present invention relates to a surfactant in the description of the preferred embodiment of the cleaning composition of the present invention, the surfactant is described and distinguished from the non-surfactant auxiliary. Detergent surfactants were described on December 30, 1975, by Laughlin et al. U.S. Patent No. 3,929,678 to Murphy and U.S. Patent No. 4,259,217 to Murphy on March 31, 1981, entitled Surfact.
ant Science ", Marcel Dekker, Inc. , New
York and Basel, "Handbook of Surfacta
nts ", M.P. R. Porter, Chapman and Hall, 2nd ed., 1994, "Surfactants in Consumer Produ.
cts ", J.M. Falbe, Ed., Springer-Verlag, 1987, and numerous cleaning-related patents assigned to Procter & Gamble, and are extensively exemplified in the manufacture of other cleaning and consumer products.

The cleaning surfactants herein include anionic, nonionic, cationic, zwitterionic, or amphoteric types known for use as cleaning agents, but are completely foamable. It does not include non-detergent or completely insoluble surfactants (these can be used as optional auxiliaries).

More specifically, detersive surfactants useful herein suitably include: (1) including hard types (ABS, TPBS) or linear types; Various HF or solid HF methods (eg, DETAL (trade name) (UOP) method)
Known method or other Lewis acid catalyst (e.g., AlCl ₃₎ conventional alkylbenzene sulfonate made by the use, or the use of use or chlorinated hydrocarbons acidic silica / alumina, such as; (2) alpha-olefin Olefin sulfonates, including sulfonates and sulfonates from fatty acids and fatty acid esters; (3) other sulfonate / carboxylate surfactants, such as diester and half ester forms and sulfosuccinates from sulfosuccinamate and ethoxylated alcohols and alkanolamides Alkyl or alkenyl sulfonates, including dosage forms; (4) paraffins or alkane sulfonates, including alkyl sulfonate products of α-olefins, and alkyl or alkenyl carboxy sulfonates. (5) alkyl naphthalene sulfonate; (6
) Alkyl isethionates and alkyl propane sulfonates and fatty isethionate esters, fatty esters of ethoxylated isethionates, and 3
-Other ester sulfonates such as hydroxypropane sulfonate or esters of the AVANEL S type; (7) benzene, cumene, toluene, xylene and naphthalene sulfonate which are particularly useful for hydrotropic properties; (8)
Alkyl ether sulfonate; (9) alkyl amide sulfonate; (10)
α-sulfofatty acid salts or esters and internal sulfofatty acid esters; (11)
(12) lignin sulfonate; (13) petroleum sulfonate (also known as heavy alkylate sulfonate); (14) diphenyl oxide disulfonate; (15) linear or branched alkyl or alkenyl sulfate; 16) Alkyl or alkyl phenol alkoxylate sulfates and corresponding polyalkoxylates (also known as alkyl ether sulfates) and alkenyl alkoxyl sulfates or alkenyl polyalkoxy sulfates; (17) alkyl amide sulfates or alkenyl amide sulfates (sulfuric acid Alkanolamides and their alkoxylates and polyalkoxylates); (18) sulfated oils, sulfated alkyls Surfactants derived from lyserides, sulfated alkyl polyglycosides, or sulfated sugars; (19) alkyl alkoxy carboxylate and alkyl polyalkoxy carboxylate (including galacturonic acid salts); (20) alkyl ester carboxylate and alkenyl ester carboxylate rate;
(21) alkyl or alkenyl carboxylates (especially conventional soaps and α, ω-dicarboxylates) (including alkyl and alkenyl succinates); (22) alkyl or alkenyl amidoalkoxy and polyalkoxy carboxylates; ) Alkyl and alkenyl amide carboxylate surfactant types (including sarcosinate, tauride, glycinate, aminopropionate, and iminopropionate); (24) amide soaps (also called fatty acid cyanamides); rate;
(26) Phosphorus based surfactants (including alkyl or alkenyl phosphates), alkyl ether phosphates (alkoxylated derivatives thereof, phosphatidates, alkyl phosphates, alkyl di (polyoxyalkylene alkanol) phosphates, amphoteric phosphates ( And / or phosphate / carboxylate, phosphate / sulfate and phosphate / sulfonate types; (27) pluronic and tetronic nonionic surfactants; (28) so-called EO / PO block polymers (diblock (29) fatty acid polyglycol esters; (30) capped and uncapped alkyl or alkylphenol ethoxylates, including triblock EPE and PEP types). Kishireto, and butoxylate (including fatty alcohols polyethylene glycol ether), (31) (present as unreacted components of particularly useful or other surfactants as viscosity surfactant) fatty alcohols; (32
) N-alkyl polyhydroxy fatty acid amides, especially N-alkyl glucamides;
(33) nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkyl polyglycosides and sucrose fatty acid esters;
) Ethylene glycol, propylene glycol, glycerol, and polyglyceryl esters and their alkoxylates, especially glycerol ethers and fatty acids / glycerol monoesters and diesters; (35) aldobionamide surfactants; (36) alkylsuccinimide nonionics Surfactant type; (37) acetylene alcohol surfactant (such as SURFYNOLS);
(38) alkanolamide surfactants and alkoxylated derivatives thereof (including fatty acid alkanolamides and fatty acid alkanolamide polyglycol ethers); (39) alkylpyrrolidones; (40) alkylamine oxides (alkoxylated or polyalkoxylated amine oxides) (41) alkyl phosphine oxide; (42) sulfoxide surfactant; (43) amphoteric sulfonate, especially sulfobetaine; (44) betaine-type amphoteric surfactant (derived from aminocarboxylate). (45) amphoteric sulfates (such as alkylammoniopolyethoxy sulfates); (46)
A) alkylamines and amine salts derived from fats and petroleum; (47) alkylimidazolines; (48) alkylamidoamines and their alkoxylates and polyalkoxylate derivatives; (49) conventional cationic surfactants (water-soluble alkyltrimethylammonium). Including salt). In addition, the following less common surfactant types are included: (50) alkylamidoamine oxides, (51) any of the sugar-derived surfactants modeled after any of the above-referenced conventional non-sugar forms; (5
(53) a biosurfactant; (54) an organosilicon compound or a fluorocarbon surfactant; (55) a gemini surfactant other than diphenyloxide disulfonate referred to above (derived from glucose). (Including surfactant);
56) polymeric surfactants (including amphoteric polycarboxyglycinates); and (5)
7) Surfactants in bolaform (ie, any surfactant known in aqueous or non-aqueous detergents).

For any of the detersive surfactants described above, the length of the hydrophobic chain is typically in the general range C ₈ -C ₂₀ , preferably in the range C ₈ -C ₁₈ , especially in the wash In the case of use, it is performed in cold water. The choice of chain length and degree of alkoxylation for conventional purposes is taught in standard texts. If the detersive surfactant is a salt, then H (ie, the acid or partial acid form of the potentially acidic surfactant can be used)
Any suitable cation may be present, including Na, K, Mg, ammonium or alkanolammonium, or a combination of cations. Generally, mixtures of detersive surfactants of different charges, especially anionic / cationic, anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / Amphoteric, nonionic / cationic and nonionic / amphoteric mixtures are preferred. Furthermore, by mixing other similar detersive surfactants with different chain lengths, degrees of unsaturation or branching, degrees of alkoxylation (especially ethoxylation) or, for example, oxygen of ethers in hydrophobic groups Insertion of substituents such as
Or any combination of these can replace any single cleaning surfactant, which may provide desirable results for cleaning with cold water.

Preferred among the detersive surfactants identified above are: acids, sodium and ammonium C ₉ -C ₂₀ linear alkyl benzene sulphonates, in particular sodium linear secondary alkyl C ₁₀ -C ₁₅ Benzenesulfonate (ABS can be used in some positions) (1); Olefin sulfonate salt (2
), I.e., olefins (especially, C ₁₀ -C ₂₀ alpha-olefin) and sulfur trioxide and the reaction product was allowed to react with neutralizing and hydrolyzing to produce substances; sodium and ammonium C ₇ -C ₁₂ dialkyl sulfo succinate (3); alkane monosulfonates, for example, by hydrolysis reaction after the base of the C ₈ -C ₂₀ alpha-olefin and those derived by reaction with sodium disulfide and paraffins and SO ₂ and C _l2 Α-sulfo fatty acid salts or esters (10); sodium alkyl glyceryl sulfonates (especially ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum), such as those derived from random sulfonates formed (4); ) (11); primary or secondary, saturated or unsaturated, branched Others unbranched alkyl or alkenyl sulfates (15). If branched, such compounds can be random or regular. If secondary, the compound is preferably of the following formula: CH _{3
(CH 2) x (CHOSO 3} - M +) CH 3 or _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 [ where, x and (y + 1) is at least 7, preferably at least 9 And M is a water-soluble cation (preferably sodium). If unsaturated, the sulfates, such as oleyl Rusuru sulfates are preferred, sodium and ammonium alkyl sulfates, especially, C ₈ -C ₁₈ alcohols (e.g., tallow or coconut oil) sulfate produced by the sulfation of also useful Alkyl or alkenyl ether sulfates are also preferred (especially about 0.5 moles or more (preferably 0.5-8 moles) of ethoxylated ethoxy sulfates (16); alkyl ether carboxylates, especially EO 1-5 ethoxycarboxylate (19); soaps or fatty acids (preferably more water-soluble) (21); amino acid surfactants (such as sarcosinates, especially oleyl sarcosinate) (23); phosphates Ester (26); Alky Le or alkylphenol ethoxylates, propoxylates and butoxylate, in particular, aliphatic having ethoxylate "AE" and C ₆ -C ₁₂ alkyl phenol alkoxylates as well as ethylene oxide (typically 2～30EO) comprising an alkyl ethoxylate-called narrow peak primary or secondary linear or branched chain C ₈ -C ₁₈ alcohols (30); N-alkyl polyhydroxy fatty acid amides, in particular, C ₁₂ -C ₁₈ N-methyl glucamide (WO
See) and N- alkoxy polyhydroxy fatty acid amide _{92/06154 (C 10 ~C 18 N- (} 3- methoxypropyl) but glucamide, or the like),
Also N- propyl ~N- hexyl C ₁₂ -C ₁₈ glucamides can be useful for low foaming (32), alkyl polyglycosides (33); amine oxide, preferably alkyldimethylamine N- oxides and dihydrate thereof (40); sulfobetaines or "sultaines"(43); betaines (44); and gemini surfactants.

[0104] Cationic surfactants suitable for use in the present invention include those having long chain hydrocarbyl groups. Examples of such cationic co-surfactants include ammonium co-surfactants such as alkyldimethyl ammonium halides and the formula [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ^- [wherein, R ² is alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R ³ is _{-CH 2 CH 2 -, - CH} 2 CH (CH 2 )-,
Selected from the group consisting of CH ₂ CH (CH ₂ OH) —, —CH ₂ CH ₂ CH ₂ — and mixtures thereof; and when y is not 0, each R ⁴ is C ₁ -C ₄ alkyl, C ₁ -C _{4 Four}
Hydroxyalkyl, a benzyl ring structure formed by the bonding of two R ⁴ groups,
_{^{-CH 2 CHOH-CHOHCOR 6 CHOHCH 2}} OH (R 6 is hexose or hexose polymer having a molecular weight of less than 1000), is selected from the group consisting of hydrogen; or R ⁵ is the same as R ^4, the R ² + R ⁵ Alkyl chains having no more than about 18 carbon atoms; y is each from 0 to about 10, and the sum of y is from 0 to about 15;
X is any compatible anion].

Examples of other suitable cationic surfactants are described in the following documents, all of which are incorporated herein by reference: C. Publishing C
o. , McCutcheon's, Detergents & Elulsif
iers, North American edition, 1997, Sch
wartz, et al., Surface Active Agents, Their
Chemistry and Technology, New York, In
terscience Publishers, 1949, U.S. Pat.
No. 5,591, No. 3,929,678, No. 3,959,461, No. 4
No. 3,387,090 and No. 4,228,044.

Examples of suitable cationic surfactants are the cations corresponding to the general formula:

[0107]

Embedded image

Wherein R ¹ , R ² , R ³ , and R ⁴ are independently an aliphatic group of from 1 to about 22 carbon atoms, an aromatic having up to about 22 carbon atoms, an alkoxy group, X is a halogen (eg, chlorine, bromine), acetate, citrate, lactate, glycolate, phosphate, Salt-forming anions, such as anions selected from nitrates, sulfates, and alkyl sulfate radicals. Aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages and other groups (such as amino groups). Aliphatic groups of longer chain length (eg, about 12 carbons or more) can be saturated or unsaturated. Preferably, R ¹ , R ² , R ³ , and R ⁴ are independently selected from C ₁ to about C ₂₂ alkyl. Cationic substances comprising two long-chain alkyls and two short-chain alkyls or comprising one long-chain alkyl and three single-chain alkyls are particularly preferred. The long chain alkyl in the above compounds has about 12 to about 22 carbon atoms, preferably about 16 to about 22 carbon atoms, and the single chain alkyl in the above compounds has about 1 to about 3 carbon atoms. Carbon atoms, preferably about 1 to about 2 carbon atoms.

Suitable levels of the cationic detergent surfactant herein are from about 0.1% to about 2%.
0%, preferably about 1% to about 15%, but at higher levels (eg, about 30%).
% Or more) may be particularly useful in non-ionic: cationic (ie, limited or anion-free) formulations. One possible use of the cationic surfactant is as a fat releasing agent. The cationic surfactant can be itself or in combination with a solvent and / or a solubilizer. See U.S. Patent No. 5,552,089.

Another type of useful surfactant is the so-called dianion (dianion). This is a surfactant that has at least two anionic groups on the surfactant molecule. Some suitable dianionic surfactants are described in co-pending US patent application Ser. No. 60 / 020,503, filed Jul. 28, 1996, having accession number 6160.
P), 60 / 020,772 (reference number 6161P), 60 / 020,928 (
Reference number 6158P), 60 / 020,832 (reference number 6159P), 60 /
020,773 (reference number 6162P), and 60 / 023,539 (reference number 6192P), 60 / 023,493 (reference number 6194P), 60 / 023,540 (reference number) filed on August 8, 1996. 6193P), and 60
/ 023,527 (atomic number 6195P), the disclosure of which is incorporated herein by reference.

More preferably, the surfactant may be a medium-chain branched alkyl sulfate, a medium-chain branched alkyl alkoxylate, or a medium-chain branched alkyl alkoxylate sulfate. These surfactants include 60 / 061,971 (attorney docket number 6881P (October 14, 1997)), 60 / 061,975 (attorney docket number 6882P (October 14, 1997)), 60 / 062,086 (agent reference number 6883P (October 14, 1997)), 60 / 061,916 (
Agent Reference Number 6884P (October 14, 1997)), 60 / 061,97
0 (agent reference number 6885P (October 14, 1997)), 60/062,
407 (Attorney Reference Number 6886P (October 14, 1997)). Other suitable medium chain branched surfactants are described in US Patent Application Serial No. 60/032,
035 (reference number 6401P), 60 / 031,845 (reference number 6402P)
, 60 / 031,916 (reference number 6403P), 60 / 031,917 (reference number 6404P), 60 / 031,761 (reference number 6405P), 60/03
1,762 (reference number 6406P) and 60 / 031,844 (reference number 6).
409P). Mixtures of these branched surfactants, including conventional linear surfactants, are also useful for use in the compositions of the present invention.

[0112] Combinations of surfactants are also contemplated. One such combination would be a modified alkylbenzene sulfonate surfactant of the present invention that forms a complex of negative charge with the alkylene carbonate surfactant. US Patent 5,736,496
See issue. Alternatively, these alkylene carbonate surfactants are combined with the modified alkylbenzene sulfonate surfactants of the present invention and do not form negatively charged complexes. Such compositions are described in U.S. Patent No. 5,733,860. For either type of composition, suitable alkylene carbonate surfactants include the formula:

[0113]

Embedded image

Wherein R ¹ is a C _n alkyl group, R ² is H or a C _m alkyl group, and n
+ M is a number from 11 to 14].

Another possible combination with a modified alkylbenzene sulfonate surfactant is
Monoalkyl succinates, more preferably up to 8 moles of alkyl groups
About 0.5 to about 6% by weight of C that can be ethoxylated with_Ten~ C ₁₈ Combination with monoalkyl succinate
The seat has the following structure.

[0116]

Embedded image

Where R is an aliphatic radical of 10 to 18 carbon atoms and M is a cation selected from sodium, potassium, ammonium, and alkanolamine. See U.S. Patent No. 5,480,586.

Suitable levels of anionic detergent surfactant herein are from about 1% to about 50% or more, preferably from about 2% to about 30%, by weight of the detergent composition. %, More preferably from about 5% to about 20% by weight.

[0119] Suitable levels of nonionic detergent surfactant herein are from about 1% to about 40%, preferably from about 2% to about 30%, more preferably about 5% by weight. %
In the range of about to 20% by weight.

The desired anionic surfactant: nonionic surfactant weight ratio to be combined in the composition is 1.0: 9.0 to 1.0: 0.25, preferably 1.0: 1.5-
1.0: 0.4.

The desired anionic surfactant: cationic surfactant weight ratio to be combined in the composition is from 50: 1 to 5: 1, more preferably from 35: 1 to 15: 1.

Suitable levels of the cationic detergent surfactant herein range from about 0.1% to about 20%, preferably from about 1% to about 15%, but higher levels. (Eg, up to about 30% or more) may be particularly useful in non-ionic: cationic (ie, limited or free of anions) formulations.

[0123] Amphoteric or amphoteric detersive surfactants, when present, are typically useful at levels ranging from about 0.1% to about 20% by weight of the detergent composition. The levels are, in particular,
When zwitterions are expensive, they are often limited to no more than about 5% by weight.

The surfactant composition preferably comprises at least 0.01%, more preferably at least 0.1%, even more preferably at least 0.2%, even more preferably at least 0.1% by weight of the composition. Contains 5% by weight of surfactant. The composition also contains no more than about 90%, more preferably no more than about 70%, even more preferably no more than about 60%, even more preferably no more than 35% by weight of the composition of surfactant.

Anionic surfactants useful herein include linear alkyl benzene sulfonates, α-olefin sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates , Alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof.

When present, the anionic surfactant is typically present in an effective amount. More preferably, the composition may comprise at least about 0.5%, more preferably at least about 5%, even more preferably at least about 10%, by weight of the composition, of an anionic surfactant. The composition also preferably comprises no more than about 90%, more preferably no more than about 50%, even more preferably no more than about 30% surfactant by weight of the composition.

[0127] Alkyl sulfate surfactants are another type of anionic surfactant that is important for use herein. Polyhydroxy fatty acid amines (see below)
Excellent overall cleaning performance when used in combination with a wide range of temperatures, cleaning concentrations,
In addition to obtaining good grease / oil washing performance at wash time), alkyl sulfates can be dissolved and the improved formulation capacity in liquid detergent formulations is of the formula ROSO ₃ M Wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component,
More preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation (e.g., alkali metal (IA Group) cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations ( Cations such as methyl, dimethyl, and trimethylammonium) and quaternary ammonium cations (eg, tetramethylammonium and dimethylpiperdinium), and cations derived from alkanolamines (ethanolamine, diethanolamine, triethanolamine, and mixtures thereof) ) is a water-soluble salt or acid such as]. typically, alkyl chains of C ₁₂ -C ₁₆ is lower wash temperatures (e.g., below about 50 ℃), C ₁₆ ~C ₁₈ alkyl chain higher Preferred for cleaning temperature (eg, above about 50 ° C) .

