KR100386760B1 - Liquid laundry detergent compositions comprising HEDP and polyamines - Google Patents

Abstract

A liquid detergent composition for laundry comprising a water soluble and / or water dispersible modified polyamine having a HEDP and a functionalized backbone portion that provides a stabilizing effect.

Description

Liquid laundry detergent compositions comprising HEDP and polyamines

Field of invention

The present invention relates to a laundry liquid detergent composition comprising a water soluble and / or water dispersible modified polyamine having a backbone functionalized with HEDP.

Background of the Invention

Liquid detergent compositions for laundry comprising HEDP (hydroxyethane-1,1-diphosphonate) are known and are described, for example, in French Patents 2,677,370, European Patents 517,605, European Patents 384,515 and Europe. Patent 3737184. For laundry liquid detergent compositions, HEDP provides improved stain removal and brightening benefits for fabrics. However, when HEDP is formulated with liquid detergents, especially concentrated liquid detergents, there is a problem that the physical stability is poor in the presence of high concentrations of surfactants and other detergent components. The use of certain salts of HEDP to improve the physical stability of the compositions is described in EP 517,605. It is an object of the present invention to formulate a physically stable liquid detergent composition comprising HEDP and a surfactant and optionally other cleaning ingredients. As a solution to this, the present invention has found that the presence of certain polymers can provide the desired stabilizing effect to formulate stable compositions comprising HEDP.

Summary of the Invention

The present invention

Surfactants,

Effective amount of HEDP and

Formula with modified polyamine of Formula 1 With a polyamine backbone or a modified polyamine of Formula 2 corresponding to wherein n is from 0 to about 200 and m is from 4 to about 400 A stabilizing amount of a water-soluble or water dispersible modified polyamine, wherein n is from 0 to about 200, m is from 4 to about 400, and k is less than or equal to n. Molecular weight of the polyamine backbone prior to being greater than about 200 daltons].

V _{(n + 1)} W _m Y _n Z

V _{(n-k + 1)} W _m Y _n Y ' _k Z

In Chemical Formulas 1 and 2 above,

n is 0 to about 200,

m is 4 to about 400,

k is less than or equal to n,

Iii) the V unit is Is a terminal unit of

Ii) W unit is represented by Is the main chain unit of,

Iii) Y unit is Is a side chain unit of,

Iii) the Z unit is Is the terminal unit of

Main chain bond R units include C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy-alkylene, C ₈ -C ₁₂ dialkyl Arylene,-(R ¹ O) _X R ¹ -,-(R ¹ O) _X R ⁵ (OR ¹ ) _X -,-(CH ₂ CH (OR ² ) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH (OR ² ) CH ₂ ) _W- , -C (O) (R ⁴ ) _r C (O)-, -CH ₂ CH (OR ² ) CH ₂ -and a combination thereof R ¹ is C ₂ -C ₃ alkylene and combinations thereof, R ² is hydrogen, — (R ¹ O) _X B and combinations thereof, R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and combinations thereof, R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene and combinations thereof, R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxy-alkylene, C ₄ -C ₁₂ dihydroxy Alkylene, C ₈ -C ₁₂ dialkylarylene, -C (O)-, -C (O) NHR ⁶ NHC (O)-, -R ¹ (OR ¹ )-, -C (O) (R ⁴ ) _r C (O)-, -CH ₂ CH (OH) CH _2- , -CH ₂ CH (OH) CH ₂ O (R ¹ O) _y R ¹ -OCH ₂ CH (OH) CH ₂ -and combinations thereof, R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene E unit is hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl,-(CH ₂ ) _p -CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) -CO ₂ M,-(CH ₂ ) _p PO ₃ M,-(R ¹ O) _X B, -C (O) R ³ And combinations thereof, provided that if any one of the E units bound to nitrogen is hydrogen, then nitrogen is also not N-oxide and B is hydrogen, C ₁ -C ₆ alkyl, — (CH ₂ ) _q -SO ₃ M,-(CH ₂ ) _P CO ₂ M,-(CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M,-(CH ₂ ) _q- (CHSO ₂ M) CH ₂ SO ₃ M ,-(CH ₂ ) _P PO ₃ M, -PO ₃ M and combinations thereof, M is hydrogen or an amount of water-soluble cation sufficient to satisfy the charge balance, X is a water-soluble anion, p is 1-6 , q is 0 to 6, r is 0 or 1, w is 0 or 1, x is 1 to 100, y is 0 to 100 and z is 0 or 1.

Unless stated otherwise, the percentages, ratios, and parts herein are all based on the weight of the total composition. Unless stated otherwise, all temperatures are in degrees Celsius (° C.) and the ratios are by weight. All cited documents, which are incorporated by reference herein, are present in relevant parts.

Detailed description of the invention

Liquid detergent composition

The compositions of the present invention are liquid detergent compositions, which typically comprise but do not necessarily comprise 20 to 70%, preferably 25 to 60%, most preferably 30 to 40% by weight of water of the total composition. Do not. Compositions containing up to 40% by weight of water are generally referred to as concentrated compositions, in which the stability problem for HEDP is particularly significant.

HEDP

The composition of the present invention comprises an effective amount of HEDP (hydroxyethane-1,1-diphosphonate). By effective amount is meant herein an amount sufficient to improve the stain removal properties of the detergent composition and / or to improve the brightening performance of the composition. Typically this amount is from 0.01 to 10%, preferably from 0.7 to 5%, most preferably from 0.2 to 2% by weight of the total composition. Suitable HEDPs for use in the present invention are HEDPs in acid form or any salt form thereof. A suitable commercial form of HEDP is Dequest ^R 2010 manufactured by Monsanto.

Polyamine

The composition of the present invention further comprises a stabilized amount of a water soluble or water dispersible modified polyamine. These polyamines include backbones which may be straight chain or cyclic. The polyamine backbone may also comprise large or small amounts of polyamine side chains. In general, the polyamine backbones described herein are modified in such a way that each nitrogen of the polyamine chain is subsequently described as a substituted, quaternized or oxidized unit or mixture thereof.

For the purposes of the present invention, the term "denaturation" refers to the substitution (substitution) of main chain -NH hydrogen atoms with E units, quaternization of the main chain nitrogen (quaternization) or oxidation (oxidation) of the main chain nitrogen with N-oxide. define. The terms "modified" and "substituted" are used interchangeably when referring to a method of replacing a hydrogen atom which is bonded with a backbone nitrogen with an E unit. Although quaternization or oxidation can occur in some unsubstituted cases, substitutions preferably involve the oxidation or quaternization of one or more backbone nitrogens.

Straight or acyclic polyamine backbones, wherein the backbone before subsequent denaturation comprises primary, secondary and tertiary amine nitrogens linked by R "bond" units.

Has The cyclic polyamine backbone, wherein the backbone before subsequent denaturation comprises primary, secondary and tertiary amine nitrogens linked by R "bond" units

Has

For the purposes of the present invention, primary amine nitrogens containing side chains or backbones once denatured are defined as V or Z "terminal" units. For example, when the primary amine moiety located at the end of the polyamine main chain or side chain of the structure H ₂ NR]-according to the present invention is modified, hereafter it is defined as a V “terminal” unit or simply V unit. However, for the purposes of the present invention, some or all of the primary amine residues may not be modified, provided they meet the limits described further herein below. Due to their position in the backbone chain these undenatured primary amine residues leave "terminal" units. Likewise, when the primary amine moiety located at the end of the polyamine main chain of the structural formula -NH ₂ is modified according to the invention, it is hereafter defined as Z "terminal" unit or simply Z unit. Such units may not be modified, provided they meet the limits described further herein below.

In a similar manner, secondary amine nitrogens containing side chains or backbones once denatured are defined as W "backbone" units. For example, according to the present invention of

When the side chain and main chain main components of the present invention which are secondary amine residues are modified, hereinafter, it is defined as W "backbone" units or simply W units. However, for the purposes of the present invention, some or all of the secondary amine residues may not be modified. Due to their location in the main chain, these unmodified secondary amine residues leave "backbone" units.