Alkyl alkoxylated sulfate surfactants are useful anionic surfactants
Another category of sexual agents. These surfactants are typically of the formula RO (A
) MSO_ThreeM [where R is C_Ten~ C_{twenty four}Unsubstituted C containing an alkyl moiety_Ten~ C_{twenty four}Al
A killed or hydroxyalkyl group, preferably C₁₂~ C₂₀Alkyl or hydro
Xyalkyl, more preferably C₁₂~ C₁₈With alkyl or hydroxyalkyl
Where A is an ethoxy or propoxy unit and m is greater than 0, typically about
0.5 to about 6, more preferably between about 0.5 and about 3, wherein M is H or positive
ON, eg, metal cations (eg, sodium, potassium, lithium, etc.)
, Ammonium or unsubstituted ammonium cations]
Is an acid. Alkyl ethoxylated sulfate and alkyl propoxyl
Fluoride sulfates are contemplated herein. Identification of substituted ammonium cations
Examples of methyl, dimethyl, trimethyl ammonium, and quaternary ammonium
Cations (tetramethylammonium, dimethylpiperidinium, etc.) and
And cations derived from alkanolamines (eg, monoethanolamine,
Anolamine, and triethanolamine and mixtures thereof). World
Examples of surfactants include C wherein M is conveniently selected from sodium and potassium.₁₂~
C₁₈Alkyl polyethoxylate (1.0) sulfate, C₁₂~ C₁₈Alkyl
Polyethoxylate (2.25) sulfate, C₁₂~ C₁₈Alkyl polyethoxy
Silate (3.0) sulfate, C₁₂~ C₁₈Alkyl polyethoxylate (4
. 0) It is sulfate. Surfactants used herein may be natural or
It can be made from synthetic alcohol feedstocks. The chain length is the average hydrocarbon content
Equivalent to cloth (including branches). The anionic surfactant component is a conventional alcohol
Source (natural alcohol, synthetic alcohol (brand name NEODOL)^TM, ALFOL ^TM , LIAL^TM, LUTENSOL^TM) Derived alkyl)
It may include sulfates and alkyl ether sulfates. Alkyl ether
Rusulphate is also known as alkyl polyethoxylate sulphate
You.

Examples of suitable anionic surfactants are described in “Surfactants and Detergents”, Volumes I and II, Schwartz, Perry and Berch. A variety of such surfactants are also commonly disclosed on December 30, 1975, La.
U.S. Pat. No. 3,929,678 to Ughlin et al., paragraph 23, paragraph 58.
It is disclosed from line 29 to paragraph 29, line 23.

One type of anionic surfactant that can be used comprises an alkyl ester sulfonate. These are desirable because they can be made using renewable non-oil sources. The preparation of the alkyl ester sulfonate surfactant component can be performed according to a known method disclosed in technical literature. For example, "The
Journal of the American oil Chemists So
ciety ", according to page 52,1975,323～329, linear esters of C ₈ -C ₂₀ carboxylic acids can be sulfonated with gaseous SO _3. Suitable starting materials include natural fatty substances such as tallow, palm, and coconut.

Preferred alkyl ester sulfonate surfactants, especially for laundry, have the following structural formula:

[0132]

Embedded image

Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl or a combination thereof, and M is a soluble salt. Alkyl cation sulfonate surfactant that is a forming cation]. Suitable salts include metal salts such as sodium, potassium, lithium; substituted or unsubstituted ammonium salts such as methyl, dimethyl, and trimethylammonium salts; and quaternary ammonium salts such as, for example, tetramethylammonium and dimethylpiperdinium Cations; and cations derived from alkanolamines such as, for example, monoethanolamine, diethanolamine, triethanolamine, and the like. 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 is especially preferred.

[0134] Other anionic surfactants useful for cleaning purposes may be included in the composition. These include soap salts such as sodium, potassium, ammonium, and substituted ammonium salts (such as mono, di, triethanolamine salts), C ₉ -C ₂₀ linear alkyl benzene sulfonates, C ₈ -C ₂₂ primary. or secondary alkane sulfonates, C ₈ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates (e.g.,
UK Patent No. 1,082,179), alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isothionate (such as acyl isothionate), N - acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, sulfosulfuron monoesters of succinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinates diesters ( In particular, saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates, sulfates of alkyl polysaccharides (sulfates of alkyl polyglucosides (described below) Nonionic nonsulfated compounds), etc.), branched primary alkyl sulfates of the formula _{RO (CH 2 CH 2 O)} k CH 2 COO - in M ⁺ (wherein, R is a C ₈ -C _{2 2} alkyl And k is an integer from 0 to 10 and M is a soluble salt-forming cation), as well as fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, resin acids and hydrogenated resin acids present or derived from tall oil are also suitable. Further examples are described in "Surfactants and Detergents", Volumes I and II, Schwartz, Perry and Berc.
h. A variety of such surfactants are also commonly described in 1975
No. 3,929,678, issued to Laughlin et al. On Feb. 30, at column 23, line 58 to column 29, line 23.

Nonionic Detergent Surfactants—Suitable nonionic detersive surfactants are generally described in US Pat. No. 3,387,984, issued to Laughlin et al. On December 30, 1975.
No. 929,678, column 13, line 14 to column 16, line 6 (incorporated by reference herein). By way of example, useful nonionic surfactants include, but are not limited to: alkyl ethoxylates,
Alkanoyl glucose amide, C ₁₂ -C ₁₈ alkyl ethoxylate (“AE”
) (Including alkyl ethoxylates of the so-called narrow peak), and C ₆ -C ₁₂
Alkylphenol alkoxylates, especially ethoxylates and mixed ethoxy / propoxy, and mixtures thereof.

When present, the nonionic surfactant is typically present in an effective amount. More preferably, the composition comprises at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5% by weight of the composition of a nonionic surfactant. obtain. The composition also preferably contains no more than about 20%, more preferably no more than about 15%, even more preferably no more than about 10% by weight of the composition of surfactant.

Polyethylene, polypropylene, 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 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 non-ionic surfactants of this type include Igepal (R) CO-630, available from GAF Corporation, and Rohn & Haas Compa.
X-45, X-114, X-100, and X-102 available from NY
Is included. 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 is straight or branched, primary or secondary,
Generally, it may contain from about 8 to about 22 carbon atoms. Particularly preferred is the condensation product of an alcohol having an alkyl group containing about 10 to about 20 carbon atoms with about 2 to about 18 moles of ethylene oxide per mole of alcohol. Commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear primary alcohol with 9 moles of ethylene oxide), Tergito
l (trade name) 24-L-6 NMW ( C 12 ~C 14 straight chain condensation product of 6 moles of ethylene oxide primary alcohol and narrow molecular weight distribution) (both Union Ca
Rbide Corporation commercially available from); Neodol (trade name) 45-9 (C ₁₄ ~C ₁₅ condensation product of linear alcohol with 9 moles of ethylene oxide), Neodol (trade name) 23-6.5 (C ₁₂ -C ₁₃ condensation product of linear alcohol with 6.5 moles of ethylene oxide), Neodol (trade name) 4
5-7 (C ₁₄ ~C ₁₅ condensation product of linear alcohol with 7 moles of ethylene oxide), generates condensation of Neodol (trade name) 45-4 (C ₁₄ ~C ₁₅ linear alcohol with 4 moles of ethylene oxide Thing) (Shell Chemical Compa
commercially available from ny); Kyro (trade name) EOB (C ₁₃ ~C ₁₅ condensation product of linear alcohol with 9 moles ethylene oxide) (Procter & Ga
mble Company). Other commercially available nonionic surfactants include Dobanol 91-8 (trade name) (Shell Ch)
electronic Co. And Genapol UD-08
0 (trade name) (commercially available from Hoechst). This category of nonionic surfactants is commonly referred to as "alkyl ethoxylates".

A condensation product of ethylene oxide and a hydrophobic base, formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the compound preferably has a molecular weight of about 1500 to about 1800 and is insoluble in water. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole and the liquid nature of the product is such that the polyoxyethylene content is about 50% of the total condensation product ( (Corresponding to condensation with up to about 40 moles of ethylene oxide). Examples of compounds of this type include commercially available Pluronic
(Trade name) surfactant (commercially available from BASF).

A condensation product of ethylene oxide with the product obtained by the reaction of propylene oxide with ethylene diamine. The hydrophobic portion of these products consists of the reaction of ethylene diamine with excess propylene oxide, generally from about 2500 to about 30
00 molecular weight. The hydrophobic portion is condensed with ethylene oxide to a extent that the condensation product comprises from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain commercially available Tetronic® compounds (commercially available from BASF).

Examples of ethylene oxide-propylene oxide block copolymers useful for use herein are described in Pancheri / Mao, December 2, 1992.
This is described in more detail in US Pat. No. 5,167,872 issued by Jpn. This patent is incorporated herein by reference.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x wherein} R ² is from about 10 to about 18, preferably about 12 alkyl groups. Selected from the group consisting of alkyl containing from about 14 carbon atoms, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein n is 2 or 3
, Preferably 2, t is 0 to about 10, preferably 0, and x is about 1.3 to
From about 10, preferably from about 1.3 to about 3, and most preferably from about 1.3 to about 2.7. Glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and reacted with glucose or a glucose source to form a glucoside (one-position bond).
Is formed. Another glycosyl unit can then be linked between this position and the aforementioned glycosyl unit at position 2, 3, 4 and / or 6 and preferably mainly at position 2.

About 6 to about 30 carbon atoms, preferably about 10 to 16 carbon atoms, and a polysaccharide such as a polyglycoside (about 1.3 to about 10, preferably about 1.
Alkylpolysaccharides having from 3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units) are Lle, published January 21, 1986.
No. 4,565,647 to Nado. 5-
Any reduced saccharide containing 6 carbon atoms can be used (eg,
The glucosyl moiety can be replaced with glucose, galactose, and galactosyl moieties). (Optionally, the attachment of a hydrophobic group at the 2-, 3-, 4-, etc. position provides glucose or galactose for glucoside or galactoside.) The linkage between the saccharides may be, for example, one of the other saccharide units. Between one position and the second, third, fourth, and / or six positions of the saccharide unit.

[0144] Although optional but less desirable, there may be a polyalkylene-oxide chain associated with the hydrophobic moiety and the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include about 8 to about 18
Saturated or unsaturated, branched or unbranched alkyl groups containing from about 10 to about 16 carbon atoms. Preferably, the alkyl group is a linear saturated alkyl group. Alkyl groups may contain up to about 3 hydroxy groups and / or polyalkylene oxide chains may contain up to about 10, preferably less than 5 alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyl,
Decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di, tri, tetra, penta, and hexaglucoside, galactoside, lactoside, glucose, fructoside, fructose, and / or galactose. Suitable mixtures include coconut alkyl, di, tri, tetra, and pentaglucoside, and tallow alkyl tetra, penta, and hexaglucoside.

Another type of suitable nonionic surfactants include all-esterified ethoxylated polyhydric alcohols, partially esterified ethoxylated polyhydric alcohols, and non-esterified ethoxylated Mixtures that are mixtures with polyhydric alcohols (referred to as ethoxylated glycerol type compounds) are included, a preferred polyhydric alcohol being glycerol, wherein the compound has the formula

[0146]

Embedded image

And, it is expressed by the following equation.

[0148]

Embedded image

[Wherein, w is 1 to 4, most preferably 1. B is selected from the group consisting of hydrogen and a group represented by the following formula:

[0150]

Embedded image

In the formula, R represents an alkyl group having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms and 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms. Most preferably a hydrogenated tallow alkyl chain or a cocoalkyl chain, and at least one of group B is represented by the following formula:

[0152]

Embedded image

Wherein R ′ is selected from the group consisting of hydrogen and methyl, and (x + y + z) is 2
X, y when it is -100, preferably 4-24, most preferably 4-19,
And z are values between 0 and 60, preferably between 0 and 40, and in formula (I) the weight ratio of monoester / diester / triester is between 45 and 90/5 to 40
/ 1 to 20, more preferably 50 to 90/9 to 32/1 to 12, and the formula (I)
And the weight ratio of formula (II) to between 3 and 0.02, preferably between 3 and 0.1,
Most preferably, between 1.5 and 0.2, the compound of formula (
Most preferably, there are more formulas (II) than I).

An ethoxylated glycerol-type compound that can be used in the composition of the present invention is manufactured by Kao Corporation and has a Levenol F-200 (average EO of 6 and a molar ratio of coco fatty acid to glycerol). Is 0.55) or Levenol V501 / 2 (average EO is 17 and the molar ratio of tallow fatty acid to glycerol is 1.0). The molar ratio of fatty acid to glycerol is less than 1.7, more preferably 1.
Preferably it is less than 5, most preferably less than 1.0. The ethoxylated glycerol type compound has a molecular weight of 400 to 1600 and a pH of 5 to 7 (50 g / liter of water). The Levenol compound is substantially non-irritating to human skin and is 90% as measured by the Bias-7d of the Wickbold method.
Shows primary biodegradability exceeding Two examples of compounds of Levenol are Level
nol V501 / 2 (derived from tallow fatty acid having 17 ethoxylated groups, the molar ratio of fatty acid to glycerol is 1.0, and has a molecular weight of 1465)
And Levenol F-200 (derived from coco fatty acids having 6 ethoxylated groups and a molar ratio of fatty acid to glycerol of 0.55). L
Evenol F-200 and Levenol V501 / 2 are both of the formula (I)
And a mixture of Formula (II). The Levenol compounds exhibit an algicidal value of algal growth inhibition greater than 100 mg / liter, daphnia acute toxicity greater than 100 mg / liter, and fish acute toxicity greater than 100 mg / liter. The Levenol compound already shows a biodegradability of more than 60%, the minimum value measured by OECD 301B, which is an acceptable biodegradability. Polyesterified nonionic compounds can also be obtained from commercially available compositions (Croda GMBH, The Netherlands).
Crovol PK-40 and Crovol PK-70 produced by
Is useful. Crovol PK-40 is a polyethylene (12) palm kernel glyceride having 12EO groups. A preferred Crovol PK-70 is 4
Polyoxyethylene (12) palm kernel glyceride having 5EO groups. Additional information regarding this nonionic surfactant is provided in US Pat. No. 5,719,114.
Can be found in the issue.

[0155] Another type of suitable nonionic surfactant includes polyhydroxy fatty acid amides. This material is more fully described in U.S. Patent No. 5,332,528 issued July 26, 1994 to Pan / Gosselink, which is incorporated herein by reference. This polyhydroxy fatty acid amide has the following general formula:

[0156]

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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 -C ₂ Alkyl is most preferably C ₁ alkyl (ie methyl); R ² is C ₅ -C ₃₁ hydrocarbyl, preferably linear C ₇ -C ₁₉ alkyl or alkenyl, more preferably linear C ₉ -C ₁₇ alkyl or alkenyl, most preferably a straight chain C ₁₁ -C ₁₅ alkyl or alkenyl, or mixture thereof;
Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain containing at least three hydroxyls directly attached to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction, and more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be used as well as the respective sugars listed above. These corn syrups can be obtained as a mixture of the sugar components of Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z
_{Preferably, -CH 2 - (CHOH) n} -CH 2 OH, -CH (CH 2 OH) -
(CHOH) _n-1 —CH ₂ OH, —CH ₂ — (CHOH) ₂ (CHOR ′) (CHO
H) —CH ₂ OH, where n is an integer from 3 to 5, and R ′ is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. n is 4, particularly -CH ₂ - (CHOH) glycityl most preferably ₄ -CH ₂ OH.

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, tallow amide, 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.

[0161] Methods for producing polyhydroxy fatty acids are known in the art. Generally, they form the corresponding N-alkyl polyhydroxyamine by the reaction of an alkylamine with a reducing sugar in a reductive amination reaction, followed by N
-By reacting an alkyl polyhydroxyamine with a fatty acid ester or triglyceride to form an N-alkyl, N-polyhydroxy fatty acid amide product. A method for producing a composition containing a polyhydroxy fatty acid is described in, for example, Thomas Hedley & Co. , Ltd. British Patent No. 809,060, issued Feb. 18, 1959; R. Wil
U.S. Pat. No. 2,965,57 issued to Dec.
No. 6, Anthony M. U.S. Pat. No. 2,703,798, issued Mar. 8, 1955 to Piggott, issued to Schwartz, and granted 1934.
No. 1,985,424, issued Dec. 25, 2014, each of which is incorporated herein by reference.

Examples of such surfactants include C ₁₀ -C ₁₈ N-methyl-, or N-hydroxypropyl-glucamide. From N- propyl N- hexyl -C ₁₂ ~
C ₁₆ glucamide can be used for low foaming.

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

[0164] Another suitable class of surfactants is the alkanolamide surfactants, including ammonia, monoethanol, and diethanolamide of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms. These substances are represented by the following formula.

[0165]

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Wherein R ₁ is a saturated or unsaturated hydroxy-free aliphatic hydrocarbon group having about 7 to 21, preferably about 11 to 17 carbon atoms; R ₂ is methylene or ethylene And m is 1, 2, or 3, preferably 1. Particular examples of such amides are monoethanolamine coconut fatty acid amide and diethanolamine dodecyl fatty acid amide. These acyl moieties can be derived from naturally occurring glycerides (eg, coconut oil, palm oil, soybean oil, and tallow), but synthetic (eg, petroleum oxidation or Fischer-Tro).
hydrogen addition of carbon monoxide by the psch method). Monoethanolamides and diethanolamides of C ₁₂ ~ ₁₄ fatty acids are preferred.

Amphoteric surfactants Amphoteric surfactants can optionally be incorporated into the cleaning composition. These surfactants are widely described as aliphatic derivatives of secondary or tertiary amines or heterocyclic secondary and tertiary amines, where the aliphatic radicals can be linear or branched. Can be. One of the aliphatic substituents is
It contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, at least one of which is an anionic water-soluble group (eg, carboxy, sulfonate,
Sulfate). For examples of amphoteric surfactants, see December 30, 1975.
U.S. Pat. No. 3,929,678, issued to Laughlin et al.
See paragraphs lines 18-35. Preferred amphoteric surfactants, C ₁₂ ~
C ₁₈ betaines and sulfobetaines ( "sultaines"), include C ₁₀ -C ₁₈ amine oxides, and mixtures thereof.

When present, the amphoteric surfactant is typically present in an effective amount. More preferably, the composition may comprise at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5%, by weight of the composition, of an amphoteric surfactant. The composition also preferably comprises up to about 20%, more preferably up to about 15%, even more preferably up to about 10% by weight of the composition of an amphoteric surfactant.

Amine oxides are amphoteric surfactants and are selected from the group consisting of alkyl moieties containing one alkyl moiety of from about 10 to about 18 carbon atoms and alkyl and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms. A water-soluble amine oxide comprising two moieties selected from the group consisting of one alkyl moiety of about 10 to about 18 carbon atoms and an alkyl group containing about 1 to about 3 carbon atoms and a hydroxyalkyl group. 2
A water-soluble phosphine oxide comprising one moiety; and an alkyl moiety comprising from about 10 to about 18 carbon atoms and an alkyl moiety comprising from about 1 to about 3 carbon atoms and a hydroxyalkyl moiety. And water-soluble sulfoxides.

A preferred amine oxide surfactant has the formula:

[0171]

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Wherein R ³ is an alkyl, hydroxyalkyl containing from about 8 to about 22 carbon atoms,
Or an alkylphenyl group be, or mixtures thereof,; R ⁴ is an alkylene or hydroxyalkylene group or mixtures thereof containing from about 2 to about 3 carbon atoms; x is 0-3; each R ⁵ Is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or a polyethylene oxide group containing about 1 to about 3 ethylene oxide groups. The R ⁵ groups can form a ring structure via a bond to each other (eg, by an oxygen or nitrogen atom).

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

[0174] When present, the amine oxide surfactant is typically present in an effective amount.
More preferably, the composition comprises at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5%, by weight of the composition.
Amine oxide surfactant. The composition also preferably comprises no more than about 20%, more preferably no more than about 15%, even more preferably no more than about 10% by weight of the composition of an amine oxide surfactant.

Examples of suitable amine oxide surfactants are described in “Surfactants and Detergents”, Volumes I and II, Schwartz, Perry and Berch.

Suitable betaine surfactants include those of the general formula:

[0177]

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Wherein R is an alkyl group containing about 10 to about 22, preferably about 12 to 18 carbon atoms, a similar number having a benzene ring treated with an equivalent of about 2 carbon atoms. an alkylaryl group and arylalkyl group, and an amino or hydrophobic groups selected from the interference of similarity of the structure of an ether bond containing carbon, each R ¹ is 1
R ² is an alkyl group containing 1 to about 6 carbon atoms, and R ² is an alkylene group containing 1 to about 6 carbon atoms.

Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyl dimethyl betaine, tetradecyl dimethyl betaine, tetradecyl amidopropyl dimethyl betaine, and dodecyl dimethyl ammonium hexanoate. Other suitable amidoalkylbetaines are described in U.S. Patent Nos. 3,950,417, 4,137,191, and 4,375.
No. 421, as well as British Patent 2,103,236, all of which are incorporated herein by reference.

Zwitter Surfactants-Zwitter surfactants can be incorporated into the cleaning composition. These surfactants can be used as derivatives of secondary or tertiary amines or heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Can be described extensively. U.S. Pat. No. 3, issued to Laughlin et al. On December 30, 1975
See, for example, column 19, line 38 to column 22, line 48 for zwitterionic surfactants in U.S. Pat. Amphoteric and zwitterionic surfactants are generally used as a combination with one or more anionic and / or nonionic surfactants.

Detergent Enzymes -Enzymes are preferably included in the cleaning compositions of the present invention for a variety of purposes, including the removal of protein-based, carbohydrate-based, or triglyceride-based soils from a substrate. Recent disclosures of enzymes in detergents useful herein include chondriotinase (EP 747,469A), protease variants (WO 96 / 28566A, WO 96 / 28557A, WO 9).
6 / 28556A, WO 96 / 25489A), xylanase (EP 7)
09,452A), keratinase (EP 747,470A), lipase (GB 2,297,979A, WO 96 / 16153A, WO 96).
/ 12004A, EP 698,659A, WO 96 / 16154A), cellulase (British Patent 2,294,269A, WO 96/27649).
A, UK Patent No. 2,303,147A), thermitase (WO 96/285)
58A). More generally, suitable enzymes include cellulases, hemicellulases, proteases, glucoamylases, amylases, lipases, cutinases, from any suitable source, such as plant, animal, bacterial, fungal, and yeast sources.
Pectinase, xylanase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, chondriotinase, thermitase, pentosanase, malanase, β
-Glucanase, arabinosidase, or a combination thereof. The preferred choice is influenced by factors such as pH activity and / or optimal stability, temperature stability, and stability against cleaning actives, builders, and the like. In this connection, bacterial or fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferred. Preferred compositions are cleaning compositions comprising a cocktail with conventional applicable enzymes such as proteases, amylases, lipases, cutinases, and / or cellulases. Suitable enzymes are also described in US Pat. No. 5,677,272.
No. 5,679,630, No. 5,703,027, No. 5,703
Nos. 034, 5,705,464, 5,707,950, and 5,7
No. 07,951, No. 5,710,115, No. 5,710,116, No. 5,710,118, No. 5,710,119, and No. 5,721,
No. 02.

The composition comprises at least about 0.0001%, more preferably at least about 0.0005%, even more preferably at least about 0.001% enzyme by weight of the composition. The cleaning composition also preferably comprises no more than about 5%, more preferably no more than about 2%, even more preferably no more than about 1% by weight of the composition.

[0183] As used herein, "detergent enzyme" means any enzyme that has an effective effect in washing, removing stains or other cleaning ingredients. Preferred detergent enzymes are hydrolases such as proteases, amylases and lipases. Amylases and / or proteases, including both currently available and improved versions, are highly preferred.

Enzymes are usually incorporated into detergents or detergent additive compositions at a level sufficient to obtain a “detergent effective amount”. "Washing effective amount" refers to any amount that can improve the effect of washing, removing stains, removing stains, whitening, deodorizing, or obtaining clarity on a substrate such as textiles and dishes. As a practical amount for currently commercially available preparations, typical amounts are up to about 5 mg per gram of cleaning composition.
More typically 0.01 mg to 3 mg of active enzyme. As described elsewhere, the compositions herein typically comprise from 0.001% to 5% by weight, preferably 0% by weight.
. Contains from 01% to 1% by weight of a commercially available enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to obtain 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, it may be desirable to increase the active enzyme content of commercial preparations to improve spots / filming or other end results with a minimum amount of non-catalytic actives. Absent. Higher activity levels may also be desirable for highly concentrated detergent formulations.

[0185] Proteolytic enzymes - proteolytic enzymes, animal, vegetable or microorganism (preferred) origin. Proteases used in the cleaning compositions herein include, but are not limited to, trypsin, subtilisin, chymotrypsin, and elastase-type proteases. Subtilisin-type proteolytic enzymes are preferred for use herein. Particular preference is given to bacterial serine proteases obtained from Bacillus subtilis and / or Bacillus licheniformis.

Suitable proteolytic enzymes include commercially available Novo Industry A / S (
Alcalase (trade name) (preferred), Esperase (trade name), Savinase (trade name), Gist of Copenhagen, Denmark.
-Maxadese of brocade (Delft, Netherlands)
(Trade name) Maxacal (trade name) and Maxapem15 (trade name)
(Protein Engineered Maxacal (trade name)), Subtilisin BPN and BP
N ′ (preferred) is included. Preferred proteolytic enzymes are also Genen
cor International, Inc. (San Francisco,
Modified bacterial serine proteases, such as those manufactured in California, California, which are described in EP 251, issued Dec. 28, 1994.
No. 446B (especially pages 17, 24 and 98), and herein referred to as "
Protease B ". July 9, 1991, granted to Venegas
U.S. Pat. No. 5,030,378, issued to the United States of America, is hereby incorporated by reference.
A "(same as BPN '), a modified bacterial serine protease (G
enencor International). In particular,
For a full description, see US Pat. No. 5,030,378, columns 2 and 3 (Pr
othease A and its amino acid variants). Other proteases are sold under the following trade names: Primase, Durazym, Op
ticlean and Optimase. A preferred proteolytic enzyme is A
Icalase (brand name) (Novo Industry A / S), BPN '
, Protease A and 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 herein. Proteases described in our co-pending application USSN 08 / 136,797 can also be included in the detergent compositions of the present invention.

[0188] Another preferred protease, called "Protease D", is a variant of carbonyl hydrolase having a non-naturally occurring amino acid sequence. This is the position in the carbonyl hydrolase equivalent to position +76, preferably +99, +
101, +103, +104, +107, +123, +27, +105, +10
9, +126, +128, +135, +156, +166, +195, +197
, +204, +206, +210, +216, +217, +218, +222,
+260, +265, and / or +274 (Genencor International's WO 95/10615 published April 20, 1995).
Bacillus amyloliquenfaces subtil as described in
isin numbering) (A. Bae filed October 13, 1994)
The combination of one or more amino acid residues equivalent to a position selected from the group consisting of: Derived from precursor carbonyl hydrolase in which different amino acids have been substituted for groups.

Useful proteases are also described in PCT Publication: WO 95/30010 from Procter & Gamble Company published November 9, 1995.
, Procter & Gamble Co, published on November 9, 1995
mpany WO 95/30011, Pr published on November 9, 1995
Octer & Gamble Company, WO 95/29979.

[0190] Protease enzymes are present in the compositions of the present invention in an amount of from 0.0001% to 2% by weight of the composition.
Active enzymes can be incorporated at the level of weight percent. The composition comprises at least about 0.0001%, more preferably at least about 0.0002%, even more preferably at least about 0.0005%, even more preferably at least about 0.001% by weight of the composition. Including active enzymes of protease enzymes. The composition also preferably comprises no more than about 2%, more preferably no more than about 0.5%, even more preferably no more than about 0.1%, even more preferably no more than about 0.05% by weight of the composition. Including active enzymes of the following protease enzymes:

Amylases -Amylases (α and / or β) can be included for the removal of carbohydrate-based soils. Suitable amylases are Termamyl (trade name) (Novo Nordisk), Fungamyl (trade name) and BAN (trade name).
Product Name) (Novo Nordisk). Enzymes can be obtained from any suitable source (
Plant, animal, bacterial, fungal, and yeast origin).

The composition may comprise at least about 0.0001%, more preferably at least about 0.0002%, even more preferably at least about 0.0005%, even more preferably at least about 0.001% by weight of the composition. Contains by weight the active enzyme of the amylase enzyme. The composition also preferably comprises no more than about 2%, more preferably no more than about 0.5%, even more preferably no more than about 0.1%, even more preferably no more than about 0.05% by weight of the composition. Includes the following amylase enzyme active enzymes:

The amylase enzyme is also available from Novo Nordisk WO 95/26397.
And those described in co-pending application PCT / DK96 / 00056. Accordingly, other specific amylase enzymes used in the cleaning compositions of the present invention include:
Includes: (A) In a temperature range of 25 ° C. to 55 ° C. and a pH range of pH 8 to 10, Phase
base (trade name) α-amylase activity was measured, and Termamyl was measured.
Α-Amylase characterized by having a specific activity at least 25% higher than that of (trade name) is included. This Phasebas (trade name) α
-Evaluation of amylase activity is described on pages 9 to 10 of WO 95/26397.

(B) The α-amylase of (a) containing the amino acid sequence described in the sequence listing (SEQ ID listing) in the above reference, or an α-amylase having at least 80% homology to the amino acid sequence described in the sequence listing.

(C) α-amylase from an alkalophilic Bacillus sp. Containing the following N-terminal amino acid sequence: His-His-Asn-Gly-Thr-Asn-Gly
-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr
-Leu-Pro-Asn-Asp. Polypeptides are synthesized using algorithms (Lipman and Pearson, S
Science 227, 1985, pp. 1435), when it is clear that the amino acid sequences are X% identical, it is considered to be X% homologous to the parent amylase.

(D) The α-amylase is an alkalophilic Bacillus species, especially NCIB 122
89, NCIB 12512, NCIB 12513, and DSM 93
Α-amylases (ac) obtainable from 5 strains. In the context of the present invention, the term "obtainable from" refers not only to the amylase produced by the Bacillus strain, but also to the amylase encoded by the DNA sequence isolated from such a Bacillus strain and to the character of the DNA sequence. It is intended to indicate amylase produced in the transformed host cell.

(E) α-amylase that is positive for immunological cross-reactivity with an antibody raised against α-amylase having an amino acid sequence corresponding to each of (ad).

(F) (i) having one of the amino acid sequences shown corresponding to the amylases of (ae), or (ii) at least 80% homology with one or more of the above amino acid sequences And / or having one of the above amino acid sequences.
Encoded by a DNA sequence that exhibits immunological cross-reactivity with an antibody raised against amylase and / or hybridizes with a probe identical to the DNA sequence encoding α-amylase having one of the above amino acid sequences A variety of the following parent amylase variants: This variant comprises: 1. at least one amino acid residue of the parent α-amylase has been deleted 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 At least one amino acid residue has been inserted into the parent α-amylase, and the variant has α-amylase activity and exhibits at least one of the following properties with respect to the parent α-amylase: improved heat resistance, oxidation Increased stability, reduced Ca ion dependence, stability at neutral to relatively high pH and / or increased α-amylase activity, increased α-amylase activity at relatively high temperatures, or pH of the medium Isoelectric point (pI) for better matching of the pI value of the α-amylase variant to
Increase or decrease. The variants are described in patent application PCT / DK96 / 00056.

Other amylases suitable herein include, for example, British Patent No. 1,296,839 to Novo, International Bio-Synt.
hetics, Inc. RAPIDASE (brand name) and Novo TE
RMAMYL (product name) is included. Novo's FUNGAMYL (trade name) is particularly useful. Enzymatic procedures for improving stability (eg, oxidative stability) are known. For example, J. Biological Chem, Vol. 260, No. 11,
See June 1985, pages 6518-6521. Certain preferred embodiments of the compositions of the present invention are directed to the stability of detergents, such as for automatic dishwashing types, especially 1993
Amylases with improved oxidative stability, as measured against the TERMAMYL (trade name) reference point, which has been used commercially since 2010, can be used. These preferred amylases herein have a oxidative stability against hydrogen peroxide / tetraacetylethylenediamine, eg, in a buffer of pH 9-10, as measured against the reference amylase described above, for example, a general oxidative stability such as about 60 ° C. Thermal stability to typical washing temperatures, or "enhanced stability" properties which are at least characterized by one or more measurable improvements in alkali stability, eg, at a pH of about 8 to about 11. ing. Stability can be measured using any of the disclosed technical tests. Stability-enhancing amylase can be obtained from Novo or Genencor Internationala
l. One class of particularly preferred amylases herein is one or more Bacillus amylase, particularly Bacillu, regardless of whether one, two, or more amylase strains are direct precursors.
Has commonality derived from site-directed mutagenesis from sα-amylase. With respect to the above-mentioned reference amylase, the oxidative stability-improving amylase is particularly preferred for use in bleaching, more preferably in oxygen bleaching (excluding chlorine bleaching) as the detergent composition herein. Such preferred amylases include: (a) Novo WO 94/02597 amylase (B. licheniformis α-amylase (TERMAMYL (published Feb. 3, 1994), incorporated by reference above).
197) or similar parent amylase (B. amyloliq)
eufaciens, B .; subtilis, or B. subtilis; stearother
mofilus, etc.), further exemplified by mutants in which a methionine residue located in a homologous position variant is substituted with alanine or threonine (preferably threonine)); 207th A by Mitchinson
American Chemical Society National Me
eting with the title "Oxidation-resistant afaamylase", Gen
A stability enhancing amylase as described by Encor International. Among them, α-amylase is inactive in bleaching in automatic dishwashing detergents, but Genencor reports that B-amylase is inactive. licheniformis NCIB
It is noted that 8061 produced an amylase with improved oxidative stability. Methionine (Met) has been identified as a residue that is likely to be modified. The methionine at positions 8, 15, 197, 256, 304, 366, and 438, responsible for the specific mutation, were substituted at one time to give specific mutants, especially M197L and M197T. Is important, and the M197T variant is the most stable expression variant. Stability was measured using CASCADE (trade name) and SUNLIGHT (
(Product name). (C) Particularly preferred amylases herein include WO
Amylase variants described in US Pat. No. 95 / 10603A and further modified by the direct parent marketed by the assignee Novo as DURAMYL. Other particularly preferred amylases with improved oxidative stability include Genencor.
Amylases described in International Publication WO 94/18314 and Novo Publication WO 94/02597 are included. For example, any other oxidative stability enhancing amylase derived by site-directed mutagenesis from the available parental forms of amylase chimeras, hybrids, or mere mutants can be used. Other preferred enzyme modifications are also available. Novo W
See O 95 / 09909A.

[0200] Cellulases useful herein include bacterial and fungal forms, particularly between pH 5 and 9.5. U.S. Patent No. 4,435,307, issued March 6, 1984 to Barbesguard, et al., Includes Humicola insol.
Suitable fungal cellulose from ens or Humicola DSM1800 strain or a cellulase 212-producing fungus belonging to the genus Aeromonas and cellulose extracted from the hepatopancreas of the marine mollusc Dolabella Auricula Solider are disclosed. Suitable cellulases are also disclosed in British Patent No. A-2.
No. 075,028, British Patent No. A-2,095,275, and German Patent No. 2,247,832. CAREZYME (trade name) and CELLUZYME (trade name) are particularly useful. Novo's WO 91/1
See also 7243.

The composition is preferably at least about 0.0001%, more preferably at least about 0.0002%, even more preferably at least about 0% by weight of the composition.
. 0005%, even more preferably at least about 0.001%, by weight of cellulase and / or peroxidase enzyme active enzyme. The composition also comprises
Preferably, no more than about 2%, more preferably no more than about 0.5%, even more preferably no more than about 0.1%, even more preferably no more than about 0.05%, by weight of the composition, of cellulase and / or Or an active enzyme of a peroxidase enzyme.

Also suitable are a special class of lipases, cutinases that are considered lipases that do not require surface activation [EC 3.1.1.150]. The addition of cutinase to the cleaning composition is described, for example, in WO-A-88 / 09367 (Genenco
r).

Lipases -Suitable lipase enzymes include the Pseudomonas group (Pseudomonas stutzeri A) disclosed in GB 1,372,034.
TCC 19.154). Suitable lipases include the microorganism Pseudomonas fluorescens I
Includes those that show a positive immunological cross-reaction with antibodies to lipase produced by AM 1057. This lipase is available from Amano Pharmaceutical (Nagoya, Japan) under the trade name L
It is commercially available as ipase P “Amano” (hereinafter, referred to as “Aano-P”). Further suitable lipases are M1 Lipase (trade name) and Lipo
lipase such as max (trade name) (Gist-Brocades). Other suitable commercially available lipases include Amano-CES, such as Chromactact
er viscosum lipase (eg, Toyo Brewery, Tagata, Jap
an Chromobacter vissum var. lypolytic
um NRRLB 3673); S. Biochemical Corp.
, U.S. S. A. And Disynth Co. , The Netherlands
ds Chromobacter viscosum lipase and, for example, P
lipase from Pseudomonas gladioli. Humi
Cola lanuginosa and derived from Novo (European Patent No. 341 947)
LIPOLASE® is a preferred lipase for use herein. Lipase and amylase variants that are stable to peroxidase enzymes are described in WO 94/14951 published by Novo. See also WO 92/05249 and RD 94359044.

Highly preferred lipases are, for example, leucine (L) at the aspartic acid (D) residue at position 96 of the natural enzyme of Humicola lauginosa.
D96, a natural lipase from Humicola lanuginosa, described in U.S. Patent Application No. 08 / 341,826 (see also WO 92/05249).
L lipolytic enzyme variant. According to this nomenclature, the substitution of leucine for the aspartic acid at position 96 is designated as D96L. Preferably, Humicola
Lauginosa DSM strain 4106 is used.

Despite the very large number of publications on lipase enzymes, Humic
ola lauginosa, and Aspergillus or
Only lipase produced in yzae is widely and generally applied as an additive for cleaning products. As mentioned above, Novo Nordisk trade name Lipol
In order to optimize the dirt removal function of Lipolase, which is commercially available as “ase” (trade name) and Lipolase Ultra (trade name), Novo No.
rdisk produces a number of variants. As described in WO 92/05249, the D96L variant of native Humicola lauginosa lipase is 4.4 times lard more than wild type lipase (enzyme compared in amounts ranging from 0.075 to 2.5 mg protein / liter). The dirt removal efficiency has been improved. Nov
o Research Disclosure No. 35994 published on March 10, 1994 by Nordisk.
Then, the lipase variant (D96L) was added in an amount of 0.001 to 1 per liter of detergent solution.
It is disclosed that an amount equivalent to 00 mg (5 to 500,000 LU / liter) can be added.

The composition may comprise at least about 0.0001%, more preferably at least about 0.0002%, even more preferably at least about 0.0005%, even more preferably at least about 0.001% by weight of the composition. Contains by weight the active enzyme of the lipase enzyme. The composition also preferably comprises no more than about 2%, more preferably no more than about 0.5%, even more preferably no more than about 0.1%, even more preferably no more than about 0.05% by weight of the composition. Includes active enzymes of the following lipase enzymes:

Various carbohydrate enzymes that confer antimicrobial activity can also be included in the present invention. Such enzymes include U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843, and 5,356,803, the disclosures of which are herein incorporated by reference. Endoglycosidases, type II endoglycosidases, and glucosidases, which are incorporated by reference herein. Of course, other enzymes having antimicrobial activity (including peroxidase, oxidase, and other enzymes) can be used as well.