In a further similar manner, tertiary amine nitrogens containing side chains or backbones once denatured are further defined as Y "side chain" units. For example, according to the present invention When the chain branching site in the polyamine backbone or other side chains or rings, which is the tertiary amine residue of, is modified, it is hereafter defined as Y "side chain" units or simply Y units. However, for the purposes of the present invention, some or all of the tertiary amine residues may not be modified. Due to their position in the main chain chain, these unmodified tertiary amine residues leave "side chain" units. The R units associated with the V, W and Y unit nitrogens used to bind the polyamine nitrogens are described herein below.

Thus, the final modified structure of the polyamines of the present invention is a linear polyamine cotton antifouling formula for (cotton soil release) can be represented by the general formula V _{(n + 1)} W _m Y _n Z for the polymer and the cyclic polyamine cotton antifouling polymer V _{( n-k + 1)} W _m Y _n Y ' _k Z. For polyamines containing rings, the formula Y 'unit is used as the branching site for the main chain or branched ring. For all Y 'units, the formula forms the linking site of the ring in the polymer backbone or side chain Y units of are present. In the unusual case that the main chain is a complete ring, the polyamine backbone is And thus do not contain a Z terminal unit and have the formula V _nk W _m Y _n Y ' _k , where k is the number of rings forming the side chain units. Preferably, the polyamine backbone of the present invention does not contain a ring.

For bicyclic polyamines, the ratio of index n to index m is related to the degree of branching. Fully unbranched straight chain modified polyamines according to the invention are compounds of the formula VW _m Z, where n is equal to 0. If the value of n is large (the ratio of m to n is small), the degree of branching of the molecule is large. Typically, the value of m ranges from 4 to about 400, which is the lowest value, but it is also preferred if the value of m is large, especially if the value of the index n is very small or nearly zero.

Each primary, secondary or tertiary polyamine nitrogen once modified according to the invention is further defined as a member of any one of the three general groups (simple substitution, quaternization or oxidation). . Depending on whether these unmodified polyamine nitrogen units are primary nitrogen, secondary nitrogen or tertiary nitrogen, they are classified into V units, W units, Y units or Z units. That is, for the purposes of the present invention, unmodified primary amine nitrogens are in V units or Z units and unmodified secondary amine nitrogens are in W units and unmodified tertiary amine nitrogens are in Y units.

Denatured primary amine residues are referred to as V "terminal" units having any of the following three forms:

a) Units in which the structural formula is simply substituted as follows:

b) quaternized units whose structural formula is:

In the structural formula above,

X is a suitable counter ion providing charge balance.

c) oxidized units whose structural formula is:

Denatured secondary amine residues are referred to as W "backbone" units having any of the following three forms:

a) Units in which the structural formula is simply substituted:

b) quaternized units whose structural formula is:

In the structural formula above,

X is a suitable counterion supply charge balance.

c) oxidized units whose structural formula is:

Denatured tertiary amine residues are referred to as Y "side chain" units having any of the following three forms:

a) Deformed units whose structural formula is:

b) quaternized units whose structural formula is:

In the structural formula above,

X is a suitable counterion supply charge balance.

c) oxidized units whose structural formula is:

Certain modified primary amine residues are referred to as Z "terminal" units having any of the following three forms:

a) Units in which the structural formula is simply substituted:

b) quaternized units whose structural formula is:

In the structural formula above,

X is a suitable counterion supply charge balance.

c) oxidized units whose structural formula is:

When neither position of nitrogen is substituted or modified, hydrogen is considered to be substituted by E. For example, a primary amine unit comprising one E unit in the form of a hydroxyethyl residue is the V terminal unit of formula (HOCH ₂ CH ₂ ) HN—.

For the purposes of the present invention, there are two forms of chain end units, the V unit and the Z unit. The Z "terminal" unit is derived from the terminal primary amino residues of the formula -NH ₂ . The bicyclic polyamine backbones according to the invention comprise only Z units, but the cyclic polyamines cannot comprise Z units. Except where the Z units are modified to form N-oxides, the Z "terminal" units may be substituted with any one of the E units described further herein below. When the Z unit nitrogen is oxidized to N-oxide, E is not hydrogen because nitrogen is modified.

The polyamines of the present invention comprise backbone R "bond" units used to link the nitrogen atoms of the backbone. R units include units called "hydrocarbyl R" units and "oxy R" units for the purposes of the present invention. “Hydrocarbyl” R units may be C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, wherein the hydroxyl moiety may occupy any position in the R unit chain, Provided that carbon atoms are directly bonded to the polyamine backbone nitrogens); C ₄ -C ₁₂ dihydroxyalkylene, wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain, provided that these carbon atoms are bonded directly to the polyamine backbone nitrogens; And C ₈ -C ₁₂ dialkylarylenes which are arylene moieties having two alkyl substitution groups as part of the binding chain for the purposes of the present invention. For example, the dialkylarylene unit is a chemical formula Although the units need not be 1,4-substituted, 1,2 or 1,3 substituted C ₂ -C ₁₂ alkylene, preferably ethylene, 1,2-propylene and mixtures thereof, more Preferably ethylene. "Oxy" R units are-(R ¹ O) _x R ⁵ (OR ¹ ) _x- , -CH ₂ CH (OR ² ) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH (OR ²⁾ ) CH ₂ ) _w- , -CH ₂ CH (OR ² ) CH ₂ -,-(R ¹ O) _x R ¹ -and mixtures thereof. Preferred R units are C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene,-(R ¹ O) _x R ^1- , -CH ₂ CH (OR ² ) CH ₂ -,-(CH ₂ CH (OH) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH- (OH) CH ₂ ) _w- ,-(R ¹ O) _x R ⁵ (OR ¹ ) _x- , more preferred R units are C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₂ dihydroxyalkyl Lene,-(R ¹ O) _x R ¹ -,-(R ¹ O) _x R ⁵ (OR ¹ ) _x -,-(CH ₂ CH (OH) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH- (OH) CH ₂ ) _w -and mixtures thereof, even more preferred R units are C ₂ -C ₁₂ alkylene, C ₃ hydroxyalkylene and mixtures thereof, most preferably C ₂ -C ₆ alkylene. Most preferred backbones of the present invention comprise at least 50% of R units which are ethylene.

R ¹ units are C ₂ -C ₆ alkylene and mixtures thereof, preferably ethylene. R ² is hydrogen and — (R ¹ O) _× B, preferably hydrogen.

R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkylene, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof, preferably C ₁ -C ₁₂ alkyl , C ₇ -C ₁₂ arylalkylene, more preferably C ₁ -C ₁₂ alkyl, most preferably methyl. R ³ units are used as part of the E units described herein below.

R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene, preferably C ₁ -C ₁₀ alkylene, C ₈ -C ₁₂ arylalkylene, more preferably C ₂ -C ₈ alkylene, most preferably ethylene or butylene.

R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, -C (O)-,- C (O) NHR ⁶ NHC (O)-, -C (O) (R ⁴ ) _r C (O)-, -R ¹ (OR ¹ )-, -CH ₂ CH (OH) CH ₂ O (R ¹ O) _y R ¹ OCH ₂ CH (OH) CH _2- , -C (O) (R ⁴ ) _r C (O)-, -CH ₂ CH (OH) CH _2- , R ⁵ is preferably ethylene , -C (O)-, -C (O) NHR ⁶ NHC (O)-, -R ¹ (OR ¹ )-, -CH ₂ CH (OH) CH _2- , -CH ₂ CH (OH) CH ₂ O (R ¹ O) _y R ¹ OCH ₂ CH— (OH) CH ₂ —, more preferably —CH ₂ CH (OH) CH ₂ —.

R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene.

Preferred "oxy" R units are R^Oneunit , R²Unit and R⁵It is further defined as a unit. Preferred "oxy" R units are preferred R^OneUnit, R²Unit and R⁵Contains units. Preferred cottonless antifouling agent of the present invention is ethylene^OneContain at least 50% of units. Preferred R^OneUnit, R²Unit and R⁵The unit is combined with the "oxy" R units to obtain the desired "oxy" R units in the following manner.