The range of enzymatic materials and methods of incorporation into synthetic detergent compositions are also described in WO 89/08694 from Novo and US Pat. No. 3,553,139 to McCarty et al. On Jan. 5, 1971. It has been disclosed. Enzymes can also be
U.S. Patent No. 4,101,457 issued to Place et al. On July 18, 78 and U.S. Patent No. 4,507 issued to Hughes on March 26, 1985.
, 219. Liquid detergent formulations and enzymatic materials useful for incorporation into the formulations are disclosed in U.S. Patent No. 4,261,868, issued to Hora et al. On April 14, 1981. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described in U.S. Patent No. 3,600,319, issued to Gedge et al. On April 17, 1971; EP 199,405, issued to Venegas on October 29, 1986; Second
No. 00,586. Enzyme stabilization systems are also described in US Pat.
570. Useful Bacillus sp. AC13 that produces proteases, xylanases, and cellulases is described in Novo published WO 94 /
01532.

If any enzymes are present in the composition, an enzyme stabilizing system can be included in the composition of the present invention. Enzyme Stabilizing System- Preferred compositions herein further comprise about 0.001% by weight
From about 0.005% to about 8%, most preferably from 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 proteases or other enzymes used herein. Such stabilizing systems include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, polyhydroxy compounds and mixtures thereof (198).
U.S. Pat. No. 4,261,868 issued to Hora on Apr. 14, 2014,
No. 4,404,543 assigned to Tai issued on September 13, 1983, L
No. 4,318,818 issued to etton et al., issued No. 4,243,543 issued to Guildert et al., issued Jan. 6, 1981, and issued to Boskamp issued Jan. 31, 1984. No. 4,462,922, 1985
No. 4,532,064 issued to Boskamp, issued on July 30, 1985, and Severson Jr. issued on Aug. 27, 1985. The fourth granted to
No. 5,537,707, all of which are incorporated herein by reference.

[0210] The compositions comprise at least about 0.001%, more preferably at least about 0.005%, even more preferably at least about 0.01%, by weight of the composition, of an enzyme stable system. The composition also preferably includes up to about 10%, more preferably up to about 8%, more preferably up to about 6%, by weight of the composition, of an enzyme stable system.

One stabilization approach is to use an aqueous source of calcium and / or magnesium ions in the final composition to introduce such ions into the enzyme.
Calcium ions are generally more effective than magnesium ions, and only one type of cation may be used herein. Typical cleaning compositions (particularly,
Liquid) contains about 1 to about 30 mmol, preferably about 2 to about 20 mmol, more preferably 8 to about 12 mmol of calcium ions per liter of final cleaning composition, but the multiplicity of enzyme incorporated Variations are possible depending on factors including, type, and level. Preferably, water-soluble calcium or magnesium salts are used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide, and calcium acetate. More generally, calcium or magnesium sulfate salts corresponding to the exemplified calcium salts can be used. Higher levels of calcium and / or magnesium may of course be useful, for example, to enhance the grease removal effect of certain types of surfactants. However, it is particularly preferred that the composition does not further comprise calcium ions, and even more preferred that the composition does not comprise calcium ions.

Another stabilization approach is through the use of borates. See U.S. Patent No. 4,537,706 to Severson. If a borate stabilizer is used, borate levels can be as high as 10% or more by weight of the composition, but more typically up to about 3% by weight of boric acid or other borate compounds (borax or boric acid). Orthoborate, etc.) are suitable for use in liquid detergents. Substituted boric acids (such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid, etc.) can be used in place of boric acid and such substituted boronic acids are reduced due to the reduction in total boron levels in the detergent composition. Derivatives can be used.

In addition, 0 to about 10%, preferably 0.01% to about 6%, by weight of chlorine bleaching or oxygen bleaching scavengers may be added to the compositions of the present invention to provide chlorine bleaching present in many waterworks. Attack and inactivation of the species, especially under alkaline conditions, can be prevented. Although the chlorine level in the water is low (typically about 0.5 ppm to about 1.75 ppm), the available chlorine in the total volume of water that contacts the enzymes during dishwashing is usually high. Thus, enzyme stability during use can be a problem.

Suitable chlorine scavenger anions are salts containing ammonium cations. These are reduced substances such as sulfite, bisulfite, thiosulfite, thiosulfate, iodide, carbonate, ascorbate, etc., organic amines (antioxidants such as ethylenediaminetetraacetic acid, or alkali metal salts thereof).
It can be selected from the group consisting of monoethanolamine, and mixtures thereof. Sulfate, bisulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate, percarbonate, phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate Other conventional anions such as, maleate, tartrate, salicylate and the like and mixtures thereof can also be used.

Builders -Detergent builders are optionally included in the compositions of the present invention.
In solid formulations, the builder may act as a surfactant absorbent. Alternatively, the composition can be formulated with a completely water-soluble builder (organic or inorganic), depending on the intended purpose.

Suitable silicate builders include water-soluble and hydrated solid forms, including linear, layered, or three-dimensional structures as well as amorphous solid silicates or other forms (eg, particularly adapted for use in non-structured liquid detergents). To include). Alkali metal silicates, especially liquid and solid silicates having a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1 (available from PQ Corp. under the trade name BRITESIL (trade name)) Solid hydrous silicate with a ratio of 2 (eg BRITESIL H
2O) and layered silicates (eg, HPR published on May 12, 1987)
silicates described in U.S. Pat. No. 4,664,839 to ieck))
Is preferred. NaSKS-6 (sometimes abbreviated as "SKS-6")
crystalline layered aluminum-free δ-Na ₂ Si available from echst
O ₅ in the form of silicates, particularly preferred in granular compositions. See German Patent Nos. 3,417,649 and 3,742,043. Formula _{NaMSi x O 2x + 1 · yH} 2 O ( wherein, M is sodium or hydrogen, x is 1
. Other layered silicates can also or alternatively be used herein, such as a number from 9 to 4, preferably 2, and y is from 0 to 20, and preferably 0. . Hoechst's layered silicates also include NaSKS-5, NaSKS-7, and NaSKS-11 as α, β, and γ layered silicate forms. Other silicates, magnesium silicate, which can act as a desiccant in the granules and a component in the foam control system, may also be useful.

US Patent No. 5,427,71 to Sakaguchi et al., Issued June 27, 1995.
As taught in No. 1, the following anhydrous form of the general formula xM ₂ O.ySiO ₂ .zM′O (
Wherein M is Na and / or K, M ′ is Ca and / or Mg, y / xP is 0.5-2.0, z / x is 0.005-1.0. Synthetic crystalline ion-exchange materials or hydrates thereof having a chain structure and composition represented by (A) are also suitable for use herein.

Aluminosilicate builders such as zeolites are particularly useful in granular detergents
However, it can also be incorporated into liquids, pastes, or gels. The empirical formula [M _z (AlO_Two)_z(SiO_Two)_v] XH_TwoO (where z and v are at least 6 integers)
M is an alkali metal, preferably Na and / or K, z and v
Is in the range of 1.0 to 0.5, and x is an integer of 15 to 264).
What has is appropriate for the purpose of the present invention. Aluminosilicate can be crystalline or amorphous
And can be obtained naturally or synthetically. The method for producing aluminosilicate is 1976
U.S. Patent No. 3,985,6, issued to Krummel et al.
No. 69. Preferred synthetic crystalline aluminosilicate ion exchange material
Are as Zeolite A, Zeolite P (B) and Zeolite X
It is commercially available and, to any extent, this is known as Zeolite P (so-called Z
elite MAP). Use natural forms containing clinoptilolite
be able to. Zeolite A has the formula Na₁₂[(AlO_Two)₁₂(SiO_Two)₁₂
] XH_TwoO, where x is 20-30, especially 27. Anhydro Zeo
Lite (x = 0-10) can also be used. Preferably, alumino
The silicate has a particle size of 0.1 to 10 microns in diameter.

Instead of or in addition to the above silicates and aluminosilicates, for example, to assist in adjusting the hardness of minerals (especially Ca and / or Mg), wash water, or to help remove surface particulate soils A detergent builder can optionally be included in the compositions herein. The builder can act by various mechanisms of forming a water-soluble or insoluble complex with the hardness-imparting ions, by ion exchange and by the surface being favored by the precipitation of the hardness-imparting ions over the surface of the wash. The amount of the builder can vary depending on the end use and the physical form of the composition. Buildered detergents typically contain at least about 1% builder. Liquid formulations typically contain from about 5% to about 50%, more typically 5% to 35% of a builder. The particle formulation typically comprises from about 10% to about 80%, more typically from about 15% to 50%, by weight of the detergent composition, of the builder. Does not exclude lower or higher levels of builders. For example, certain formulations may be non-builders (ie, such as in some hand dishwashing compositions, the composition does not include a builder).

Useful builders herein are phosphates and polyphosphates (especially sodium salts), carbonates, bicarbonates, sesquicarbonates, carbonate minerals other than sodium carbonate or sesquicarbonates;
Di, tri, and tetracarboxylates, especially acids, sodium, potassium,
Or alkanol ammonium salt forms of water-soluble non-surfactant carboxylates (including aliphatic and aromatic forms); and phytic acid. Borates (for pH buffering), sulphates (especially sodium sulphate), and any other fillers or carriers which may be important for the operation of detergent compositions containing these stable surfactants and / or builders Can compensate.

A builder mixture, sometimes called a “builder system”, can be used,
This may typically include two or more conventional builders, optionally chelates, pH buffers, or fillers, although the latter materials will generally have a reduced amount of material herein. It is explained separately from the description. With respect to the relative amounts of surfactant and builder in the detergents of the present invention, a preferred builder system typically comprises about 60: 1 to 1
Formulated in a weight ratio of surfactant to builder of about 1:80. Certain preferred laundry detergents are from 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1.
It has the above ratio in the range of 0-3.0: 1.0.

Where permitted by law, detergent builders containing P may be preferred, including alkali metal, ammonium, and alkali ammonium salts of polyphosphorates (eg, tripolyphosphate, pyrophosphate, glass, etc.). Polymerized meta-phosphate) and phosphonates.

Suitable carbonate builders include the alkaline earth metals and alkali metal carbonates described in German Patent Application No. 2,321,001 published Nov. 15, 1973, including sodium bicarbonate, Mineral salts of sodium carbonate, sodium sesquicarbonate, and other carbonates (such as trona) or any complex salt of sodium carbonate and calcium carbonate (for anhydrous, composition 2
Na ₂ CO ₃ · CaCO ₃ etc.), calcite, aragonite,
Higher surface area morphologies as compared to calcium carbonate, including and vaterite, especially dense calcite, may be useful.

[0224] Suitable "organic detergent builders" as described herein for use in the cleaning components include water-soluble, non-surfactant polycarboxylate compounds, including dicarboxylates and tricarboxylates. . More typically, the builder polycarboxylate has multiple carboxylate groups, preferably at least three carboxylate. The carboxylate builder can be formulated in an acidic, partially neutral, neutral or overbased form. In the case of salt forms, alkali metal (such as sodium, potassium and lithium) or alkanol ammonium salts are preferred. U.S. Patent No. 3,128,287 to Berg, issued April 7, 1964; Lamberti, issued January 18, 1972.
No. 3,635,830, granted to Bush issued May 5, 1987.
"TMS / TDS" builder described in U.S. Pat. No. 4,663,071 and U.S. Pat. Nos. 3,923,679, 3,835,163, and 4
Nos. 4,158,635, 4,120,874 and 4,102,90.
See other ethers, including cyclic and acyclic compounds described in No. 3.

Other suitable organic detergent builders are ether hydroxy polycarboxylates,
Copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3
Various alkali metal salts (ammonium and substituted ammonium salts) of polyacetic acids such as carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid; and mellitic acid Succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

Citrates such as citric acid and its soluble salts) are important carboxylate builders, for example for light duty liquid detergents, due to their availability from a renewable resource and biodegradable point of view. Citrates can also be used in particulate compositions, especially in combination with zeolites and / or layered silicates.
Oxydisuccinates are also particularly useful in such compositions and combinations.

Where permitted, alkali metal phosphates (such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate) can be used, particularly in rod-like formulations. Phosphate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (U.S. Pat. Nos. 3,159,581, 3,213,030, 3,422,021) No. 3,400,148 and No. 3,422,137) can also be used and can have the desired anti-scaling properties.

Certain detersive surfactants or single-chain homologs thereof also have a builder effect. In a clear formula to illustrate the purpose, these substances are included as detersive surfactants if they have a surfactant ability. Preferred types for the builder function are exemplified below: 3,3-Dicarboxy-4-oxa-1 as disclosed in U.S. Pat.
, 6-Hexanediolate and related compounds. The succinate builders, C ₅
-C ₂₀ alkyl and alkenyl succinic acids and salts thereof include. Succinate builders also include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinate is described in European Patent Application No. 86000690.5 / 0,200,263 published November 5, 1986. Fatty acids (e.g., C ₁₂ -C ₁₈ monocarboxylic acids) are also surfactant / builder materials alone or the builder (especially citrates and / or succinate builders) as a combination of incorporated into the composition, Additional builder activity can be obtained. Other suitable polycarboxylates are disclosed on March 13, 1979
U.S. Patent No. 4,144,226 issued to Crutchfield et al. And 3,308,06 issued to Diehl issued March 7, 1967.
No. 7. See also U.S. Patent No. 3,723,322.

[0229] Another type of inorganic builder materials which can be used have the formula _{(M x) i Ca y (} CO 3) z [ wherein, x and i are integers of 1 to 15, y is 1 An integer of 10;
z is an integer from 2 to 25, M _i are cations, at least one these are water-soluble, wherein sigma _i = 1 as formula has a neutral or "balanced came off the" charge
−15 (valence of x _i × Mi) + 2y = 2z]. These builders are referred to herein as "mineral builders" and examples, uses, and preparations of such builders can be found in US Pat. No. 5,707,959. Another suitable class of inorganic builders is magnesium silicate (WO 97/017)
9).

Suitable polycarboxylate builders for use herein include maleic acid, citric acid, preferably in the form of a water-soluble salt, of the formula R—CH (COOH) CH ₂ (C
OOH) [wherein, R C ₁₀ -C ₂₀ alkyl or alkenyl, preferably C ₁₂ ~
C ₁₆ , or R can be substituted with hydroxyl, sulfosulfonyl, or sulfone substituents]. Mixtures of these suitable polycarboxylate builders, such as a mixture of maleic acid and citric acid, are also envisioned. Specific 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 alkanol ammonium salts.

Other suitable polycarboxylates are the oxodisuccinates described in US Pat. No. 4,663,071 and mixtures of tartrate monosuccinate and tartrate disuccinate.

In particular, for use herein as liquids, suitable fatty acid builders herein are saturated or unsaturated C ₁₀ -C ₁₈ fatty acids as well as the corresponding soaps. Preferred saturated species have 12 to 16 carbon atoms in the alkyl chain. A preferred saturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are dodecyl succinic and citric acid.

The composition preferably comprises at least about 0.2%, more preferably at least about 0.5%, even more preferably at least about 3%, even more preferably at least about 5% by weight of the composition. Includes% builder. The cleaning composition also comprises
Preferably, it comprises no more than about 50%, more preferably no more than about 40%, even more preferably no more than about 30%, even more preferably no more than about 25% by weight of the composition.

Magnesium Ion- The presence of magnesium ions (divalent) improves the detergency of various compositions, ie, compositions containing alkyl ethoxy sulfate and / or polyhydroxy fatty acid amide, for grease stains. This is especially true when the composition is used in soft water containing almost no divalent ions. Without wishing to be limited by theory, it is believed that magnesium ions increase surfactant loading at the oil / water interface, thereby reducing interfacial tension and improving grease cleaning. The compositions of the present invention herein containing magnesium ions exhibit good grease removal properties, are clearly gentle on the skin, and enhance storage stability.

The composition preferably comprises at least about 0.01%, more preferably at least about 0.015%, even more preferably at least about 0.02% by weight of the composition.
%, Even more preferably at least about 0.025% by weight of magnesium ions. The cleaning composition also preferably comprises no more than about 5%, more preferably no more than about 2.5%, even more preferably no more than about 1%, even more preferably no more than about 0.05% by weight of the composition. Including builders. In any case, the amount of magnesium ions present is always less than or equal to the amount of diamine present in the composition. Preferably, magnesium ions are added to the compositions of the present invention as hydroxide, chloride, acetate, formate, oxide, or nitrate salts.

The formulation of a composition comprising such a divalent ion in a substrate at an alkaline pH is:
It may be difficult due to the incompatibility between divalent ions (especially magnesium) and hydroxides. When both divalent ions and alkaline pH are combined with the surfactant mixture of the present invention, the grease detergency is superior to that obtained with either alkaline pH or divalent ions alone. However, during storage, the stability of these compositions becomes insufficient due to hydroxide precipitate formation. Therefore, the chelating agents discussed below would also be needed.

Diamine-The diamine used in the present invention is preferably essentially free of impurities. That is, “substantially free” means that the diamine is more than 95% pure,
That is, it is preferably 97%, more preferably 99%, and still more preferably 99.%.
5%, meaning that no impurities are contained. Examples of impurities that may be present in commercially available diamines include 2-methyl-1,3-diaminobutane and alkyl hydropyrimidine. In addition, it is believed that the diamine should be free from oxidation reactions to avoid diamine decomposition and ammonia formation. Further, if amine oxides and / or other surfactants are present, the amine oxides or surfactants should not include hydrogen peroxide. Preferred hydrogen peroxide levels in the amine oxide or amine oxide surfactant paste are 0 to 40 ppm, more preferably 0 to 15 ppm. If amine oxides and amine impurities in betaine are present, they should be minimized to the above levels for hydrogen peroxide.

Where the composition includes an enzyme, making a composition that is free of hydrogen peroxide is important.
Hydrogen peroxide reacts with the enzyme to destroy any functional benefits that the enzyme imparts to the composition. Even small amounts of hydrogen peroxide can cause problems with formulations containing enzymes. However, diamines can act as enzyme stabilizers by reacting with any existing peroxides and can prevent the enzyme from reacting with hydrogen peroxide. The only drawback of this enzyme stability with diamines is that the nitrogen compounds formed are thought to cause the malodors present in the diamine-containing compositions. When the diamine acts as an enzyme stabilizer, the advantage that the diamine originally gives to the composition, namely, grease washing, foaming,
Solubility and low temperature stability are also hindered. Accordingly, diamines may be used as enzyme stabilizers due to the use of compositions that are substantially free of hydrogen peroxide and / or the production of malodorous compounds and the reduced amount of diamines present to play their major role. Nevertheless, it is preferred to minimize the amount of hydrogen peroxide present as an impurity in the compositions of the present invention by using a non-diamine antioxidant.

It is further preferred that the compositions of the present invention do not emit a “foul odor”. That is, the odor existing in the upper space does not cause a negative reaction of the consumer. This can be accomplished in a number of ways, including the use of fragrances to mask any unwanted odors, the use of stabilizers such as antioxidants, chelating agents, and / or the use of diamines that are substantially free of impurities. Can be achieved. Without wishing to be limited by theory, it is believed that the major source of malodor in the compositions of the present invention is due to the presence of impurities in the diamine. These impurities can be formed during the preparation and storage of the diamine. Impurities can also be formed during the preparation and storage of the compositions of the present invention. The use of stabilizers, such as antioxidants and chelating agents, prevents and / or prevents the formation of impurities during the period between preparation and consumer use or thereafter. Therefore, it is most preferred to eliminate, suppress, and / or prevent this malodor formation by the addition of fragrances, stabilizers and / or the use of substantially impurity-free diamines.

One type of preferred organic diamine is pK₁And pK_TwoIs about 8.0 to about 11.
5, preferably in the range of about 8.4 to about 11, even more preferably about 8.6.
~ 10.75. Preferred materials for performance and consideration are 1,3
-Bis (methylamine) -cyclohexane, 1,3-propanediamine (pK₁
= 10.5, pK_Two= 8.8), 1,6-hexanediamine (pK₁= 11, pK _Two = 10), 1,3-pentanediamine (Dytek EP) (pK₁= 10.5
, PK_Two= 8.9), 2-methyl-1,5-pentanediamine (Dytek A)
) (PK₁= 11.2, pK_Two= 10.0). Other preferred materials are C_Four~
C₈Primary / primary diamines containing alkylene spacers in the range General
It is believed that primary diamines are preferred over secondary and tertiary diamines.
You.

Definition of pK1 and pK2. As used herein, "pKa1" and "pKa1"
"pKa2" is a type of quantity collectively known by those skilled in the art as "pKa". As used herein, pKa is used as well as those known to those of skill in the chemical arts. The values referred to herein are referred to as “Critical Stabili”.
ty Constants: Volume 2, Amines ", Smith and M
artel, Plenum Press, NY and London, 197
5 and the like. Further information on pKa can be obtained from the literature of the affiliates (information provided by Dupont, the supplier of the diamine).

As a tentative definition herein, the pKa of the diamine is specified in a total aqueous solution at 25 ° C. and an ionic strength between 0.1 and 0.5. pKa is an equilibrium constant that can vary with temperature and ionic strength. Therefore, the values reported in the literature may not match depending on the measurement method and measurement conditions. For clarity,
The relevant conditions and / or criteria used in the pKa of the present invention are defined herein or are described in "Critical Stability Constants, Volume 2,
Amines ". One typical assay is the potentiometric measurement of an acid with sodium hydroxide and "The Chemist's Re.
dy Reference Handbook ", Shugar and D
ean, McGraw Hill, NY, 1990, identification of pKa by the appropriate method.

[0243] Substituent and structural modifications that reduce pK1 and pK2 to less than about 8.0 include:
It has been identified that it is undesirable and causes a loss in performance. This includes
Ethoxylated diamines, hydroxyethyl-substituted diamines, diamines by substituting oxygen in the β-position (less often in the γ-position) with nitrogen in the spacer group (eg,
Jeffamine EDR 148). In addition, ethylenediamine-based materials are unsuitable.

Some of the diamines useful herein have the formula:

[0245]

Embedded image

Wherein R _2-5 are independently selected from H, methyl, —CH ₃ CH ₂ , and ethylene oxide, and C _x and C _v are such that x + v is from 3-6 methyl or branched alkyl groups. And A is optionally present and is selected from electron donating or accepting moieties selected to adjust the pKa of the diamine to the desired range. If A is present, x and y must both be one or more.

Alternatively, the diamine can be an organic diamine having a molecular weight of 400 g / mol or less. These diamines preferably have the following formula:

[0248]

Embedded image

Wherein R ⁶ is independently hydrogen, C ₁ -C ₄ straight or branched chain alkyl, the following formula — (R ⁷ O) _m R ^{8 wherein} R ⁷ is C ₂ -C ₄ linear or branched alkylene, and be a mixture thereof; R ⁸ is hydrogen, C ₁ -C ₄ alkyl, and mixtures thereof; m is selected from the group consisting of alkyleneoxy having 1 to 10] ; X is, i) C ₃ ~C ₁₀ linear alkylene, C ₃ -C ₁₀ branched alkylene, C ₃ -C ₁₀ cyclic alkylene, C ₃ -C ₁₀ branched cyclic alkylene, the following formula - (R ⁷ O) _m R ⁷ - [wherein, R ⁷ and m are the same as defined above alkyleneoxyalkylene having; ii) C ₃ ~C ₁₀ straight-chain, C ₃ -C ₁₀ branched, C ₃ ~ C ₁₀ cyclic, C ₃ -C ₁₀ branched cyclic alkylene, C ₆ -C ₁₀ arylene, wherein the unit is the pK of the diamine. comprising one or more electron donating or accepting moieties that make a higher than 8; and iii) units selected from the mixture of (i) and (ii), wherein the pKa of the diamine is at least 8. Having.

Examples of preferred diamines include dimethylaminopropylamine, 1,6-hexanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, and 1,3-pentanediamine (trade name: Dytek Marketed in EP),
1,3-diaminobutane, 1,2-bis (2-aminoethoxy) ethane (commercially available under the trade name Jeffamine EDR 148), isophoronediamine, 1,3-bis (methylamine) -cyclohexane, and mixtures thereof Is included.

Polymerizable Foam Stabilizers- The compositions of the present invention may optionally include a heavy duty foam stabilizer. These polymerized foam stabilizers enhance foam volume and foam persistence without sacrificing the grease removal capacity of the liquid detergent composition. These polymerization type foam stabilizers,
i) The following equation

[0252]

Embedded image

[Wherein R is independently hydrogen, C₁~ C₈Alkyl, and mixtures thereof, ¹ Is hydrogen, C₁~ C₆Alkyl, and mixtures thereof, wherein n is 2-6]
Of (N, N-dialkylamino) alkyl acrylate ester having
And ii) if the ratio of (ii) to (i) is 2: 1 to 1: 2, then (i) and
Remar

[0254]

Embedded image

Preferably, R ¹ is selected from hydrogen, C ₁ -C ₆ alkyl, and mixtures thereof. As identified by conventional gel permeation chromatography, the molecular weight of the polymerized blowing agent is from about 1,000 to about 2,000,000, preferably about 5
From about 10,000 to about 1,000,000, more preferably from about 10,000 to about 750
2,000, even more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to about 200,000. The polymerizable foam stabilizer can optionally be present in the form of either an inorganic or organic salt, such as a citrate, sulfate, or nitrate salt of an (N, N-dimethylamino) alkyl acrylate ester.

One preferred polymerizable foam stabilizer is a (N, N-dimethylamino) alkyl acrylate ester, ie, of the formula:

[0257]

Embedded image

The composition comprises preferably at least about 0.01%, more preferably at least 0.05%, even more preferably at least 0.1% by weight of the composition of a polymerizable blowing agent. The cleaning composition also preferably comprises no more than about 15% by weight of the composition,
More preferably, it contains 10% by weight or less, even more preferably 5% by weight or less of a polymerizable foaming agent.

Other suitable polymerized blowing agents, including viscosity enhancing foam stabilizers and zwitterionic foam stabilizers, are described in PCT / US98 / 24853 filed Nov. 20, 1998 (accession number 6938), 1998. PCT / US98 / 24 filed on November 20, 2008
707 (reference number 6939), PCT / U filed on November 20, 1998
S98 / 24699 (atomic number 6943) and PCT / US98 / 24852 (atomic number 6944) filed on November 20, 1998.

Another preferred type of foam stabilizer is a cationic copolymer stabilizer, which comprises
Comprising from about 0.5% to 2% by weight of pendant quaternary nitrogen groups, comprising from about 50% by weight of units derived from acrylamide, methacrylamide, or mixtures thereof, from about 0.1% to 10% by weight % _C8-24 pendant hydrophobic groups, preferably the copolymer is about 55% to 95% by weight units derived from acrylamide, methacrylamide, or a mixture thereof, and at least one monoethylene substituted. About 4 to 3 having a molecular arrangement unit derived from a monomer containing a quaternary ammonium group
It contains 0% hydrophilic functional units and about 1 to 15% of units derived from monomers containing _C8-24 hydrophobic groups lacking a quaternary nitrogen substituted with at least one monoethylene. The quaternary ammonium group-containing monomer has the following formula

[0261]

Embedded image

Wherein R ₁ is H or CH ₃ , R ₂ and R ₃ are independently C _1-4 alkyl, R ₄ is C _1-4 alkyl, C _2-3 hydroxyalkyl or Benzyl, R ₂ , R ₃ , and R _{4 all} contain less than 9 carbon atoms, Z is a water-soluble salt-forming anion, and when M is —CO—X—, X is —O - or -NR ₅ - in and, R ₅ is H or C _{1 to 4} alkyl, x is either 1 to 6, when M is phenylene, x is has a 1], hydrophobic The group-containing monomer has the following formula

[0263]

Embedded image

Wherein R ₁ is H or CH ₃ , X is —O— or —NR ₇ —, Y is —C ₂ H ₄ O— or —C ₃ H ₇ O—, y is 0 to 60, when X is -O-, R ₆ is C _{8 to 24} hydrocarbyl, X is -NR ₇ - If a, R ₆ is C _{1 to 24} hydrocarbyl, R ₇ is H or _C1-24 hydrocarbyl;
At least one of R ₆ and R ₇ is C _8-24 hydrocarbyl]. See US Pat. No. 4,454,060 for details on these cationic copolymer stabilizers.

Thickeners- The dishwashing detergent compositions of the present invention may also contain from about 0.2% to 5% of a thickener. More preferably, the thickener comprises from about 0.5% to 2.5% of the composition herein.
%included. Thickeners are typically selected from the class of cellulose derivatives. Suitable thickeners include hydroxyethylcellulose, hydroxyethylmethylcellulose, carboxymethylcellulose, Quatrisoft LM200, and the like. A preferred thickener is hydroxypropyl methylcellulose.

The composition may comprise preferably at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 5% by weight of the composition of a thickening agent. The composition also preferably comprises up to about 5%, more preferably up to 3%, even more preferably up to 2.5% by weight of the composition of a thickener.

[0267] Hydroxypropyl methylcellulose polymer is about 50,000-125,
000 and a 2% by weight aqueous solution at 25 ° C. (ADTM D2363)
) Is from about 50,000 to about 100,000 cps. A particularly preferred hydroxypropyl cellulose polymer is Methocel (trade name) J75MS
-N (2.0% by weight aqueous solution at 25 ° C. has a viscosity of about 75,000 cps)
It is. Particularly preferred hydroxypropylcellulose polymers have been surface treated so that the hydroxypropylcellulose polymer is readily dispersed in an aqueous solution at 25 ° C. and at least about pH 8.5.

When formulated in the dishwashing detergent composition of the present invention, the hydroxypropyl methylcellulose polymer has a Brookfield of about 500-3500 cps at 25 ° C.
A viscosity is imparted to the cleaning composition. More preferably, the hydroxypropyl methylcellulose material provides a viscosity of about 1000-3000 cps at 25C. For the purposes of the present invention, the viscosity was set at 12 rpm with a Brook using an RV # 2 spindle.
Measured with a kfield LVTDV-11 viscometer.

Clay thickeners are also suitable for use as thickeners. One suitable clay thickener is Laponite. When Laponite clay is used, it is present in the composition of the present invention at a concentration of about 0.25% to about 2.0% by weight, more preferably about 0.5% to about 1.75% by weight; At least about 5.0% by weight of Lapon
It is a synthetic colored clay optionally having a tetra-potassium pyrophosphate peptizer, which is an item RDS. Laponite Inorganics of Gre, UK
The particle size of Laponite RDS manufactured at at Britain is 2
Big thing is less than 2% than 50 microns, a surface area of bulk density of about 1000 Kg / m ^3, and from about 330 m ² / g. Laponite RD contains no peptizer, less than 2% greater than 250 microns, a surface area of about 370 m ² / g, and a bulk density of about 1000 Kg / m ³ .

If the composition includes an abrasive, the dishwashing composition may also include a colloid-forming swelling clay that functions as a thickener of the formulation and a suspending agent for the abrasive. This expansive clay is a clay that is geologically classified as smectite and attapull guide. Suitable smectite clays are montmorillonite, which is primarily a hydrated aluminosilicate, and hectorite, which is primarily a hydrated magnesium silicate. It should be understood that the proportion of hydrated water in the semectite clay will vary with the mode of treatment of the clay. However, since the swellability of hydrated semectite clay is determined by the crystal structure of the silicate, the amount of water present is not large. In addition, the defect charge of the semectite is corrected by cations such as sodium, calcium, potassium and the like adsorbed between the three layers of clay minerals (two layers are tetrahedral and one layer is octahedral). The semectite used in the liquid composition was Thixogel No.
. 1 and Gelwhite GP (Georgia KaolinCompa)
ny (both montmorillonite)) and Veegum Pro and Vee
gu F (RT Vanderbilt (both hectorite)) and the like. A preferred clay is Georgia Kaolin
Gelwhite GP, a high-viscosity colloidal montmorillonite available from the company. This clay contains about 6% to 10% by weight of water and is a mixture of the following oxides: 59% SiO ₂ , 21% Al ₃ O ₃ , 1% F
e ₂ O ₃ , 2.4% CaO, 3.8% MgO, 4.1% Na ₂ O, and 0.4%
K ₂ O. 100% by weight of clay passes through a 200 mesh sieve. It disperses easily in water, but needs to be maximally swelled before use. This swelling of the clay is important to avoid stratification in the liquid. During this swelling process, the clay / water mixture becomes very viscous. It is also thixotropic and therefore exhibits a yield point as well. In this regard, 350 dyne / cm ² is a clay / water mixture of Gelwhite GP as the final composition and other physical properties (eg, flowability, dispersibility, suspendability, and liquid layering) are satisfied. Was determined to be the preferred yield point. (The term "layering"
Refers to the amount of clear liquid (mm) found on the surface of the final formulation after aging at 1 week and 49 weeks at 49 ° C. ) A clay / water mixture having a yield point of 350 dyne / cm ² is acceptable irrespective of the concentration of Gelwhite GP. Usually, the yield point is HAAKE rv12, MVIP, E = 0.3, R = 100, O = 11
The measurement is performed using a grooved rotor cup for 3 minutes and 18 minutes. Another expansive clay material suitable for use in liquid compositions is geologically classified as attapulgite,
It is a clay rich in magnesium. A typical attapulgite analysis shows that 55.0
2% SiO ₂ , 10.24% Al ₂ O ₃ , 3.53% Fe ₂ O ₃ , 10.49% Mg
O, 0.47% K ₂ O, 9.73% H ₂ O are obtained. 9.73% H ₂ O 150
C. and 10.13% H ₂ O was removed at a higher temperature. These clays have a small particle size, with 100% of the clay passing through a 200 mesh screen.
Attapulgite clay is available from Engelhard Minerals & Chem
Attagel 40, Attage from icals Corporation
It is commercially available under various trade names, such as 150 and Attagel 150. Of course, mixtures of smectite clay and attapulgite clay are stable, resulting in a combination of features not available from any class of clay. To achieve the desired swelling, the suspension of clay in water is subjected to high shear mixing for a sufficient time to substantially completely hydrate the clay before introduction into the organic portion of the formulation. For example, the desired swelling can be achieved by high speed shearing of an 8% aqueous clay dispersion for 25 minutes. When the clay is fully hydrated, the viscosity of the aqueous suspension increases dramatically and swelling allows the use of lower concentrations of clay. For example, 1% to 1.55% by weight and up to 3% by weight, preferably as low as 1.2% to 2% by weight, without affecting the dispersibility in water, the abrasive of the present invention. Effectively stabilizes the composition. As mentioned above, the clay / water mixture used in the described composition is preferably about 350 d
ynes / cm ² , but with a satisfactory polishing composition of about 300 dyne
It can be prepared with a hydrous clay dispersion having a yield point as low as s / cm ^{2 and} as high as about 450 dynes / cm ² . The water insoluble, low density abrasive is suspended in the dishwashing liquid composition and is from 3% to 15%, preferably from 5% to 5% by weight.
A Moisture hardness (such as silica or calcium carbonate) of from 2 to 7 in a concentration range of 15% by weight, if desired, in small amounts (for example 1% to 25% by weight) (based on the total weight of the abrasive in the composition). The crystalline abrasive can be replaced with a portion of the low density abrasive when a substantially stable liquid dishwashing composition is obtained.

Abrasives- The cleaning components of the present invention may optionally comprise from about 0 to about 20%, more preferably from 0.5% to 10%, by weight of an abrasive. The abrasive is preferably
It is selected from the group consisting of amorphous hydrated silica, calcite which is limestone calcium carbonate, and polyethylene powder and mixtures thereof. A suitable amorphous silica (oral great) for improving the polishing ability of the composition is Zeoffin. Z
The average particle size of eoffin silica is 8-10 mm. Its apparent density is between 0.32 and 0.37 g / ml. Another silica is Rhone-Poul
Tixosil 103 manufactured by Enc. Crossfield amorphous hydrated silica of the same apparent density at different particle sizes (9, 15, and 300 mm) was also used. One polyethylene powder suitable for use in the present invention is from about 200 to
It has a particle size of about 500 microns and a density of about 0.91 to about 0.99 g / l, more preferably about 0.94 to about 0.96 g / l. Another preferred abrasive is used at a concentration of about 0-20% by weight, more preferably 1% -10% by weight. M. Huber Corporation of Illinoi
The calcite is manufactured in s. Calcite contains mainly calcium carbonate and 1% to 5% magnesium carbonate, has an average particle size of 5 microns,
It is a limestone with a rubout of about 10 and a hardness of about 3.0 Mohs.

Solvents Various water-miscible liquids (lower alkanols, diols, other polyols, ethers, amines, etc.) can be used, and C ₁ -C ₄ alkanols are particularly preferred. Such solvents may be present in the compositions herein in a range from about 1% to 8%.

When present, the composition preferably comprises at least about 0.01% by weight of the composition,
More preferably, it comprises at least 0.5% by weight, even more preferably at least 1% by weight of solvent. The cleaning composition also preferably comprises no more than about 20% by weight of the composition;
More preferably, it contains 10% by weight or less, even more preferably 8% by weight or less of a solvent.

These solvents can be used in combination with an aqueous liquid carrier (such as water), and the solvent can be used without any aqueous liquid carrier present. Solvents are broadly defined as compounds that are liquid at 20 ° C to 25 ° C and are not considered surfactants. One of the unique features is that solvents tend to exist as discrete entities rather than as a broad mixture of compounds. Examples of suitable solvents of the present invention include methanol, ethanol, propanol, isopropanol, 2-
Includes methylpyrrolidinone, benzyl alcohol, and morpholine n-oxide. Of these solvents, methanol and isopropanol are preferred.

Suitable solvents for use herein include ethers and diethers containing 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 8 to 10 carbon atoms. Is included. Also, other suitable solvents are glycols or alkoxylated glycerols, alkoxylated aromatic alcohols, aromatic alcohols,
Aliphatic branched alcohols, alkoxylated fatty branched alcohols, alkoxylated linear C ₁ -C ₅ alcohols, linear C ₁ -C ₅ alcohols, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C ₆ To rC16 glycol esters, and mixtures thereof.

Suitable glycols that can be used herein are of the formula HO—CR ₁ R ₂ —
OH, wherein R ₁ and R ₂ are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and / or cyclic. A suitable glycerol as used herein is dodecane glycol and / or propanediol. Polypropylene glycol (such as those having a molecular weight range of about 100 to 1000)
Is also appropriate. One suitable polypropylene glycol has a molecular weight of about 2
700.

Suitable alkoxylated glycols that can be used herein are of the formula R
(A) _n- R ₁ -OH (wherein R is H, OH, a linear chain of 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms) R ₁ is H or 1 to 20 carbon atoms, preferably 2 to
Is a linear, saturated or unsaturated alkyl of 15 carbon atoms, more preferably 2 to 10 carbon atoms, A is an alkoxy group, preferably ethoxy, methoxy, and / or propyl, and n is 1 to 5 , Preferably 1-2). Suitable alkoxylated glycols for use herein are methoxyoctadecanol and / or ethoxyethoxyethanol.

A suitable alkoxylated aromatic alcohol that can be used herein is:
Formula R (A) _n -OH wherein R is an alkyl- or non-alkyl-substituted aryl of 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably from 1 to 2. Suitable alkoxylated aromatic alcohols are benzoxyethanol and / or benzoxypropanol.