Iii) more preferably, R ⁵ is substituted with-(CH ₂ CH ₂ O) _x R ⁵ (OCH ₂ CH ₂ ) _x -and-(CH ₂ CH ₂ O) _x CH ₂ CHOHCH ₂ (OCH ₂ CH ₂ ) to obtain _x −,

Ii) preferably, R ¹ and R ² are substituted with-(CH ₂ CH (OR ² ) CH ₂ O) _z (R ¹ O) _y R ¹ O (CH ₂ CH (OR ² ) CH ₂ ) _w- -(CH ₂ CH (OH) CH ₂ O) _z (CH ₂ CH ₂ O) _y CH ₂ CH ₂ O (CH ₂ CH (OH) CH ₂ ) _w-

Ⅲ) Preferably, the _{^{R 2 -CH 2 CH (OR 2}} ) CH 2 - substituted by a _{-CH 2 CH (OH) CH 2} - , to obtain the.

E units are hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl,-(CH ₂ ) _p CO ₂ M,-(CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M,-(CH ₂ ) _p PO ₃ M,-(R ¹ O) _m B, -C (O) R ³ , preferably Is hydrogen, C ₂ -C ₂₂ hydroxyalkylene, benzyl, C ₁ -C ₂₂ alkylene,-(R ¹ O) _m B, -C (O) R ³ ,-(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M, more preferably C ₁ -C ₂₂ alkylene,-(R ¹ O) _x B, -C (O) R ³ ,-(CH ₂ ) _p CO ₂ M,-(CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M, most preferably C ₁ -C ₂₂ alkylene,- (R ¹ O) _x B and —C (O) R ³ . If nitrogen is modified or unsubstituted, the hydrogen atom will remain as a residue representing E.

When V units, W units or Z units are oxidized, the E units do not contain hydrogen atoms, ie nitrogens are N-oxides. For example, the main chain or side chains may be structural It does not contain units of.

Also, when V units, W units or Z units are oxidized, the E units do not contain carbonyl moieties that are bonded directly to the nitrogen atom, ie nitrogens are N-oxides. According to the invention, the E unit -C (O) R ³ residues are not bound to N-oxide modified nitrogen, i.e. N-oxide amides or mixtures thereof are absent.

B is hydrogen, C ₁ -C ₆ alkyl,-(CH ₂ ) _q SO ₃ M,-(CH ₂ ) _p CO ₂ M,-(CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M,-( CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M,-(CH ₂ ) _p PO ₃ M, -PO ₃ M, preferably hydrogen,-(CH ₂ ) _q SO ₃ M,-(CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M,-(CH ₂ ) _q (CHSO ₂ M) CH ₂ SO ₃ M, more preferably hydrogen or-(CH ₂ ) _q SO ₃ M.

M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance. For example, sodium cations satisfy-(CH ₂ ) _p CO ₂ M and-(CH ₂ ) _q SO ₃ M equally, so-(CH ₂ ) _p CO ₂ Na and-(CH ₂ ) _q SO ₃ Generate Na residues. One or more monovalent cations (sodium, potassium, etc.) may be combined to satisfy the necessary chemical charge balance. However, one or more anionic groups may be charge balanced by divalent cations, or one or more monovalent cations may be necessary to meet the charge requirements of multiple anionic radicals. For example, a-(CH ₂ ) _p PO ₃ M residue substituted with sodium atoms has the formula-(CH ₂ ) _p PO ₃ Na ₃ . Divalent cations such as calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ) may be substituted with or combined with other suitable monovalent water soluble cations. Preferred cations are sodium and potassium, more preferably sodium.

X is a water-soluble anionic [e.g., chlorine (Cl ^-), bromine (Br ^-) and iodine (I ^-)] or, X is a charged radical with negative [e.g., sulfate (SO ₄ ^2-) and methosulfate (CH ₃ SO ₃ ^-)] it can be.

Formula exponents have the following values: p has a value of 1 to 6, q has a value of 0 to 6, r has a value of 0 or 1, w has a value of 0 or 1, and x is Has a value of 1 to 100, preferably 5 to 30, y has a value of 0 to 100, z has a value of 0 or 1, m has a value of 4 to about 400, n has a value of 0 to Has a value of about 200 and the sum of m and n has a value of 5 or greater.

Preferred polyamines of the invention comprise backbones wherein up to about 50%, preferably up to about 20%, more preferably up to 5% of the R groups comprise “oxy” R units, most preferably the R units It does not include "oxy" R units.

Most preferred polyamines that do not include "oxy" R units include backbones wherein up to 50% of the R groups contain at least 3 carbon atoms. For example, ethylene, 1,2-propylene and 1,3-propylene contain up to 3 carbon atoms and "hydrocarbyl" R units are preferred. That is, when the main chain R units are C ₂ -C ₁₂ alkylene, C ₂ -C ₃ alkylene is preferred, with ethylene being most preferred.

Cotton polyamines of the present invention include modified homogeneous and heterogeneous polyamine backbones, where up to 100% of the -NH units are modified. For the purposes of the present invention, the term "uniform polyamine backbone" is defined as a polyamine backbone having the same R units (ie all ethylene). However, this identity means that due to the artificial structure of the chosen chemical synthesis method it does not exclude polyamines comprising other external units comprising the polymer backbone present. For example, it is known to those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polyethyleneimine, and thus a sample of polyethyleneimine comprising one hydroxyethyl moiety generated from the polymerization "initiator". May be considered to include a homogeneous polyamine backbone for the purposes of the present invention. The polyamine backbone comprising all of the ethylene R units in which unbranched Y units are present is a homogeneous backbone. Polyamine backbones containing all ethylene R units are homogeneous backbones regardless of the number or degree of branching of the cyclic side chains present.

For the purposes of the present invention, the term "heterogeneous polymer backbone" refers to a polyamine backbone that is a complex of various R unit lengths and R unit types. For example, the heterogeneous backbone includes R units that are a mixture of ethylene units and 1,2-propylene units. For the purposes of the present invention, a mixture of "hydrocarbyl" units and "oxy" R units is not necessary to provide a heterogeneous backbone.

Preferred polyamines of the invention include homogeneous polyamine backbones wholly substituted or partially substituted with polyethyleneoxy moieties, wholly quaternized or partially quaternized amines, nitrogen oxidized wholly or partially oxidized with N-oxides and mixtures thereof. Include. However, not all of the backbone amine nitrogens are modified in the same manner, and the choice of the modification is a specific requirement of the formulation agent. In addition, the degree of ethoxylation is determined by the specific requirements of the formulation agent.

Preferred polyamines comprising the backbone of the compounds of the invention are generally polyalkyleneamines (PAA), polyalkyleneimines (PAI), preferably polyethyleneamines (PEA) or polyethyleneimines (PEI), or the parent ) Is a PEA or PEI linked by residues longer in R units than PAA, PAI, PEA or PEI. Typical polyalkyleneamines (PAAs) are tetrabutylenepentamine. PEA is obtained by a reaction involving ammonia and ethylene dichloride, accompanied by fractional distillation. Typical PEAs obtained are triethylenetetraamine (TETA) and tetraethylenepentamine (TEPA). In addition to pentamine, ie hexamine, heptamine, octamine and possibly nonamine, suitably derived mixtures are not separated by distillation and may include other substances such as cyclic amines and especially piperazine. There may also be cyclic amines with side chains in which nitrogen atoms appear (see, for example, US Pat. No. 2,792,372, Dickinson, issued May 14, 1957, which describes a process for PEA).

Preferred amine polymer backbones also include R units, which are C ₂ alkylene (ethylene) units known as polyethyleneimine (PEI). Preferred PEIs have at least a moderate degree of branching, ie, the ratio of m to n is less than 4: 1, but PEI with a ratio of m to n of about 2: 1 is most preferred. Prior to denaturation, preferred backbones are

(Where m and n are as defined above). Prior to denaturation, the preferred molecular weight of PEI is greater than about 200 Daltons, preferably 3,000 Daltons or less.

In the case of polyamine backbones, in particular PEI, the relative proportions of the respective primary amine, secondary amine and tertiary amine units vary depending on the mode of preparation. Each hydrogen atom bonded to each nitrogen atom of the polyamine backbone chain represents a potential position for subsequent substitution, quaternization or oxidation.

These polyamines can be produced, for example, by polymerizing ethyleneimine in the presence of a catalyst (eg, carbon dioxide, sodium disulfide, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.). Particular methods for making such polyamine backbones are all described in US Pat. No. 2,182,306, Ulrich et al., Issued Dec. 5, 1939; US Patent No. 3,033,746, Mayle et al., Issued May 8, 1962; US Patent No. 2,208,095, Esselmann et al., Issued July 16, 1940; US Patent No. 2,806,839, Crowther, issued September 17, 1957 and US Patent No. 2,553,696, Wilson, issued May 21, 1951.