Suitable aromatic alcohols that can be used herein are of the formula R—OH (
Wherein R is an alkyl- or non-alkyl-substituted aryl group of 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. For example, a suitable aromatic alcohol used is benzene alcohol.

Suitable aliphatic branched alcohols that can be used herein are of the formula RO
H wherein R is a branched saturated or unsaturated alkyl group of 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 5 to 12 carbon atoms. Particularly suitable aliphatic branched alcohols used herein include 2-ethylbutanol and / or 2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols that can be used herein are of the formula R (A) _n —OH, where R is 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms.
A branched or saturated alkyl group of 15 carbon atoms, more preferably 5 to 12 carbon atoms, A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is 1 to 5, Preferably an integer of 1 to 2). Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol.

Suitable alkoxylated linear C1-C5 alcohols that can be used herein are of the formula R (A) _n —OH, where R is 1 to 5 carbon atoms, preferably 2
Is a linear, saturated or unsaturated alkyl group of from 4 to 4 carbon atoms, A is an alkoxy group, preferably butoxy, propoxy, and / or ethoxy;
5, preferably an integer of 1 to 2). Suitable alkoxylated aliphatic linear C ₁ -C ₅ alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxy propanol, ethoxy ethanol, or a mixture thereof. Butoxypropoxypropanol is commercially available from Dow chemical under the trade name n-BPP (trade name).

Suitable C ₁ -C ₅ alcohols that can be used herein are of the formula R—OH
Wherein R is a linear saturated or unsaturated alkyl group of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms. Suitable straight chain C ₁ -C ₅ alcohol is methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyl triglycol ether, teramyl alcohol, and the like. Particularly preferred solvents that can be used herein are butoxypropoxypropanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol, and mixtures thereof.

Other suitable solvents for use herein include propylene glycol derivatives (
n-butoxypropanol or n-butoxypropoxypropanol), a water-soluble CARBITOL (trade name) solvent or a water-soluble CELLOSOLVE (trade name). Water-soluble CARBITOL (trade name) solvents are of the 2- (2-alkoxyethoxy) ethanol class, where the alkoxy groups are derived from ethyl, propyl, or butyl. A preferred water-soluble carbitol is 2- (2-butoxyethoxy) ethanol, also known as butyl carbitol. Water soluble CELLO
The SOLVE (trade name) solvent is a compound of the 2-alkoxyethoxyethanol class, with 2-butoxyethoxyethanol being preferred. Other suitable solvents include
Benzyl alcohol, diol (2-ethyl 1,3-hexanediol, 2,2
, 4-trimethyl-1,3-pentanediol, and mixtures thereof). Some preferred solvents used herein are n-butoxypropoxypropanol, BUTYL CARBITOL®, and mixtures thereof.

The solvent may also be selected from the group of compounds including mono, di and triethylene glycol, ether derivatives of propylene glycol, butylene glycol ether and mixtures thereof. The molecular weight of these solvents is preferably less than 350, more preferably 100-300, even more preferably 115-250. Examples of preferred solvents include, for example, monoethylene glycerol-n-hexyl ether, monopropylene glycol-n-butyl ether, and tripropylene glycol methyl ether. Ethylene glycol and propylene glycol ether are sold under the trade name "Dowanol" by Dow Chemical.
Arco Ch from L Company and under the trade name "Arcosolv"
Commercially available from the Electronic Company. Other preferred solvents, including mono and diethylene glycol-n-hexyl ether, are Union Carn.
It is commercially available from the bid company.

[0287]Solubilizer -The composition of the present invention optionally comprises from 0 to about 12% by weight, more preferably
About 1% to about 10% by weight of at least one solubilizer. This is nato
Lium xylene sulfonate or sodium cumene sulfonate, C_2-3mono
Or dihydroxyalkanols (ethanol, isopropanol, and
Hydrotropes such as pyrene glycol), and mixtures thereof.
Solubilizing agents are included to adjust the clarity of the haze at low temperatures. Optional
Specifically, urea is present in the composition of the present invention at 0-10% by weight, more preferably at about 0.5% by weight.
It can be used as a supplemental solubilizer in a concentration of from% to about 8% by weight. Other appropriate
Glycerol, a water-soluble polyethylene glycol having a molecular weight of 300 to 600
The formula HO (CH_ThreeCHCH_TwoO)_nH (where n is an integer of 2 to 18)
Of propylene glycol, polyethylene glycol and polypropylene glycol
Mixture (Synalox), and Mono C₁~ C₆Alkyl ethers and structures
Formulas R (X) nOH and R₁(X)_nOH (where R is C₁~ C₆An alkyl group
, R₁Is C_Two~ C_FourX is an acyl group, and X is (OCH_TwoCH_Two) Or (OCH_Two(CH _Three ) CH), wherein n is a number from 1 to 4)
It is an ester with glycol. Typical members of polypropylene glycol
Include dipropylene glycol and polypropylene having a molecular weight of 200 to 1000
Glycol (eg, polypropylene glycol 400). Other satisfaction
Glycol ether is ethylene glycol monobutyl ether (butyl cello).
Solve), diethylene glycol monobutyl ether (butyl carbitol),
Triethylene glycol monobutyl ether, mono, di, tripropylene glycol
Monobutyl ether, tetraethylene glycol monobutyl ether, mono
, Di, tripropylene glycol monomethyl ether, propylene glycol
Nomethyl ether, ethylene glycol monohexyl ether, diethylene glycol
Coal monohexyl ether, propylene glycol quaternary butyl ether,
Tylene glycol monoethyl ether, ethylene glycol monomethyl ether
, Ethylene glycol monopropyl ether, ethylene glycol monopentyl
Ether, diethylene glycol monomethyl ether, diethylene glycol
Noethyl ether, diethylene glycol monopropyl ether, diethylene glycol
Recall monopentyl ether, triethylene glycol monomethyl ether,
Triethylene glycol monoethyl ether, triethylene glycol monopro
Pill ether, triethylene glycol monopentyl ether, triethylene glycol
Recall monohexyl ether, mono, di, tripropylene glycol monoethyl
Ruether, mono, di, tripropylene glycol monopropyl ether, mono
, Di, tripropylene glycol monopentyl ether, mono, di, tripropy
Lenglycol monohexyl ether, mono, di, tributylene glycol mono
Methyl ether, mono, di, tributylene glycol monoethyl ether, mono
, Di, tributylene glycol monopropyl ether, mono, di, tributylene
Glycol monobutyl ether, mono, di, tributylene glycol mono pliers
Mono-, di-, butylene glycol monohexyl ether,
Ethylene glycol monoacetate and dipropylene glycol propione
It is.

Polymerized Soil Release Agents- The compositions of the present invention may optionally include one or more soil release agents. The polymerized soil release agent has a hydrophilic segment to make the surface of the hydrophobic fibers (such as polyester and nylon) hydrophilic, deposits on the hydrophobic fibers and soil that remains attached after the completion of the washing cycle, It is characterized by having both, thereby acting as an anchor for the hydrophilic segment. Thereby, the stain can be more easily removed in the washing step after the treatment with the stain releasing agent.

If used, soil release agents generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably 0.2% by weight of the composition. % ~
It may contain about 3% by weight.

The following, all of which are incorporated herein by reference, describe soil release agents suitable for use herein. Gos, issued November 25, 1997
U.S. Pat. No. 5,691298 to Selink et al., Feb. 4, 1997.
No. 5,599,782 issued to Pan et al., Issued Mar. 1, 1995
Nos. 5,415,807 and 19, issued to Gosselink, issued on the 6th
No. 5,182,043 issued to Morral on Jan. 26, 1993 and 4,956 issued to Gosselink et al. Issued on Sep. 11, 1990.
No. 4,447, issued Dec. 11, 1990, issued to Maldonado et al .;
No. 4,968,451 issued to Bor, issued May 15, 1990.
cher, Sr. No. 4,925,577 granted elsewhere, August 2, 1989
No. 4,861,512 granted to Gosselink issued on the 9th, 1989
No. 4,877,89 granted to Maldonado et al.
No. 6, issued on October 27, 1987 to Gosselink et al.
No. 4,711,730 granted to Gosselink et al., Issued on Dec. 8, 1987, and Gosseli issued on Jan. 26, 1988.
No. 4,721,580 issued to nk et al .; No. 4,000,093 issued to Nicol et al. issued on Dec. 28, 1976; granted to Hayes issued May 25, 1976. U.S. Pat. No. 3,893,929 issued to Basadur, issued Jul. 8, 1975, and US Pat.
European Patent Application 0 219 0, published on April 22, 1987 by Kud et al.
No. 48.

In addition, suitable soil release agents are disclosed in US Pat.
No. 4,240,918 granted to Lagase et al.
No. 4,525,524 to Tung et al., And No. 4,579,681 to Ruppert et al., Rhone-Poulenc in 1988.
No. 4,220,918 assigned to Chemie and 4,787,9
89, EP 279,134A, EP 457,205A granted to BASF (1991), and Univer N. V. In 1974
German Patent No. 2,335,044, which is incorporated by reference herein, which is incorporated by reference herein in its entirety.

Polymerized Fat Release Agents- The compositions of the present invention may also optionally include a polymerized oil release agent. Suitable polymerized fat releasing agents include the following formula:

[0293]

Embedded image

Wherein x is hydrogen or an alkali metal cation, n is a number from 2 to 16,
R ₁ is selected from the group consisting of methyl or hydrogen, R 2 is a C ₁ -C ₁₂ straight or branched chain alkyl group, and R ₃ is a C ₂ -C ₁₆ straight or branched chain alkyl group. , And y are such that a molecular weight of about 5,000 to about 15,000 is obtained. See U.S. Pat. No. 5,573,702.

Clay Removal / Anti-Redeposition Agents— The compositions of the present invention may also optionally include a water-soluble ethoxylated amine having clay removal and anti-redeposition properties. Particle detergent compositions containing these compounds typically comprise from about 0.01% to about 10.
It contains 0% by weight of a water-soluble ethoxylated amine, and for liquid detergents is typically about 0.1%.
From 0.01% to about 5% by weight.

A preferred soil release and redeposition inhibitor is ethoxylated tetraethylenepentamine. By way of example, ethoxylated amines are available from Va.
No. 4,597,898 to nderMeer. Another group of preferred clay soil removal-redeposition inhibitors are EP 111,965, filed on July 27, 1984 and filed by Oh and Gosselink. Other clay soil removal / redeposition inhibitors that may be used include 1984 June
Ethoxylated amine polymers disclosed in European Patent Application No. 111,984, filed by Gosselink, published on July 27, Gosselink, published July 4, 1984
The zwitterionic polymer disclosed in the filed European Patent Application No. 112,592, and 1985
U.S. Pat. No. 4,548,74, issued to Connor on Oct. 22, 1998, issued for value
No. 4 includes the disclosed amine oxides. Other clay soil removal and / or redeposition inhibitors known in the art can also be used in the compositions herein. U.S. Pat. No. 4 to VanderMeer, issued Jan. 2, 1990
No. 891,160 and WO 95/3227 published November 30, 1995.
See FIG. Another type of preferred anti-redeposition agent includes carboxymethyl cellulose (CMC) materials. These materials are well-known in the art.

Polymerizable Dispersant-The polymerizable dispersant may be present in the compositions herein in the presence of a zeolite and / or a layered silicate builder in an amount of from about 0.1% to about 7% by weight.
Can be used advantageously. Suitable polymerizable dispersants include polymerized polycarboxylates and polyethylene glycols, but other materials known in the art can also be used. Without intending to be limited by theory, the polymerizable dispersants, when used in combination with other builders (low molecular weight polycarboxylates), inhibit crystal growth, release particulate soil, deflocculate, and regenerate. It is believed that the prevention of deposition improves the overall performance of the detergent builder.

The polymerized polycarboxylate material can be prepared by the polymerization or copolymerization of a stable unsaturated monomer, preferably in the acid form. Unsaturated monomers that can be polymerized to form suitable polymerized polycarboxylates include acrylic acid,
Includes maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid. If the segment is not included in excess of about 40% by weight, it will be stabilized by the presence in the polymerized polycarboxylate or monomer segment herein without carboxylate radicals (vinyl methyl ether, styrene, ethylene, etc.).

[0299] Particularly suitable polymerized 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 between about 2,000 and
It ranges from 10,000, more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000. Such water-soluble salts of acrylic acid polymers can include, for example, alkali metal, ammonium, and substituted ammonium salts. This type of soluble polymer is a known substance. The use of this type of polyacrylate in detergent compositions is described, for example, in Diehl, published March 7, 1967.
No. 3,308,067, issued to U.S. Pat.

Acrylic / maleic acid based copolymers can be used as a preferred component of the dispersing / redeposition inhibitor. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably between 2,000 and 100,000, more preferably about 5
5,000 to 75,000, most preferably in the range of 7,000 to 65,000. The ratio of acrylate to maleate segment in such a copolymer is:
Generally it ranges from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Such water-soluble salts of acrylic acid / maleic acid copolymers can include, for example, alkali metal, ammonium and substituted ammonium salts. This form of the soluble acrylate / maleate copolymer is a known material and is described in
EP-A-66915 published on March 15, and EP-A-193,360 published September 3, 1986, which also describes such polymers including hydroxypropyl acrylate. . Still other useful dispersants include maleic / acrylic / vinyl alcohol terpolymers. Such materials may also include, for example, acrylic acid / maleic acid / vinyl alcohol 45 /
EP 193,360, including a 45/10 terpolymer, is disclosed.

Another polymeric material that may be included is polyethylene glycol (PEG).
PEG may not only act as a stain removal-redeposition agent, but may also exhibit performance as a dispersant. Typical molecular weight ranges for these purposes are from about 500 to about 1
00,000, preferably about 1,000 to about 50,000, more preferably about 1
, 500 to about 10,000.

[0302] Polyaspartate and polyglutamate dispersants can also be used, especially with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (average) of about 10,000.

Other polymer types that are more desirable for improving biodegradability, bleaching stability or for cleaning purposes include Rohm & Haas, BASF Corp. And various terpolymers and hydrophobically modified copolymers, including polymers commercially available from Nippon Shokubai, and for all modes of water treatment, textile treatment or detergent application.

Chelating Agents- The compositions herein may also optionally include one or more chelating agents, especially those for ancillary transition metals. Transition metals commonly found in wash water include water-soluble, colloidal or particulate iron and / or manganese, which can associate as oxides or hydroxides, or with soils such as organic substrates. Can be found. Preferred chelators are chelators that efficiently suppress such transition metals, especially the precipitation of such transition metals or compounds thereof on fabrics, and / or in cleaning media and / or on fabrics or hard surfaces. Is a chelating agent that suppresses an undesirable reduction reaction at the interface of the polymer. Such chelating agents include, in addition to polymer type chelating agents, low molecular weight chelating agents, typically chelating agents having at least one, preferably two or more donor heteroatoms such as O and N capable of coordinating with a transition metal. Is included. Common chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators, and mixtures thereof.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilo-triacetate, ethylenediaminetetrapropionate,
Includes triethylenetetramine hexaacetate, diethylenetriaminepentaacetate, and ethanol diglycine, alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

The aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention if at least low levels of total phosphorus are tolerated in the cleaning composition;
Amino phosphonates include ethylenediaminetetrakis (methylene phosphonate), commercially available as DEQUEST. Aminophosphates containing no alkyl or alkenyl having more than about 6 carbon atoms are preferred.

[0307] Polyfunctionally substituted aromatic chelators are also useful in the compositions herein. 1974
See U.S. Patent No. 3,812,044, issued to Connor et al. In acid form, preferred compounds of this type are 1,2-dihydroxy-3
Form dihydroxydisulfobenzene, such as 5, disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediaminedisuccinate ("EDDS"), particularly US Pat. No. 4,704, issued Nov. 3, 1987 to Hartman and Perkins. No. 233, [S,
[S] isomer.

The compositions herein can also include a water-soluble methyl glycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or cobuilder. Similarly, so-called "weak" builders, such as citrate, can also be used as chelating agents.

[0310] When used, chelating agents generally comprise about 0.001 of the cleaning compositions herein.
1% to about 15% by weight. More preferably, if used, the chelating agent will comprise from about 0.01% to about 3.0% by weight of such compositions.

Antifoaming agents- Where necessary for the intended use, especially for washing laundry in a washing machine, compounds for reducing or inhibiting foam formation can be incorporated into the compositions of the present invention. . Other compositions, such as handwashing compositions, can be omitted because high foaming is desired. Defoamers are disclosed in U.S. Pat. No. 4,489,4.
It can be particularly important in so-called "high-concentration washing steps", as described in US Pat.

[0312] A wide variety of materials can be used as defoamers and are known to those skilled in the art. For example, Kirk Othmer Encyclopedia of Chemi
cal Technology, 3rd edition, volume 7, pages 430-470 (Wil
ey, 1979).

[0313] Compositions herein generally comprise from 0% to about 10% of an antifoam. When utilizing monocarboxy fatty acids and salts thereof as an antifoaming agent, typically up to about 5%, preferably from 0.5% to 3% by weight of the detergent composition, even when used in large amounts.
Present in weight percent. Preferably from about 0.01% to about 1%, more preferably from about 0.
Use from 25% to about 0.5% of the silicone antifoam. These weight percentages include any available defoamer adjuvant materials, as well as any silica available in combination with the polyorganosiloxane. Monostearyl phosphate antifoams are generally utilized in amounts ranging from about 0.1% to about 2% by weight of the composition. Hydrocarbon defoamers, even when available in large amounts, can contain from about 0.01% to about 5%.
Used in amounts in the% range. Alcohol defoamers are typically used in the final composition at 0%.
. Used at 2% to 3% by weight.

Alkoxylated polycarboxylates- Alkoxylated carboxylates, such as those prepared from polyacrylates, are useful herein to provide additional grease removal performance. Such materials are described on page 4 of WO 91/0821 and PCT 90/01815, incorporated by reference herein, and on the next page. Chemically, these materials contain one epoxy side chain per 7-8 acrylate units. The side chain is-(CH ₂ C
_{H 2 O) m (CH 2} ) n CH 3 [ wherein, m is 2 to 3, n is 6 to 12 is a. The side chains are ester-linked to the polyacrylate "backbone", providing a "comb" type polymer structure. The molecular weight can vary, but typically ranges from about 2000 to about 50,
000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein.

[0315] Perfume - Useful perfumes and perfume ingredients in the compositions and methods of the present invention include a wide variety of natural and synthetic chemical components, aldehydes, ketones, and esters, such as including but not limited to. Also includes various natural extracts and extracts that may include complex mixtures of components, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic extract, sandalwood oil, pine oil, cedar and the like. It is. The finished perfume contains a very complex mixture of such components. The finished perfume will typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, with the individual perfume ingredients comprising from about 0.000% to about 0.000% of the finished perfume composition.
1% to about 90% may be contained.

Non-limiting examples of perfume ingredients useful herein include 7-acetyl-1,2,3
4,4,5,6,7,8-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-tertbutyl-1,1- Dimethylindane; para-hydroxyphenylbutanone; benzophenone; methyl beta naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethylindane; 5-acetyl-3-isopropyl-1,1,2,2; 6-tetramethylindane;
1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde; 7-hydroxy3,7-dimethyloctanal; 10-undec-1-al; iso-hexenylcyclohexylcarboxy Aldehyde; formyltricyclodecane; condensation product of hydroxycitronellal and methylanthranilate; condensation product of hydroxycitronellal and indole; condensation product of phenylacetaldehyde and indole; 2-methyl-3- (Para-tert-butylphenyl) propionaldehyde; ethyl vanillin; nerotropin; hexylcinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde; Decalactone gamma; cyclopentadecanolide; 1
6-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-
Benzopyran; Betanaphthol methyl ether; Amboroxane; Dodecahydro-3a, 6,6,9a-tetramethyl-naphtho [2,1b] furan; Cedar oil, 5- (2,2,3-trimethylcyclopent-3-enyl) 3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; carirophylene alcohol;
Tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; seryl acetate; and para- (tert-butyl) cyclohexyl acetate.