Examples of polyamines of the present invention comprising PEI are illustrated in Formulas I-V.

Formula I represents a preferred polyamine comprising a PEI backbone in which all of the substitutable nitrogens are modified by replacing hydrogen with a polyoxyalkyleneoxy unit-(CH ₂ CH ₂ O) ₂₀ H:

Formula II represents a polyamine comprising a PEI backbone in which all of the nitrogens that can be substituted are replaced by replacing hydrogen with a polyoxyalkyleneoxy unit-(CH ₂ CH ₂ O) ₇ H:

This is an example of a polyamine completely modified in one moiety form.

Formula III replaces hydrogen with a polyoxyalkyleneoxy unit-(CH ₂ CH ₂ O) ₇ H so that all substitutable primary amine nitrogens are denatured, and oxidizable primary and secondary nitrogens are all converted to N-oxides. Subsequent oxidation results in polyamines in which the molecule comprises a modified PEI backbone:

Formula IV represents a polyamine comprising a PEI backbone in which all of the backbone hydrogen atoms are substituted and some backbone amine units are quaternized. Substituents are polyoxyalkyleneoxy units — (CH ₂ CH ₂ O) ₇ H or methyl groups. Modified PEI polyamines are compounds of Formula IV:

Formula V represents a polyamine comprising a PEI backbone wherein the backbone nitrogens have been modified by substitution or quaternization [ie with-(CH ₂ CH ₂ O) ₇ H or methyl] or oxidation with N-oxides or mixtures thereof. The resulting polyamine is a compound of Formula V:

In the above example, not all of the unit groups of nitrogen are modified identically. The formulation agent of the present invention has some secondary amine nitrogens ethoxylated with some secondary amine nitrogens oxidized to N-oxide. This also applies to primary amine nitrogens, wherein the formulation agent may be selected to denature all or some of the primary amine nitrogens with one or more substituents before being oxidized or quaternized. Mixtures of any of the possible E groups can be substituted for primary and secondary amine nitrogens, with the exception of the limitations described herein above.

Ethoxylated PEIs having a molecular weight of 200 to 3,000, preferably 400 to 700 and an average degree of ethoxylation of 4 to 30, preferably 15 to 25 are very preferred for use in the present invention.

The composition of the present invention comprises a polyamine in an amount sufficient to solve the stabilization amount, ie the instability problem caused by the presence of HEDP. The amount of polyamine required depends on the amount of HEDP present, but is typically from 0.05 to 20% by weight, preferably from 0.1 to 10% by weight and most preferably from 0.2 to 5% by weight of the total composition. The polyamines of the present invention also have the advantage of providing stain removal and brightening benefits.

Detergent Surfactant

The composition of the present invention comprises a surfactant. In addition to the preferred anionic and nonionic detergent surfactants described herein, other detergent surfactants suitable for use in the present invention are cationic, anionic, nonionic, both described further below in this specification. Sex, zwitterionic, and mixtures thereof.

Non-limiting examples of other surfactants useful herein, typically at concentrations of about 1 to about 55 weight percent, include conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates (“LAS”), formula CH ₃ (CH ₂ ) _{x ^{(CHOSO 3 - M +) CH}} 3 and the general formula _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 [ wherein, x and (y + 1) is about 7 or higher, preferably about 9 or more Integer, M is a water soluble cation, in particular sodium], C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfate, unsubstituted sulfate (eg oleyl sulfate), C ₁₀ -C ₁₈ alkyl alkoxy carboxylate ( In particular ethoxycarboxylates of EO 1 to 5), C ₁₀ -C ₁₈ glycerol ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₂ -C ₁₈ alpha-sulfo Acrylated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants such as so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy) C ₁₂ -C ₁₈ alkyl ethoxylates (“AEs”), C ₁₂ -C ₁₈ betaines and sulfobetaines (“sultaines”), C ₁₀ -C ₁₈ amine oxides, etc. It may be. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methylglucamide (see International Publication No. 9,206,154). Other sugar derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. In addition, C ₁₀ -C ₂₀ conventional soaps may be used. Where more foam is desired, branched C ₁₀ -C ₁₆ soaps can be used. Particularly useful are mixtures of anionic and nonionic surfactants. Other conventional useful surfactants are described in standard documents.

Other anionic surfactants useful for cleaning purposes may also be included in the compositions thereof. These include salts of soaps [eg, sodium, potassium, ammonium and substituted ammonium salts such as monoethanolamine salts, diethanolamine salts and triethanolamine salts), C₉-C₂₀Straight chain alkylbenzenesulfonates, C₈-C₂₂ Primary or secondary alkanesulfonates, C₈-C₂₄Olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates (e.g. acyl isothio ), N-acyl taurate, fatty acid amide of methyl tauide, alkyl succinate and sulfosuccinate, monoesters of sulfosuccinate (especially saturated and unsaturated C₁₂-C₁₈Monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C₆-C₁₄Diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides (e.g. sulfates of alkylpolyglucosides), side chain primary alkyl sulfates, alkyl polyethoxy carboxylates [e.g.₂CH₂O)_kCH₂COO^-M⁺Alkyl polyethoxy carboxylates, wherein R is C₈-C₂₂Alkyl, k is an integer from 0 to 10, M is a soluble salt forming cation)], and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Another example is described in Surface Active Agents and Detergents (Vol. I and II, Schwartz, Perry and Berch).

The composition of the present invention preferably comprises at least about 0.01%, preferably at least 0.1%, more preferably about 1 to about 95%, most preferably about 1 to about 80% of the anionic detersive surfactant Contains by weight. Primary or secondary alkyl sulfate surfactants are an important form of anionic surfactants for use in the present invention. Alkyl sulfates are compounds of the formula ROSO ₃ M wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably straight or branched alkyl, or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component, more preferably Is C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is hydrogen or a water soluble cation [e.g. alkali metal cation (e.g. sodium, potassium, lithium), unsubstituted or substituted ammonium cation e.g. methyl ammonium, dimethyl ammonium And trimethyl ammonium) and cations derived from quaternized ammonium cations (eg tetramethyl-ammonium and dimethyl piperidinium) and alkanolamines (eg ethanolamine, diethanolamine, triethanolamine and mixtures thereof); Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for low wash temperatures (eg up to about 50 ° C.) and C ₁₆ -C ₁₈ alkyl chains are preferred for high wash temperatures (eg about 50 ° C.).

Alkyl alkoxylated sulfate surfactants are another category of preferred anionic surfactants. These surfactants are either water soluble salts or acids typically of the formula RO (A) _m SO ₃ M, wherein R is an unsubstituted C ₁₀ -C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl component, preferably C ₁₂ -C Hydroxyalkyl group having ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy unit or propoxy unit, m is greater than 0, typically about 0.5 to about 6, more preferably about 0.5 to about 3, M is hydrogen or, for example, metal cations (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations Water soluble cations. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are envisioned in the present invention. Specific examples of substituted ammonium cations include cations derived from methyl ammonium, dimethyl ammonium, trimethyl ammonium and quaternized ammonium cations such as methmethylammonium, dimethyl piperidinium and alkanolamines such as monoethanolamine, di Ethanolamine and triethanolamine) and mixtures thereof. Exemplary surfactants include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate, wherein M is conveniently selected from sodium and potassium.

The composition of the present invention also preferably comprises at least about 0.01%, preferably at least 0.1%, more preferably about 1 to about 95%, most preferably about 1 to about 1% by weight of the nonionic detergent surfactant. 80 wt%. Preferred nonionic surfactants such as C ₁₂ -C ₁₈ comprising so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy) Alkyl ethoxylates (“AE”)], block alkylene oxide condensates of C ₆ to C ₁₂ alkyl phenols, alkylene oxide condensates of C ₈ -C ₂₂ alkanols and ethylene oxide / propylene oxide block polymers [Fluro Pluronic ^™ -BASF Corp.], and semipolar nonionic polymers such as amine oxides and phosphine oxides can be used in the compositions of the present invention. Details of these types of surfactants are described in US Pat. No. 3,929,678, published on December 30, 1975, incorporated herein by reference.