Particularly preferred perfume substances are those substances which significantly improve the odor of the final product composition comprising cellulase. These flavors include, but are not limited to:
Hexylcinnamic aldehyde; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 7-acetyl-1,2,3,4,5,6,7
7,8-octahydro-1,1,6,7-tetramethylnaphthalene; benzyl salicylate; 7-acetyl 1,1,3,4,4,6-hexamethyltetralin;
Para-tert-butylcyclohexyl acetate; methyl dihydrojasmonate; beta naphthol methyl ether; methyl beta naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde;
, 4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran; dodecahydro-3a, 6,6,9a-
Tetramethylnaphtho [2,1b] furan; Anisaldehyde; Coumarin; Cedar oil; Vanillin; Cyclopentadecanolide; Tricyclodecenyl acetate;
And tricyclodecenyl propionate.

Other perfume substances include, but are not limited to, peruvian balsam, frankincense resinoids, sesame seeds, labtanum resin, nutmeg, guar oil, benzoin resin, cilantro, and lavandin. Essential oils, resins, and resins. Still other perfume chemicals include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1,1-dimethylethyl)-
Includes cyclohexanol acetate, benzyl acetate and eugenol. Carriers such as diethyl phthalate can be used in the final product composition.

Instead of perfume, especially in microemulsions, the composition may comprise a water-insoluble organic compound such as an essential oil or a water-insoluble hydrocarbon having 6 to 18 carbons (eg paraffin or isoparaffin such as isopar H, isodecane). , Alpha pinene, beta pinene, decanol and terpineol) can be used. Suitable essential oils are selected from the group consisting of: Anethole 20/21 Natural, Anise Fruit Oil China Star, Anise Fruit Oil Glove Band, Balsam (Peru), Basil Oil (India), Black Pepper Oil, Black Pepper Oleoresin 40/20, Rose Forest (Brazil) F
OB, Borneol flakes (China), camphor oil, white, camphor powder synthetic product, Kananga oil (Java), Shahzu oil, Kawaraketsumei oil (China), Cedar oil (China) BP, cinnamon bark oil, cinnamon leaf Oil, citronellal oil, asparagus bud oil, aspergillus leaf, cilantro (Russia), coumarin 69 ° C (China), cyclamenaldehyde, diphenyl oxide, ethyl vanillin, eucalyptol, eucalyptus oil, eucalinoxy triodora, fennel oil, fusarium oil, ginger Oil, ginger oleoresin (India), white grapefruit oil, rapeseed oil, garjan balsam, heliotropin, isobornyl acetate, isolongifolene (Isolongif)
olene), juniper berry oil, L-methyl acetate, lavender oil, lemon oil, lemongrass oil, diluted lime oil, Litsea Cubeba oil, longifolene, menthol crystal, methyl cerdyl ketone, methyl chabicol, Seeds of musk troglodytes, musk ketone, musk xylol, nutmeg oil, orange oil, pachipouri (P
achpouli) oil, peppermint oil, phenylethyl alcohol, pimento berry oil, pimento leaf oil, rosalin, sandalwood oil, sandenol, sage oil, cressage, sassafras oil, Dutch peppermint oil, spiky lavender, manjogiku, tea tree Oil, vanillin, vetiver oil (Java), Himekoji.

Composition pH- The dishwashing composition of the present invention, when used, ie, diluted and applied to soiled dishes, is subjected to the acidic conditions created by food soil. If a composition having a pH greater than 7 is more effective, the composition is optionally in a composition and a dilute solution (i.e., from about 0.1% by weight of the composition to 0% by weight).
. (A 4% by weight aqueous solution) may generally include a buffer to make it more alkaline. The pH value of this buffer should be about 0.5 to 1.0 pH units below the desired pH of the composition (determined as described above). Preferably, the buffer p
H should be from about 7 to about 10. Under such conditions, the pH can be efficiently controlled even when the buffer is used in a minimum amount.

The compositions of the present invention have a pH (measured as a 10% aqueous solution) of about 2.0 to about 12.5, more preferably about 約, and even more preferably about.

The buffering agent may itself be an active detergent, or may be a low molecular weight organic or inorganic substance used alone in the composition to maintain an alkaline pH. Preferred buffers for the composition of the present invention are nitrogen-containing substances. Some examples are amino acids such as lysine, lower alcohol amines such as mono, di and triethanolamine. 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, N′-tetra-methyl-1,3-diamino-2-propanol, N, N-bis (2-hydroxyethyl) glycine (bicine) and N-tris (Hydroxymethyl) methylglycine (tricine). Any mixture of the above is also applicable. Useful inorganic buffers / alkaline sources include alkali metal carbonates and phosphates, such as sodium carbonate, sodium polyphosphate. Additional buffers include McCutcheon's EMULSI
FIERS AND DETERGENTS, North America E
edition, 1997, McCutcheon Division, MC
Publishing Company Kirk and WO 95/0797
See 1. Both documents are incorporated herein by reference.

The composition may preferably comprise at least about 0.1%, more preferably at least about 1%, even more preferably at least about 2% by weight of the composition of a buffer. The composition also preferably contains up to about 15%, more preferably up to about 10%, even more preferably up to about 8% by weight of the composition, of a buffer.

[0324]Hydrotrope -A water-soluble liquid carrier is one or more hydrotropes;
Material. Suitable hydrotropes for use in the compositions herein
Is C₁~ C_ThreeAlkyl aryl sulfonate, C₆~ C₁₂Alkanol, C₁~ C ₆ Carboxyl sulfate, and sulfonate, urea, C₁~ C₆Hydrocal
Boxylate, C₁~ C_FourCarboxylate, C_Two~ C_FourOrganic diacids, and these
A mixture of hydrotrope substances is included. The liquid cleaning composition of the present invention comprises
Selected from potassium metal and calcium xylene and toluene sulfonate
Preferably, the hydrotrope comprises about 0.5% to 8% by weight of the liquid cleaning composition.
Including.

Suitable C ₁ -C ₃ alkylaryl sulfonates include sodium, potassium,
Calcium, and ammonium xylene sulfonate; sodium, potassium, calcium, and ammonium toluene sulfonate; sodium, potassium, calcium, and ammonium cumene sulfonate; sodium, potassium, calcium, and ammonium substituted or unsubstituted naphthalene sulfonate; And mixtures thereof.

Suitable C ₁ -C ₈ carboxyl sulfates or sulfonates are substituted with any water soluble salt, or sulfate or sulfonate, and have 1 to 8 carbon atoms (excluding substituents) having at least one carboxyl group ). The substituted organic compound may be cyclic, acyclic, or aromatic, ie, a benzene derivative. Preferred alkyl compounds have 1 to 4 carbon atoms substituted with sulfate or sulfonate and have 1 to 2 carboxyl groups. Examples of this type of hydrotrope include sulfosuccinates, sulfophthalates, sulfoacetates, m-sulfobenzoates and sulfosuccinate diesters, preferably the sodium disclosed in U.S. Pat. No. 3,915,903. Or a potassium salt is included.

The C ₁ -C ₄ hydrocarboxylates and C ₁ -C ₄ suitable for use herein
The C ₄ carboxylate include acetate and propionate and citrate. The C ₂ -C ₄ diacids suitable for use herein include succinic acid, glutaric acid and adipic acid.

Other compounds that provide a hydrotrope effect suitable for use herein as a hydrotrope include C ₆ -C ₁₂ alkanols and urea.

Preferred hydrotropes for use herein are sodium, potassium, calcium, and ammonium cumene sulfonate; sodium, potassium, calcium, and ammonium xylene sulfonate; sodium, potassium, calcium, and ammonium Monium toluenesulfonate; and mixtures thereof. The most preferred substances are sodium cumene sulfonate and calcium xylene sulfonate and mixtures thereof. These preferred hydrotropes can be present in the composition on the order of about 0.5% to 8% by weight.

The composition preferably comprises at least about 0.1%, more preferably at least about 0.2%, even more preferably at least about 0.5%, by weight of the composition, of a hydrotrope. The composition also preferably comprises no more than about 15%, more preferably no more than about 10%, even more preferably no more than about 0.5% by weight of the composition of the hydrotrope.

[0331]Other ingredients -The cleaning composition is more preferably one or more selected from:
Can include detergent adjuvants: soil release polymer
polymer), polymer dispersant, polysaccharide, abrasive, bactericide, discoloration inhibitor, colorant
Agents, dyes, electrolytes (eg, NaCl), antifungals or fungicides,
Insect repellent, miticide, hydrotrope, processing aid, foaming agent, brightener, rust prevention aid
Agents, stabilizers, and antioxidants. Other active ingredients, carriers, antioxidants, processing aids
Auxiliaries, dyes or pigments, solvents for liquid preparations, solid fillers for rod-shaped compositions, etc.
A wide variety of other ingredients useful in cleaning compositions, including, are included in the compositions herein.
Can be rare. If you want high foaming,_Ten~ C₁₆Derivation of alkanolamides
Foams can be incorporated into the composition, typically at a concentration of 1% to 10%. C _Ten ~ C₁₄Monoethanol and diethanolamide are typical of such blowing agents.
Kind. In addition, such a foaming agent may be used in combination with the aforementioned amine oxide,
It is advantageous to use with high foaming co-surfactants such as
You.

[0332] Optionally, an antioxidant can be added to the cleaning compositions of the present invention.
They can be any of the conventional antioxidants used in cleaning compositions (eg, 2,6
-Di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine, etc.). Preferably, the antioxidant, when present, is present in the composition at about 0.001% to about 5% by weight.

The various detergent components used in the compositions of the present invention are optionally further adsorbed on a porous hydrophobic substrate and further stabilized by coating the substrate with a hydrophobic coating. it can. Preferably, the cleaning composition is mixed with a surfactant before being adsorbed on the porous substrate. In use, the cleaning composition is released from the substrate into an aqueous cleaning liquid in which the cleaning composition exhibits a desired cleaning function.

In order to describe this technique in detail, a porous hydrophobic silica (trade name: SIPERN)
AT D10, the DeGussa), 3% ~5% of C _{13 to 15} ethoxylated alcohol (EO 7) is mixed with a proteolytic enzyme solution containing a nonionic surfactant. Typically, the enzyme / detergent solution is 2.5 times by weight silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oils having a viscosity in the range of 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or added to the final wash matrix. By this means, the enzyme, bleach, bleach activator, bleach catalyst, photoactivator, dye, fluorescent material,
Components such as textile conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.

Composition Forms The compositions herein may be in any of the conventional forms for hand dishwashing compositions, such as pastes, liquids, granules, powders, gels, liquid gels, microemulsion liquid crystals and mixtures thereof. May be in any form. A more preferred embodiment is a liquid or a gel. Liquid compositions can be either aqueous or non-aqueous. When the composition is an aqueous liquid, the composition preferably further comprises an aqueous liquid carrier that dissolves, disperses, or suspends other essential and additional composition components.

When the composition is an aqueous liquid, the composition is preferably at least about 5% by weight
, More preferably at least about 10%, even more preferably at least about 30% by weight of the aqueous liquid carrier. The composition also includes up to about 95%, more preferably up to about 60%, even more preferably up to 50% by weight of the aqueous liquid carrier of the composition.

One essential component of the aqueous liquid carrier is, of course, water. However, aqueous liquid carriers include other substances that are liquid or that dissolve in the liquid carrier at room temperature, and other substances that, besides functioning as a simple filler, may also exhibit some other function. You may go out. Such materials can include, for example, hydrotropes and solvents. Suitable are low molecular weight primary or secondary alcohols represented by methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred to dissolve the surfactant, but polyhydric alcohols containing 2 to about 6 carbon atoms and containing 2 to about 6 hydroxyl groups (e.g., 1,3- Propanediol, ethylene glycol, glycerin, and 1,2
-Propanediol) can also be used.

An example of a method of making the granules of the cleaning composition herein is as follows: modified alkylbenzene sulfonate, citric acid, sodium silicate, sodium sulfate, fragrance, diamine and water. Add, heat and mix with a crusher. The resulting slurry is spray-dried to a fine-grained form.

An example of a method of making a liquid cleaning composition herein is as follows: Add and dissolve free water and citrate. In this solution, amine oxide, betaine,
Add ethanol, hydrotrope and nonionic surfactant. If free water is not available, citrate is added to the above mixture and then stirred until dissolved. At this point, the preparation is neutralized by adding an acid. The acid is preferably selected from organic acids such as maleic acid and citric acid, but inorganic mineral acids can likewise be used. In a preferred embodiment, these acids are added to the preparation before the addition of the diamine. AExS is added last.

Non-Aqueous Liquid Detergent The preparation of a liquid detergent composition comprising a non-aqueous carrier medium is described in US Pat.
No. 4,767,558; No. 4,772,413;
889,652; 4,892,673; British Patent 2,158,838.
No. 2,195,125; No. 2,195,649; U.S. Pat.
Nos. 88,462; 5,266,233; and EP 225,654 (1
No. 510,762 (October 28, 1992); No. 540,089 (May 5, 1993); No. 540,090 (1993)
U.S. Pat. No. 4,615,820; EP 565,017 (October 13, 1993); and U.S. Pat. No. 030,096 (June 10, 1981).
(These documents are incorporated by reference herein). Such compositions may include various particulate cleaning components stably suspended therein. Thus, such non-aqueous compositions comprise a liquid phase and optionally, but preferably, a solid phase, as described in detail below and in the references.

The compositions of the present invention are used to form aqueous wash solutions for use in hand dishwashing. 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, tableware, kitchen utensils.

An effective amount of a detergent composition herein that is added to water to form an aqueous cleaning solution includes an amount sufficient to form about 500-20,000 ppm of the composition in an aqueous solution. obtain. More preferably, about 800-5,000 ppm of the cleaning compositions herein are provided in the aqueous cleaning liquid.

The following examples illustrate the invention, but are not meant to be limiting or defined. All parts, percentages, and ratios are expressed by weight unless otherwise noted.

In the following examples, all concentrations are expressed as% by weight of the composition.

Examples of Detergent Compositions In these examples, the following abbreviations are used for the modified alkylbenzenesulfonates in the form of the sodium or potassium salts prepared according to any of the preceding preparations; MLAS.

The following abbreviations have been used for cleaning product adjunct materials: Cxy amine oxide Alkyldimethylamine N- with a given chain length Cxy
Oxide RN (O) Me ₂ (where the average total carbon range of the non-methylalkyl moiety R is 10 + x to 10 + y) CxyAPG Formula R ₂ O (C _n H _2n O) _{t for a} given chain length Cxy An alkyl polyglycoside represented by _{x wherein} R ₂ is C _10-18 alkyl;
Is 2 or 3, and t is from 0 to about 10, preferably 0; and x is about 1.3.
~ About 2.7). Glycosyl is preferably derived from glucose. Amylase Trade name Termamyl 60T as NOVO Indus
An amylolytic enzyme with an activity of 60 KNU / g, commercially available from tries A / S. Alternatively, amylase can be obtained from Fungamyl (trade name); Duramyl (
Trade name); BAN (trade name) and WO95 / 26397 and Novo N
ordisk is selected from the α-amylase enzymes described in co-pending application PCT / DK96 / 00056. APA C ₈ -C ₁₀ amidopropyl dimethylamine. Cxy betaine An alkyldimethyl betaine having an alkyl moiety with an average total carbon range of 10 + x to 10 + y. Calcium salts Calcium chloride, calcium sulfate, calcium hydroxide and mixtures thereof. Carbonate anhydrous Na ₂ CO ₃ , 200 μm to 900 μm. Citrate Trisodium citrate hydrate, 86.4%, 425 μm-
850 μm. Citric acid Citric acid, anhydride. CMC Carboxymethylcellulose sodium salt.

CxyAS Alkyl sulfates, Na salts or other salts as specified, having an alkyl moiety with an average total carbon range of 10 + x to 10 + y. CxyEz Commercially available linear or branched alcohol ethoxylate having an alkyl moiety with an average total carbon range of 10 + x to 10 + y and an average of z moles of ethylene oxide (no methyl branch in the chain). CxyEzS Alkyl ethoxylate sulfate having an average total carbon range of 10 + x to 10 + y alkyl moieties and an average of z moles of ethylene oxide, Na salt (or other salt if specified). DEA diethanolamine. Diamine Alkyl diamine, for example, 1,3 propanediamine, Dy
tek EP, Dytek A (Dupont) or selected from: dimethylaminopropylamine; 1,6-hexanediamine; 1,3-propanediamine; 2-methyl1,5 pentanediamine; 1,3-pentanediamine; 1-methyl-diaminopropane; 1,3-cyclohexanediamine; 1,2-cyclohexanediamine; 1,3 bis (methylamine) -cyclohexane. DTPA diethylenetriaminepentaacetic acid. DTPMP diethylene triamine penta (methylene phosphonate), M
onsanto (Dequest 2060). EtOH ethanol.

Hydrotropes are selected from sodium, potassium, magnesium, calcium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid. LAS linear alkyl benzene sulfonate (eg, C11.8,
Na or K salt). Lipase lipolytic enzyme, 100 kLU / g, NOVO, Lipola
se (product name). Alternatively, the lipase is selected from: Amano-P; M
l Lipase (trade name); Lipomax (trade name); US Application No. 08
Humicola Lanuginosa described in US Pat.
D96L and Humic Mutants of Lipase Degrading Natural Lipase Derived from
ola Lanuginosa strain DSM4106. LMFAA C12-14 alkyl N-methylglucamide. MA / AA Sodium salt of maleic / acrylic acid (1: 4) copolymer, average molecular weight 70,000. MBAxEy medium chain branched primary alkyl ethoxylate (average total carbon = x,
Average EO = y).

MBAxEyS Medium-chain branched or modified primary alkyl ethoxylate sulfate according to the invention, Na salt (average total carbon = x, average EO = y). (Example 9
reference). MBAyS Medium-chain branched primary alkyl sulfate, Na salt (average total carbon = y). MEA Monoethanolamine. CxyMES Alkyl methyl ester sulfonate Na salt having an alkyl moiety with an average total carbon range of 10 + x to 10 + y. Magnesium salt Magnesium chloride, magnesium sulfate, magnesium hydroxide and mixtures thereof. NaOH sodium hydroxide. CxyNaPS Paraffin sulfonate Na salt having an alkyl moiety with an average total carbon range of 10 + x to 10 + y. NaTs Sodium toluenesulfonate. PAA polyacrylic acid (mw = 4500). PAE ethoxylated tetraethylenepentamine PEG polyethylene glycol (mw = 4600). PG propanediol

Protease Proteolytic enzyme, 4K NPU / g, NOVO, Savi
case (product name). Alternatively, the protease is selected from: Maxat
ase (trade name); Maxacal (trade name); Maxapem15 (trade name)
Subtilisin BPN and BPN '; Protease B; Proteas
eA; Protease D; Primase (trade name); Durazym (trade name); Opticlean (trade name); and Optimase (trade name);
And Alcalase (trade name). CxySAS Secondary alkyl sulfates, Na salts, having an alkyl moiety with an average total carbon range of 10 + x to 10 + y. Sodium silicate silicate, amorphous (SiO ₂ : Na ₂ O = 2.0 ratio)
. Solvent Hexylene glycol, ethanol, or propylene glycol. STPP Sodium tripolyphosphate, anhydride blowing agent polymer (N, N-dimethylamino) alkyl acrylate;
, N-dimethylamino) ethyl methacrylate homopolymer; dimethylaminoethyl methacrylate / dimethylacrylamide copolymer; poly (DAM) homopolymer; poly (DAM-co-AA) (2: 1) copolymer; average molecular weight of about 52,000 daltons. Lys, Ala, Glu, Tyr (5: 6: 2
Polypeptides comprising: 1) sodium sulfate anhydrous TFA C16-18 alkyl N-methylglucamide Typical components often referred to as "minor components" include fragrances, dyes, pH
Modifiers (trims) and the like are included.