Alkylpolysaccharides known from US Pat. No. 4,565,647, Llenado (incorporated herein by reference) are also preferred nonionic surfactants in the compositions of the present invention.

Another preferred nonionic surfactant is a formula Polyhydroxy fatty acid amides wherein R ⁷ is C ₅ -C ₃₁ alkyl, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferred Preferably straight chain C ₁₁ -C ₁₅ alkyl or alkenyl or mixtures thereof, R ⁸ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, preferably methyl or ethyl, more preferably Is selected from the group consisting of methyl, Q is a polyhydroxyalkyl moiety having at least three hydroxyls and linear alkyls directly connected to the chain, or alkoxylated derivatives thereof, preferably alkoxy is ethoxy, propoxy and their Mixture. Preferably Q is derived from reducing sugars in a reducing amidation reaction. More preferably, Q is a glycidyl residue. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, as well as the respective sugars listed above, corn syrup with high dextrose, corn syrup with high fructose and corn syrup with high maltose can be used. These corn syrups can produce a mixture of sugar components in the case of Q. It should be understood that this is in no way intended to exclude other suitable raw materials. Q is more preferably -CH ₂ (CHOH) _n CH ₂ OH, -CH (CH ₂ OH) (CHOH) _n-1 CH ₂ OH, -CH ₂ (CHOH) _2- (CHOR ') (CHOH) CH ₂ OH and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5 and R 'is hydrogen or a cyclic or aliphatic monosaccharide. More preferred substituents for the Q moiety are glycidyl, where n is 4 and in particular -CH ₂ (CHOH) ₄ CH ₂ OH.

R ⁷ CO-N <may be, for example, cokeamide, stearamide, oleamide, lauamide, myristicamide, capricamide, palmitamide, tallowamide and the like.

R ⁸ may be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl or 2-hydroxypropyl.

Q is 1-deoxyglycityl, 2-deoxyfructitil, 1-deoxymaltyl, 1-deoxylactyl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotrio Titanium, and the like.

Particularly preferred surfactants of this type for use in the compositions of the present invention are compounds of the formula wherein R ⁷ is alkyl (preferably C ₁₁ -C ₁₃ ), R ⁸ is methyl and Q is 1- Deoxyglycityl].

Other sugar derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamide can be used to reduce foaming. C ₁₀ -C ₂₀ conventional soaps may also be used. If it is desired to increase the foam, branched C ₁₀ -C ₁₆ soaps can be used.

Random ingredient

The composition of the present invention may further comprise various optional components.

Various other ingredients useful in detergent compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid filters for bar compositions, and the like, can be included in the compositions of the present invention. If it is desired to increase the foam, foam promoters (eg C ₁₀ -C ₁₆ alkanolamides) may be incorporated into the composition, typically at a concentration of 1 to 10% by weight. C ₁₀ -C ₁₄ monoethanol and diethanol amides illustrate a typical group of such foam promoters. It is also useful to use such foam promoters while increasing the above-mentioned foam addition surfactants such as amine oxides, betaines and sultaines. If desired, soluble magnesium salts (eg, MgCl ₂ · MgSO _4, etc.) may typically be added at a concentration of 0.1 to 2% by weight to provide additional foam and improve grease removal performance.

The various cleaning components used in the compositions of the present invention may optionally be further sterilized by absorbing the above components into a porous hydrophobic substrate and coating the substrate with a hydrophobic coating. Preferably, the cleaning component is mixed with the surfactant before being absorbed into the porous substrate. When the cleaning component is used to release from the substrate into the aqueous cleaning liquid, its desired cleaning action is carried out.

To explain this technique in more detail, porous hydrophobic silica (tradename, SIPERNAT D10, DeGussa) is a 3 to 5% C ₁₃ -C ₁₅ ethoxylated alcohol (EO 7) nonionic surfactant. It is mixed with a proteolytic enzyme solution containing. Typically, the enzyme / surfactant solution is 2.5 times the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oils with a viscosity of 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or added to the final cleansing matrix. Accordingly, the above-mentioned components such as enzymes, bleaches, bleach activators, bleach catalysts, light activators, dyes, fluorescent agents, fabric conditioners and hydrolyzable surfactants may be used in detergents including laundry liquid detergent compositions. In that case it may be "protected".

Liquid detergent compositions may include water and other solvents (eg, carriers). Low molecular weight primary or secondary alcohols listed as methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for dissolving surfactants, but polyols containing 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups, such as 1,3-propanediol, ethylene glycol, glycerin and 1,2- Propanediol) may be used. The composition may comprise 5 to 90%, typically 10 to 50%, by weight of the carrier.

The detergent composition of the present invention is preferably formulated such that the pH of the wash water is from about 6.0 to about 11, preferably from about 7.0 to 10.0 during use in the liquid washing action. Laundry liquid products typically have a pH of 7-9. Techniques for adjusting pH at recommended use concentrations include the use of buffers, alkalis, acids, and the like, which are well known to those skilled in the art.

enzyme

Enzymes may be used for various purposes including removal of protein based, carbohydrate based or triglyceride based stains from surfaces such as fabrics, for the prevention of residue dye migration, for illustration at washing and for fabric recovery. It may be included in the detergent composition of the invention. Suitable enzymes of any suitable origin (eg, vegetable, animal, bacterial, fungal and yeast origin) include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof. Preferred choices are influenced by factors such as pH activity and / or stability optimum conditions, thermal stability, and stability to active detergents, enhancers and the like. In this regard, bacterial enzymes or fungal enzymes such as bacterial amylases and proteases and fungal cellulase are preferred.

As used herein, "cleaning enzyme" means an enzyme that has a washing, stain removal or other beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases.

Enzymes are generally incorporated into detergents or detergent additive compositions at concentrations sufficient to provide a "wash effective amount". The term “clean effective amount” means an amount that can provide freshness that enhances the effect on substrates such as washing, stain removal, decontamination, brightening, deodorization, or textiles. In particular, for commercially available formulations, typical amounts are up to about 5 mg of active enzyme per gram of detergent composition, more typically 0.01 to 3 mg. In other words, the compositions of the present invention typically comprise from 0.001 to 5% by weight, preferably 0.01 to 1% by weight of commercial enzyme preparations. Protease enzymes are generally present in the commercial formulation at a concentration sufficient to provide an activity of 0.005 to 0.1 anneal units (AU) per gram of composition. For certain detergents, it is desirable to increase the active enzyme content of commercially available formulations to minimize the total amount of noncatalytically active substances and to increase spot removal / encapsulation or other final products. Higher activity may also be desirable in highly concentrated detergent compositions.

Suitable amylases in the present invention include, for example, α-amylases (British patent 1,296,839, Novo), RAPIDASE ^R [International Bio-Synthetics, Inc.]. )] And TERMAMYL ^R [Novo]. Novo manufactured FUNGAMYL ^R is particularly useful. Enzyme engineering to improve stability (eg oxidative stability) is described in J. Biological Chem., Vol. 260, no. 11, June 1985, pp 6518-6521. Certain preferred embodiments of the compositions of the present invention may employ amylases with improved stability to detergents, in particular improved oxidative stability, as measured for the reference point of Teramyl ^R for routine use in 1993. Such preferred amylases of the present invention have, to a minimum, oxidative stability [eg, for hydrogen peroxide / tetraacetylethylenediamine in a buffer solution of pH 9 to 10], eg conventional washing temperatures (eg, about 60 Properties of the "stable improved" amylase, characterized by one or more measurable improvements in thermal stability (at &lt; RTI ID = 0.0 &gt; C), &lt; / RTI &gt; or alkali stability [at pH about 8 to about 11 measured for the abovementioned reference point amylase]. Share. Stability can be measured using any technical test known in the art, for example, as described in WO 9,402,597. Stability enhanced amylases can be purchased from Novo or Genencor International. One group of highly preferred amylases of the invention is site specific mutagenesis from one or more Bacillus amylases, particularly Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are direct precursors. It has a shared attribute that is derived using. Amylase with Improved Oxidation Stability vs. Reference Amylase as mentioned above is preferred for use of the detergent compositions of the invention in particular for bleaching, more preferably for oxygen bleaching other than chlorine bleaching. Such preferred amylases are (a) a ratio known as termamyl ^R. Mutant strains substituted with alanine or threonine, preferably threonine, a methionine residue located at position 197 of B. Licheniformis alpha-amylase, or a homologous positional variant of a similar parent amylase, for example ratio. B. amyloliquefaciens, b. B. subtilis, or b. Amylases according to the above-incorporated document as further mentioned by B. Stearothermophilus (see, eg, International Publication No. 9,402,597, Novo, published February 3, 1994); (b) in the article "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting held from March 13-17, 1994 by C. Mitchinson. As described) stability-enhanced amylase. Here, in the automatic dish washing detergent, the bleach inactivates alpha-amylase, but the amylase with improved oxidative stability is non. It is noted that it is produced by Jennenker from Rihenipomis NCIB8061. Methionine (Met) has been identified as the residue with the highest denaturation potential. Met is replaced at one time at positions 8, 15, 197, 256, 304, 366 and 438 which induce specific mutants, particularly important forms are M197L and M197T and M197T, with the M197T modification being the most stable expression variant. Stability is measured in cascade ^R and sunlight ^R. (c) Particularly preferred amylases of the present invention are commercially available as DURAMYL ^R from assignee Novo, including amylase variants which are further modified in the direct base material as described in WO 9,510,603 A. . Other particularly preferred amylases with enhanced oxidative stability include amylases described in Genenker International Publication No. 9,418,314 and Novo International Publication No. 9,402,597. Any other enhanced oxidative stability amylase can be used, for example, as derived by site specific mutagenesis from known chimeric hybrid mutants or simple mutant parent forms of commercial amylases. Other preferred enzyme denaturations are accessible (see Novo International Publication No. 9,509,909 A).

Cellulases usable in the present invention preferably include both bacterial and fungal forms having a pH optimum of 5 to 9.5. Liver pancreas of Dolabella Auricula Solander, a fungal cellulase belonging to the genus Funicululase or Aeromonas from Humicola Insolens or Dumicola DSM1800, and Dolabella Auricula Solander, a marine mollusc Cellulase extracted from is described in US Pat. No. 4,435,307, issued March 6, 1984 to Barbesgoard et al. Suitable cellulases are also known from British Patent Publication No. 2,075,028, British Patent Publication No. 2,095,275 and DE-OS No. 2,247,832. CAREZYME ^R (Novo) is particularly useful (Novo International Publication No. 9,117,243).

Suitable lipase enzymes for detergents include enzymes produced by Pseudomonas group microorganisms (e.g. Pseudomonas stutzeri ATCC 19.154 as disclosed in British Patent No. 1,372,034), 1978. Japanese Patent Application No. 53,20487, published on February 24]. Such lipases can be purchased from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade names Lipase P “Amino” or “Amino-P”. Other suitable commercial lipases are Amano-CES, ie Chromobacter viscosum lipases (e.g., Chromobacter viscosum var. Manufactured by Toyo Jozo Co., Tagata, Japan, Dagata, Japan). lipolyticum NRRLB 3673]]; U of America. s. Chromomobacter biscosum lipases from US biochemical Corp. (USA) and Deisoynth Co., The Netherlands; And Pseudomonas gladioli lipase. A lipolase ^R enzyme derived from Humicola lanuginosa and sold by Novo (European Patent No. 341,947) is a preferred lipase for use in the present invention. Lipase and amylase modifications that are stable to peroxidase enzymes are described in Novo International Patent Publication Nos. 9,414,951 (International Patent Publication Nos. 9,205,249 and RD 94,359,044). Cutinase enzymes are described in Genenker International Publication No. 8809367 A.

Suitable examples of proteases include B. a. Subtilis and b. There is subtilisin obtained from certain strains of rihenomymis. One suitable protease is obtained from a strain of Bacillus with maximum activity at pH 8-12, developed and marketed by Danish Nomo Industries A / S as ESPERASE ^R. Methods of making such and similar enzymes are described in Novo's British Patent 1,243,784. Other suitable proteases are Alcala claim (ALCALASE) ^R and the Sabina (SAVINASE) Inter National bio ^R and the Netherlands by Novo manufacturing-synthetase ticks, Inc. ray is a barracks hydratase (MAXATASE) Preparation suited ^R; And Protease A described in European Patent Publication No. 130,756 A, published January 9, 1985 and European Patent Publication No. 303,761 A, published April 28, 1987 and Protease B described in European Patent Application Publication No. 130,756 A, published January 9, 1985. See Bacillus sp. In Novo International Publication No. 9,318,140. High pH protease from NCIMB 40338]. Enzymatic detergents comprising proteases, one or more enzymes and reversible protease inhibitors are described in Novo International Publication No. 9,203,529 A. Other preferred proteases include the proteases of International Publication No. 9,510,591 A of Procter Gamble. In some cases, proteases with reduced uptake and increased hydrolysis are commercially available, as described in Procter & Gamble International Publication No. 9,507,791. Recombinant trypsin-type proteases for detergents suitable for the present invention are described in Novo International Publication No. 9,425,583.

Preferred laundry liquid detergent compositions according to the invention further comprise at least 0.001% by weight protease enzyme. However, an effective amount of protease enzyme is sufficient for use in the laundry liquid detergent compositions described herein. The term "effective amount" means an amount that can provide an effect of increasing cleaning, stain removal, decontamination, whitening, deodorization, or freshness to a substrate such as fabric. In particular, for commercially available formulations, typical amounts are up to about 5 mg of active enzyme per gram of detergent composition, more typically 0.01 to 3 mg. In other words, the compositions of the present invention typically comprise from 0.001 to 5% by weight, preferably 0.01 to 1% by weight of commercial enzyme preparations. Protease enzymes of the present invention are generally present in the commercial formulation at a concentration sufficient to provide an activity of 0.005 to 0.1 anneal units (AU) per gram of composition.

Preferred laundry liquid detergent compositions of the present invention comprise a protease enzyme called "protease D", which is a carbonyl hydrolase variant having an amino acid sequence not found in nature and wherein the corresponding amino acids correspond to position 76 Derived from precursor carbonyl hydrolase by substitution of a plurality of amino acid residues at one position of the neil hydrolase, preferably published by Genenker International on April 20, 1995; +99, +101, +103, +104, +107, +123, +27 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in 10615. , +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, + Corresponding to a position selected from the group consisting of 260, +265 and / or +274 By combination with one or more amino acid residue positions it is derived from a precursor carbonyl hydrolase zero.

Useful proteases can also be found in International Publication No. 95/30010, published November 9, 1995, The Procter Gamble Company; International Publication No. 95/30011, published November 9, 1995, The Procter Gamble Company; International Publication No. 95/29979, published November 9, 1995, The Procter Gamble Company.

Preferred proteolytic enzymes also include the proteases described in modified bacterial serine proteases (e.g., European Patent Application No. 87 303.761.8, filed April 28, 1987, in particular pages 17, 24 and 98). Refers to the proteases (denatured bacterial serine proteolytic enzymes) described in European Patent Application No. 199,404 to Venegas, published October 29, 1986, protease in this document. (Protease A is described in European Patent Publication No. 130,756 A published January 9, 1985 and protease B is published in European Patent Publication No. 303, published April 28, 1987). 761 A and European Patent Publication No. 130,756 A published January 9, 1985).

Peroxidase enzymes provide an oxygen source (e.g., percarbonate, perborate, hydrogen peroxide, etc.) to prevent migration of pigments or dyes that are removed for "solution bleaching" or during the wash from the substrate to other substrates present in the wash solution. It can be mixed with. Known peroxidases include heart radiciperoxidase, ligninase and haloperoxidase such as chloroperoxidase or bromoperoxidase. Peroxidase-containing detergent compositions are known from WO 89,099,813 A, published October 19, 1989, Novo and WO 8,909,813 A, Novo.