The following examples illustrate the invention, but are not meant to be limiting or defined. All parts, percentages, and ratios are expressed by weight unless otherwise noted.

[0352]

[Table 1]

[0353]

[Table 2]

[0354]

[Table 3]

[0355]

[Table 4]

[0356]

[Table 5]

[0357]

[Table 6]

[0358]

[Table 7]

[0359]

[Table 8]

[0360]

[Table 9]

[0361]

[Table 10]

[0362]

[Table 11]

[0363]

[Table 12]

[0364]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 1/28 C11D 1/28 1/29 1/29 1/68 1/68 1/72 1/72 1 / 75 1/75 1/90 1/90 1/92 1/92 3/04 3/04 3/30 3/30 3/37 3/37 3/386 3/386 10/02 10/02 17/04 17/04 17/06 17/06 17/08 17/08 17/08 (72) Inventor Cott, Kevin Lee, Cincinnati, Ohio, United States of America, Bentbrook, Drive 2920 (72) Inventor Sebel, Jeffrey John, Ohio, United States of America, Loveland, Miami, Trails, Drive 6651 (72) Inventor Connor, Daniel Steadman, Cincinnati, Ohio, United States of America, Sage Meadow, Drive 9217 (72) Inventor Kryp, Thomas Anthony Ohio, United States of America Lavland, Three, Chimneys, Lane 599 (72) Inventor Vinson, Philip Kyle Ohio, USA, Fairfield, Windermere, Lane 5803 (72) Inventor Shaper, William Michael Laurensburg, Indiana, United States of America, Picnic, Woods, Drive 2393 (72) Inventor Casturi, Chandrica Cincinnati, Cliffwood, Court, Ohio, USA 10044 F-term (reference) 4H003 AB05 AB10 AB14 AB15 AB18 AB19 AB21 AB23 AB27 AB28 AB31 AC05 AC08 AC10 AC13 AC15 AD04 AD05 AE02 BA09 BA12 BA15 DA17 EA09 EA12 EA15 EA16 EA19 EA21 EB04 EB08 EB13 EB14 EB22 EB28 EB30 EB36 EB41 EB42 EC01 EC02 EC03 ED02 ED28 FA05 FA07 FA12 FA26 FA28 FA29 FA34 FA36

Claims (30)

[Claims] 1. i) 0.01% to 99.99% by weight of the composition is a surfactant mixture, said surfactant mixture having the formula: ## STR1 ## Wherein L is an acyclic aliphatic hydrocarbyl of a total of 6 to 18 carbon atoms; M is a cation or a mixture of cations, q is its valency; A number selected such that the surfactant mixture is electrically neutral;
R 'is selected from H and C ₁ -C ₃ alkyl; R''is selected from H and C ₁ -C ₃ alkyl; R''' is selected from H and C ₁ -C ₃ alkyl; R ' And R ″ are both non-terminally attached to said L, and at least one R ′ and R ″ is C ₁ -C ₃ alkyl; A is aryl] of the alkylarylsulfonate surfactant of An alkylaryl sulfonate surfactant system comprising at least two isomers, wherein said alkylaryl sulfonate surfactant system comprises R ′, R ″, and A
-Contains two or more isomers with respect to the point of attachment of -L;
0% of said alkylaryl sulfonate surfactant system, wherein A is attached to L at any of the two terminal carbon atoms at a position selected from the α-position and the β-position; and further, said alkylaryl sulfonate surfactant The system is characterized in that, when quaternary carbon atoms are present, the alkylaryl sulfonate surfactant system has a weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in L of at least 10: 1. And at least one of the following properties: a loss of less than 40% by weight as measured by a hardness resistance test; ii) 0.0001% to 99.99% by weight of the composition is conventional hand washing Iii) 0.01 to 7% by weight of the composition is a divalent ion selected from the group consisting of magnesium, calcium, and mixtures thereof. A dishwashing composition for hand washing, comprising the above. 2. i) 0.01% to 99.99% by weight of the composition is surface active
A mixture of surfactants, wherein said mixture of surfactants has the following formula:Wherein M is a cation and q is the valency of said cation; a and b are
A is a number selected such that the mixture is electrically neutral; A is aryl
R "" is hydrogen and C₁~ C_ThreeR 'is hydrogen and C₁
~ C_ThreeR ″ is hydrogen and C₁~ C_ThreeSelected from alkyl
R "" is hydrogen and C₁~ C_FourV is an integer from 0 to 10;
X is an integer from 0 to 10; y is an integer from 0 to 10]
Excludes ortho, meta, para, and stereoisomers of aryl sulfonate surfactants
Alkylaryl sulfonate containing at least two isomers calculated according to
A surfactant system; wherein the total number of carbon atoms attached to A is less than about 20;
The phonate surfactant system comprises R '' ''-C (-) H (CH_Two
)_vC (-) H (CH_Two)_xC (-) H (CH_Two)_y-CH_ThreeR ', R' ', to
And two or more isomers with respect to the point of attachment of A and R ';
At least one is C₁~ C_ThreeAlkyl; R "" is C₁In the case of v + x +
the sum of y is at least 1; the sum of v + x + y when R "" is H
Is at least 2; less of the alkylaryl sulfonate surfactant system
In at least 60%, A is part of the above formula R '' "-C (-) H (CH _Two )_vC (-) H (CH_Two)_xC (-) H (CH_Two)_y-CH_ThreeAnd the two terminal charcoals
A bond at any position selected from the α-position and the β-position to any one of the elementary atoms;
The activator system is R '' "-C (-) H (CH_Two)_vC (-) H (
CH_Two)_xC (-) H (CH_Two)_y-CH_ThreeNon-quaternary carbon atoms and quaternary carbon atoms in
At least 10: 1 by weight; loss as measured by hardness test
Is at least 40% by weight; ii) from 0.0001% to 99.99% by weight of the composition is conventional hand-washed dishwashing.
And iii) 0.01% to 7% by weight of the composition comprises magnesium, calcium,
And a divalent ion selected from the group consisting of a mixture thereof and a mixture thereof. 3. i) 0.01% to 99.99% by weight of the composition is a surfactant mixture, said surfactant mixture comprising: a) 0.01% by weight of said surfactant mixture ９９99.99% by weight has the following formula: Wherein L is an acyclic aliphatic hydrocarbyl of a total of 6 to 18 carbon atoms; M is a cation or a mixture of cations; q is its valency; A number selected such that the surfactant mixture is electrically neutral;
'Is selected from H and C ₁ -C ₃ alkyl; R''is selected from H and C ₁ -C ₃ alkyl; R''' is selected from H and C ₁ -C ₃ alkyl; R 'and R ″ is non-terminally bound to the L, and at least one of R ′ and R ′
'' Is C ₁ -C ₃ alkyl; A is aryl], wherein said alkyl aryl sulfonate surfactant system comprises at least two isomers of said alkyl aryl sulfonate surfactant; Contains two or more isomers with respect to R ′, R ″, and the point of attachment of AL; in at least 60% of the alkylaryl sulfonate surfactant systems, A is two terminal carbon atoms And wherein the alkylaryl sulfonate surfactant system further comprises, when a quaternary carbon atom is present, the alkylaryl sulfonate interface. The activator system has a weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in L of at least 1
0: 1 and having a loss of less than or equal to 40% by weight as measured by a hardness resistance test; b) 0.01% to 99% by weight of said surfactant mixture. 99% by weight are at least one isomer of the linear analogue of said alkylaryl sulfonate surfactant (a); ii) 0.0001% to 99.99% by weight of the composition are conventional hand dishwashing And iii) 0.01% to 7% by weight of the composition is a divalent ion selected from the group consisting of magnesium, calcium, and mixtures thereof; hand dishwashing containing Composition. 4. i) 0.01% to 99.99% by weight of the composition is a surfactant mixture, said surfactant mixture comprising: a) 0.01% by weight of the surfactant mixture; 99.99% by weight has the following formula: Wherein M is a cation, q is the valency of the cation, a and b are numbers selected so that the mixture is electrically neutral; A is aryl; R ′ ″ is selected from H and C ₁ -C ₃ alkyl; R ′ is hydrogen and C ₁ -C ₃ alkyl.
It is selected from C ₃ alkyl; R '' is selected from hydrogen and C ₁ -C ₃ alkyl; R '''' is selected from hydrogen and C ₁ -C ₄ alkyl; v is an integer of 0 X is an integer from 0 to 10; y is an integer from 0 to 10]. Wherein the total number of carbon atoms attached to A is less than 20; and wherein the alkylaryl sulfonate surfactant system is part of the formula, _{C (-) H (CH 2} ) v C (-) H (CH 2) x C (-) H (CH 2) R to _{y -CH 3 ', R''} , and two with respect to the bonding position of a Or more isomers; R 'and R'
At least one is C ₁ -C ₃ alkyl; when R ″ ″ is C ₁ , v +
when R ″ ″ is H, the sum of v + x + y is at least 2; and in at least 60% of the alkylaryl sulfonate surfactant systems, A is part of the formula R ″ ″-C (−) H
(CH ₂ ) _v C (−) H (CH ₂ ) _x C (−) H (CH ₂ ) _y —CH ₃ at one of its two terminal carbon atoms selected from α-position and β-position Further, the alkylaryl sulfonate surfactant system may further comprise, if a quaternary carbon atom is present, the alkylaryl sulfonate surfactant system may be a compound of the formula C (−) H (CH ₂ ) _v C (−) H (
_{CH 2) x C (-)} H (CH 2) weight ratio of the non-quaternary carbon atom and the quaternary carbon atom in the _y -CH ₃ of at least 10: and it is 1, by hardness tolerance test Has at least one of the following properties: a loss of no more than 40% by weight; and b) 0.01% to 99.99% by weight of said surfactant mixture is said alkylaryl sulfonate surfactant. At least one isomer of the linear analog of (a); ii) from 0.0001% to 99.99% by weight of the composition is a conventional hand dishwashing aid; and iii) 0.01 to 7% by weight is a divalent ion selected from the group consisting of magnesium, calcium, and a mixture thereof; a dishwashing composition for hand washing, comprising: 5. The dishwashing composition for hand-washing according to claim 1, wherein the loss is not more than 20% by weight as measured by a hardness resistance test. 6. A is i) benzene, ii) toluene, iii) xylene, iv)
The dishwashing composition for hand washing according to any one of claims 1 to 5, wherein the composition is selected from the group consisting of naphthalene, and v) mixtures thereof. 7. The method according to claim 1, wherein A is benzene.
Item 9. The dishwashing composition for hand washing according to item 9. 8. The dishwashing composition for hand washing according to claim 1, wherein one of R ′ and R ″ is methyl or ethyl. 9. The dishwashing composition for hand washing according to claim 1, wherein one of R ′ and R ″ is methyl. 10. In at least 80% of the alkylaryl sulfonate surfactant systems, A is attached to the L at a position selected from the α-position and the β-position of any of the two terminal carbon atoms. The dishwashing composition for hand washing according to any one of claims 1 to 9. 11. The hand-washing dishwashing composition according to claim 1, wherein R ″ ″ is hydrogen, methyl, or ethyl. 12. In at least 80% of the alkylarylsulfonate surfactant systems, A is R ″ ″-CH (A) at a position selected from the α-position and the β-position of any of the two terminal carbon atoms. CH ₂ ) _v CH (CH ₂ ) _x CH (CH ₂
) Bonded to _y -CH _3, hand dishwashing cleaning composition according to any one of claims 1 to 11. 13. The cleaning composition according to claim 1, wherein the cleaning composition is in the form of a liquid, paste, liquid gel, gel, microemulsion, liquid crystal, granule, agglomerated powder, or powder.
The dishwashing composition for hand washing according to any one of claims 12 to 12. 14. The cleaning composition adjuvant further comprises a surfactant selected from the group consisting of alkylene carbonates, monoalkyl succinates, alkyl polysaccharides, ethoxylated glycerol type compounds, and mixtures thereof. The dishwashing composition for hand washing according to any one of claims 1 to 11. 15. The conventional hand-washing dishwashing aid comprises a surfactant other than (i), a builder, a detergent enzyme, at least a part of a water-soluble or water-dispersible polymer, an abrasive, a disinfectant, Discoloration inhibitor, dye, solvent, hydrotrope, fragrance, thickener, antioxidant, processing aid, foaming agent, defoamer, foam stabilizer, diamine, carrier,
15. The method according to claim 1, which is selected from the group consisting of an enzyme stabilizer, an antioxidant, a polysaccharide, a buffer, an antifungal agent, a fungicide, an insect repellent, an anticorrosion aid, a chelating agent, and a mixture thereof. The dishwashing composition for hand washing according to any one of the above. 16. further comprising a nonionic surfactant at a level of 0.5 wt% to 25 wt% of the detergent composition, the nonionic surfactant, - a straight-chain C ₁₀ -C A hydrophobic group selected from ₁₆ alkyl, medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, Guerbet branched C ₁₀ -C ₁₆ alkyl, and mixtures thereof, and 1-15 ethoxylates in capped or uncapped form , 1-15 propoxylate, 1-15 butoxylate, and hydrophilic groups selected from mixtures thereof, wherein the polyalkoxylated alcohol is in the form of a cap or uncapped.
The dishwashing composition for hand washing according to any one of claims 1 to 15. 17. The detergent composition further comprising an alkyl sulfate surfactant at a level of 0.5% to 25% by weight of the detergent composition, wherein the alkyl sulfate surfactant is a linear C ₁₀ -C ₁₈ alkyl. , medium chain C ₁ -C ₃ branched C ₁₀ -C ₁₈ alkyl, a Guerbet branching C ₁₀ -C ₁₈ alkyl, and mixtures thereof, as well as Na, K, and a cation selected from the mixture, according to claim 1 The dishwashing composition for hand washing according to any one of claims 16 to 16. 18. The detergent composition further comprising an alkyl (polyalkoxy) sulfate surfactant at a level of 0.5% to 25% by weight of the detergent composition, wherein the alkyl (polyalkoxy) sulfate surfactant comprises: linear C ₁₀ -C ₁₆ alkyl, mid-chain C ₁ -C ₃ branched C ₁₀ -C ₁₆ alkyl, hydrophobic group selected from Guerbet branching C ₁₀ -C ₁₆ alkyl, and mixtures thereof, - the cap or uncapped form 1 to 15 polyethoxy sulfate, 1 to 1
An alkyl (polyalkoxy) sulfate hydrophilic group selected from 15 polypropoxy sulfate, 1 to 15 polybutoxy sulfate, and 1 to 15 mixed poly (ethoxy / propoxy / butoxy) sulfate, and a mixture thereof; 18. The dishwashing composition for hand washing according to any one of claims 1 to 17, having a cation selected from: and a mixture thereof. 19. The method of claim 1, further comprising a surfactant, wherein said surfactant is selected from the group consisting of anionic, nonionic, amphoteric, zwitterionic, and mixtures thereof. A dishwashing composition for hand washing according to any one of the preceding claims. 20. An organic diamine, wherein the diamine has the following formula: Wherein R _2-5 are independently selected from H, methyl, ethyl, and ethylene oxide; C _x and C _v are independently selected from a methylene group or a branched alkyl group, wherein x + v is 3 to A is optionally present and has a pKa of the diamine
Is selected from electron donating or electron accepting moieties selected to adjust to a desired range; when A is present, x and y must both be 2 or more. 20. The dishwashing composition for hand washing according to any one of claims 1 to 19, which is performed. 21. An organic diamine, wherein the diamine has the following formula: Wherein R ⁶ is independently hydrogen, C ₁ -C ₄ linear or branched alkyl, formula-(R ⁷
O) _m R ^{8 wherein} R ⁷ is C ₂ -C ₄ linear or branched alkylene, and mixtures thereof, R ⁸ is hydrogen, C ₁ -C ₄ alkyl, and mixtures thereof, and m is 1 to 1
0 and a) is selected from the group consisting of alkyleneoxy having; X is, i) C ₃ ~C ₁₀ linear alkylene, C ₃ -C ₁₀ branched alkylene, C ₃ -C ₁₀ cyclic alkylene, C ₃ ~ C ₁₀ branched cyclic alkylene, formula _{^{- (R 7 O) m R}} 7 - ( wherein, R ⁷ and m are as defined above and is identical) alkyleneoxyalkylene having; is ii) units pKa of the diamines containing one or more electron donor moieties or electron acceptor moieties to higher than 8, C ₃ ~C ₁₀ straight-chain, C ₃ -C ₁₀ branched linear, C ₃ -C ₁₀
Cyclic, C ₃ -C ₁₀ branched cyclic alkylene, C ₆ -C ₁₀ arylene; is a unit chosen from mixtures and iii) (i) and (ii), pKa of the diamines is at least 8 The dishwashing composition for hand washing according to any one of claims 1 to 20, which is an organic diamine. 22. The diamine is dimethylaminopropylamine, 1,6
-Hexanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-pentanediamine, 1,3-diaminobutane, 1,2-bis (2-aminoethoxy) ethane, isophorone 22. The dishwashing composition for hand washing according to claim 20, wherein the composition is selected from the group consisting of diamines, 1,3-bis (methylamine) -cyclohexane, and mixtures thereof. 23. An anionic surfactant, wherein the anionic surfactant is alkyl sulfate, alkyl alkoxy sulfate, linear alkyl benzene sulfonate, α-olefin sulfonate, paraffin sulfonate, methyl ester sulfonate, alkyl ester 23. The dishwashing composition according to any one of claims 1 to 22, wherein the composition is selected from the group consisting of sulfonates, alkyl alkoxylated sulfates, sarcosinates, taurinates, alkyl alkoxy carboxylates, and mixtures thereof. 24. The composition further comprising a nonionic surfactant, wherein said nonionic surfactant is selected from the group consisting of alkyl ethoxylates, polyhydroxy fatty acid amides, alkyl polyglycosides, alkyl ethoxylates, and mixtures thereof. 24. The dishwashing composition for hand washing according to any one of claims 1 to 23. 25. The method according to claim 1, further comprising an amphoteric surfactant, wherein the amphoteric surfactant is selected from the group consisting of betaines, sulfobetaines, amine oxides, and mixtures thereof. Item 9. The dishwashing composition for hand washing according to item 9. 26) i) FormulaWherein R is independently hydrogen, C₁~ C₈Alkyl, and mixtures thereof, ¹ Is hydrogen, C₁~ C₆Alkyl, and mixtures thereof, wherein n is 2-6.
Having (N, N-dialkylamino) alkyl acrylate ester homopoly
And ii) (i) with the following formula:[Wherein, R¹Is hydrogen, C₁~ C₆Alkyl, and mixtures thereof]
A) wherein the ratio of (i) to (i) is from 2: 1 to 1: 2, further comprising a polymerizable foam stabilizer selected from the group consisting of:
3. The composition of claim 1 having a molecular weight of 1,000 to 2,000,000 daltons.
26. The dishwashing composition for hand washing according to any one of claims 25. 27. The handwash according to any one of claims 1 to 26, further comprising an enzyme, wherein the enzyme is selected from the group consisting of amylase, protease, cellulase, lipase, and a mixture thereof. Dishwashing composition. 28. A method for washing dishes, comprising the step of contacting soiled dishes which need to be washed with an aqueous solution of the composition according to any one of claims 1 to 27. 29. The method of claim 28, further comprising diluting said composition with water. 30. The method of claim 28, further comprising applying the composition directly to a sponge or a cleaning cloth.