The range of enzymatic materials and their incorporation into synthetic detergent compositions is also described in Genenker International Publications 9,307,263 A and 9,307,260 A, Novo International Publications. 8,908,694 A and McCarty, U.S. Patent No. 3,553,139, issued January 5, 1971. Enzymes are further known from US Pat. No. 4,101,457, Place et al., Issued July 18, 1978 and US Pat. No. 4,507,219, Hughes, issued March 26, 1985. Enzyme materials useful in liquid detergent compositions and their incorporation into such compositions are known from US Pat. No. 4,261,868, issued to Hora et al., April 14, 1981. Enzymes for use in detergents can be stabilized by a variety of techniques. Enzyme stabilization techniques are known from US Pat. No. 3,600,319, issued August 17, 1971, Gedge et al., European Patent No. 199,405 and European Patent No. 200,586, issued October 29, 1986, Venegas. It is illustrated. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. Useful Bacillus sp. To provide proteases, xylanases and cellulase. AC13 is described in Novo International Publication No. 9,401,532 A.

Enzyme stabilization system

Enzyme-containing liquid compositions of the present invention comprise from about 0.001 to about 10 weight percent, preferably from about 0.005 to about 8 weight percent, most preferably from about 0.01 to about 6 weight percent of an enzyme stabilization system, including but not limited to no. The enzyme stabilization system may be a stabilization system that is miscible with the washable enzyme. Such a system may be originally supplied by another formulation activator, or may be added separately, for example, by formulation agents or preparations of washed enzymes. Such stabilizing enzymes include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof, and pose different stabilization problems depending on the physical form and type of detergent composition.

One stabilization method is to use a water soluble source of such ions in a processing composition that supplies calcium and / or magnesium ions to the enzyme. Calcium ions are generally more effective than magnesium ions and are preferred when only one type of cation is used in the present invention. Typical detergent compositions, particularly liquid detergent compositions, contain from about 1 to about 30 mmol, preferably from about 2 to about 20 mmol, more preferably from about 8 to about 12 mmol, of calcium ions per liter of processed detergent composition, Modifications are possible depending on factors including diversity, type and concentration. Preferably, the water soluble calcium salt or water soluble magnesium salt comprises calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate, more generally magnesium salts corresponding to calcium sulfate or calcium salts exemplified. Can be used. In addition, increasing the concentration of calcium and / or magnesium may, of course, be useful for, for example, promoting the grease cleavage of certain types of surfactants.

Another stabilization method is the use of borate species (Severson, US Pat. No. 4,537,706). If a borate stabilizer is used, its concentration may be up to 10% or more than 10% of the composition, but more typically up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate Suitable for liquid detergent applications. Substituted boric acids (eg phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid, etc.) can be used in place of boric acid and it is possible to use these substituted boron derivatives when the total boron concentration in the detergent composition is reduced. Can be done.

The stabilization system of certain cleaning compositions further comprises from 0 to about 10% by weight of chlorine bleach scavenger, preferably from about 0.01 to about 6% by weight, and in particular in chlorine bleach scavengers present in multiple feed rates under alkaline conditions. It can be added to prevent the attacker from attacking and inactivating the enzyme. While chlorine concentrations in water are typically as low as about 0.5 to about 1.75 ppm, for example, commercially available chlorine concentrations in the total volume of water contacted with enzymes during fabric washing can sometimes be relatively high, resulting in enzymatic stability to chlorine in use. there is a problem. Since perborate or percarbonate having the ability to react with chlorine bleach may be present in some of the compositions in amounts calculated separately from the stabilization system, it is most generally not necessary to use additional stabilizers for chlorine, By using these, improved results can be obtained. Suitable chlorine scavenger anions are well known and readily commercially available and, if used, may be salts containing ammonium cations such as sulfites, bisulfites, thiosulphates, thiosulfates, iodides and the like. Antioxidants (eg carbamate, ascorbate, etc.), organic amines (eg ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof), monoethanolamine (MEA) and mixtures thereof can likewise be used. Likewise, certain enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility. Other common scavengers (e.g. bisulfite, nitrates, chlorides), hydrogen peroxide sources (e.g. sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate) and phosphates, condensed phosphates, acetates, benzoates, sheets Laterate, formate, lactate, maleate, tartrate, salicylate and the like and mixtures thereof may be used, if desired. In general, chlorine scavenger action can be carried out by separately listed components (e.g., hydrogen peroxide source) under better recognized action, so that compounds performing the action to the desired extent are absent from the enzyme containing embodiments of the present invention. As long as there is no absolute condition for adding a separate chlorine scavenger, the scavenger is applied only for optimum results. In addition, when formulating agents are used, this will affect the chemist's normal skill in avoiding the use of enzyme scavengers or stabilizers that are primarily incompatible with other reactive ingredients, as formulated. With regard to the use of ammonium salts, the salts can be simply mixed with the detergent composition, but are easy to absorb water and / or liberate ammonia during storage. Thus, these materials are preferably protected in the particles as they are described in US Pat. No. 4,652,392 to Baginski et al.

Enhancer

Detergent enhancers may optionally be included in the compositions of the present invention to assist in controlling mineral hardness. Inorganic and organic enhancers can be used. Enhancers are typically used in fabric laundering compositions to assist in the removal of particulate dirt.

The concentration of the enhancer can vary widely depending on the end use of the composition and its preferred physical form. When present, the composition typically contains at least about 1% by weight of an enhancer. Liquid compositions typically comprise from about 5% to about 50%, more typically from about 5% to about 30% by weight of a detergent enhancer. However, this does not mean that low or high concentrations of the enhancer are excluded.

Inorganic or P-containing detergent enhancers include alkali metal, ammonium and alkanolammonium salts, phosphonates, phytic acid, silicates, (bicarbonates and ses) of polyphosphates (listed as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates) Carbonates, sulfates, and aluminosilicates, including, but not limited to, quicarbonates. However, in some cases a nonphosphate enhancer is needed. Importantly, the compositions of the present invention are surprisingly (relative to phosphates) so-called "underbuilt" which can occur in the presence of so-called "about" enhancers (e.g. citrate) or using zeolites or layered silicate enhancers. "It works in situations.

Examples of silicate enhancers include alkali metal silicates, in particular alkali metal silicates having a SiO ₂ : Na ₂ O ratio of 1.6: 1 to 3.2: 1 and laminated silicates (e.g., sodium silicate described in US Pat. No. 4,664,839). to be.

Examples of carbonate enhancers are alkaline earth metal carbonates and alkali metal carbonates, as known from German Patent Application No. 2,321,001 published November 15, 1973.

Aluminosilicate enhancers are useful in the present invention. Aluminosilicate builders are the empirical formula M _z (zAlO _{2) y]} · Compound (wherein, z and y are at least 6 integer xH ₂ O, molar ratio of z for y is from 1.0 to about 0.5, x is from about 15 to It is an integer of about 264).

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be commonly occurring aluminosilicates or may be synthetically derived. Methods of making aluminosilicate ion exchange materials are known from US Pat. No. 3,985,669 to Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are commercially available under the names Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is a compound of formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O, wherein x is from about 20 to about 30, in particular about 27). This material is known as zeolite A. Dehydrated zeolites (x is 0 to 10) may also be used in the present invention. Preferably, the particle size of the aluminosilicate is about 0.1 to 10 microns in diameter.

Organic cleansing enhancers suitable for the purposes of the present invention include, but are not limited to, various polycarboxylate compounds. "Polycarboxylate" as used herein means a compound having a plurality of carboxylate groups, preferably three or more carboxylates. Polycarboxylate enhancers can generally be added to the composition in acid form, but may also be added in neutralized salt form. When used in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

Among the polycarboxylate enhancers are useful materials of various categories. One important category, polycarboxylate enhancers, is known from Berg, US Pat. No. 3,128,287, issued April 7, 1964, and Lamberti et al., US Pat. No. 3,635,830, issued January 18, 1972. Ether polycarboxylates, including oxydisuccinates, as is described in US Pat. No. 4,663,071, "TMS / TDS" enhancer, Bush et al., Issued May 5, 1987. Suitable ether polycarboxylates are also described in cyclic compounds, in particular alicyclic compounds (e.g., U.S. Pat. Nos. 3,923,679, U.S. Patent 3,835,163, U.S. Patent 4,158,635, U.S. Patent 4,120,874, and U.S. Patent 4,102,903). Alicyclic compound).

Other useful detergent enhancers include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl Oxysuccinic acid, various alkali metals, ammonium and substituted ammonium salts of polyacetic acid (e.g. ethylenediamine tetraacetic acid and nitrilotriacetic acid) and polycarboxylates (e.g. melic acid, succinic acid, oxydisuccinic acid, polymaleic acid Benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof).

Citrate enhancers (e.g. citric acid) and their soluble salts (especially sodium salts) are particularly useful in heavy duty liquid detergent compositions due to their availability from renewable resources and their biodegradability. Carboxylate enhancer.

Also known are 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds known from US Pat. No. 4,566,984, Bush, issued January 28, 1986. It is suitable for the cleaning composition of the. Useful succinic acid enhancers include C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. Particularly preferred in this type is dodecenyl succinic acid. Specific examples of succinic acid enhancers include: lauryl succinate, myristyl succinate, palmitytuccinate, (preferably) 2-dodecenyl succinate, 2-pentadecenyl succinate Etc. Laurylsuccinate is a preferred enhancer of this group and is described in European Patent Application 86,200,690.5 / 0,200,263, published November 5, 1986.

Other suitable polycarboxylates are known from US Pat. No. 4,144,226, Crutchfield et al., Issued March 13, 1979 and US Pat. No. 3,308,067, Diehl, issued March 7, 1967. Diehl , US Patent No. 3,723,322.

Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids may also be incorporated into the composition alone or used in admixture with the above-mentioned enhancers, in particular citrate enhancers and / or succinate enhancers, to provide additional enhancer activity. . Such use of fatty acids generally reduces foaming, which is believed to be due to formulation agents.

Where phosphorus enhancers can be used, in particular in the formulation of bars used in hand washing operations, various alkali metal phosphates such as the well known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. have. Phosphonate enhancers (see, eg, US Pat. No. 3,159,581, US Pat. No. 3,213,030, US Pat. No. 3,422,021, US Pat. No. 3,400,148 and US Pat. No. 3,422,137) may also be used.

Chelating agent

Detergent compositions of the invention may also optionally include one or more iron and / or manganese chelating agents. Such chelating agents as defined below may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctional substituted aromatic chelating agents, and mixtures thereof.

While not wishing to be bound by theory, it is believed that the benefit of these materials is to some extent due to their exceptional ability to remove iron and manganese ions from the wash solution by the formation of soluble chelates.

Amino chelates useful as any chelating agent include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol Diglycine, alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferably, these amino phosphonates do not contain alkyl groups or alkenyl groups of about 6 carbon atoms or more.

Multifunctional substituted aromatic chelating agents are also useful for use in the compositions (US Pat. No. 3,812,044, issued May 21, 1974, Connor et al.). Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use in the present invention are those described in ethylenediamine disuccinate (“EDDS”), in particular US Pat. No. 4,704,233, issued November 3, 1987 to Hartman and Perkins. It is the same [S, S] isomer.

When using these chelating agents, they generally comprise about 0.1 to about 10 weight percent of the detergent composition of the present invention. More preferably, when chelating agents are used, they comprise from about 0.1 to about 3.0 weight percent of the composition.

Clay Stain Removal / Redeposition Agent

The composition of the present invention may also optionally comprise a water soluble ethoxylated amine having clay dirt removal and anti-deposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01 to about 10.0 weight percent of water soluble ethoxylated amines and liquid detergent compositions typically contain from about 0.01 to about 5 weight percent.

Most preferred dirt release agents and re-deposition inhibitors are ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in US Pat. No. 4,957,898, VanderMeer, issued July 1, 1986. Another group of preferred clay dedusting-redeposition inhibitors is the cationic compounds disclosed in European Patent Application No. 111,965, Oh and Gosselink, issued June 27, 1984. Other clay dirt removal / re-deposition inhibitors that may be used are ethoxylated amine polymers disclosed in European Patent Application No. 111,984, issued on June 27, 1984, European Patent Application No. 112,592, Gosselink, published July 4, 1984; zwitterionic polymers and amine oxides disclosed in US Pat. No. 4,548,744, published on October 22, 1985. do. Other clay dirt removal and / or re-deposition inhibitors known in the art may be used in the compositions in the art. Another type of preferred antideposition agent includes a carboxy methyl cellulose (CMC) material. These materials are well known in the art.

Polymeric dispersants

The polymeric dispersant may be advantageously used at a concentration of about 0.1 to about 7 weight percent of the composition of the present invention, especially in the presence of zeolites and / or layered silicate enhancers. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other polymeric dispersants known in the art may be used. While not wishing to be bound by theory, polymeric dispersants are detergent enhancers when used in admixture with other enhancers (including low molecular weight polycarboxylates) by crystal growth inhibition, particulate dirt release peptidation and re-deposition prevention. It is thought to improve overall performance.

Polymeric polycarboxylate materials can preferably be prepared by polymerizing or copolymerizing suitable unsaturated monomers in their acid form. Unsaturated monomeric acids that may be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconic acid, mesaconic acid, citraconic acid and methylenemalonic acid. . The presence of the polymeric polycarboxylates or monomeric segments of the present invention that do not contain carboxylate radicals (eg, vinylmethyl ether, styrene, ethylene, etc.) is provided such that these segments do not occupy at least about 40% by weight. Suitable.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably about 2,000 to 10,000, more preferably about 4,000 to 7,000, most preferably about 4,000 to 5,000. Water soluble salts of such acrylic acid polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Water-soluble polymers of this type are known materials. The use of this type of polyacrylate in detergent compositions is disclosed, for example, in diehl, US Pat. No. 3,308,067, issued March 7, 1967.

Acrylic acid copolymers / maleic acid copolymers may also be used as preferred components of the dispersant / antideposition agent. Such materials include water-soluble salts in copolymers of acrylic acid and maleic acid. The average molecular weight of the copolymer in acid form is preferably about 2,000 to 100,000, more preferably about 5,000 to 75,000, most preferably about 7,000 to 65,000. The ratio of acrylate segment to maleate segment in the copolymer is generally from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Water soluble salts of such acrylic acid / maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are also described in European Patent Application No. 66,915, published December 15, 1982 and in European Patent Application, referring to the polymer comprising hydroxypropylacrylate. 193,360, published September 3, 1986]. Another useful dispersant includes maleic / acrylic acid / vinyl alcohol terpolymers. Such materials, including for example acrylic acid / maleic acid / vinyl alcohol 45/45/10 terpolymers, are also disclosed in EP 193,360.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG not only exhibits dispersant performance but also acts as a clay dedusting-redeposition inhibitor. Typical molecular weight ranges for this purpose are from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersants may also be used, in particular in combination with zeolite enhancers. The average molecular weight of the dispersant (eg polyaspartate) is preferably about 10,000.

Brightener

Any fluorescent brightener or other brightener or white agent known in the art may typically be incorporated into the detergent composition at a concentration of about 0.05 to about 1.2% by weight. Conventional fluorescent brighteners that may be useful in the present invention include stilbenes, pyrazolines, coumarins, carboxylic acids, methacyanines, dibenzotifen-5,5-dioxides, azoles, 5- and 6-membered ring heterocycles, and various other agents. It may be classified as an auxiliary group containing a derivative of, but is not necessarily limited thereto. Examples of such brighteners are disclosed in "The production and Application of Fluorescent Brightening Agents", published by M. Zahradnik, John Wiley Sons, New York (1982).

Specific examples of fluorescent brighteners useful in the compositions of the present invention are the fluorescent brighteners described in US Pat. No. 4,790,856, Wixon, issued December 13, 1988. Such brighteners include the PHORWHITE family of brighteners manufactured by Verona. Other brighteners known in this document include: Tinopal UNPA, Nitopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic White CC and Artic White CWD available from Hilton-Davis, Italy; 2- (4-stryl-phenyl) -2H-naphthol [1,2-d] thiazole; 4,4'-bis- (1,2,3-triazol-2-yl) -stilbene; 4,4'-bis (stryl) bisphenyl; And aminocoumarins. Specific examples of such brighteners include 4-methyl-7-diethyl-amino coumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 1,3-diphenyl-prazoline; 2,5-bis (benzooxazol-2-yl) thiophene; 2-stryl-naphth- [1,2-d] oxazole; And 2- (Stilben-4-yl) -2H-naphtho- [1,2-d] triazole (US Pat. No. 3,646,015, issued February 29, 1972, Hamilton). Anionic brighteners are described herein.

Foam inhibitor

Compounds that reduce or inhibit foam formation can be incorporated into the compositions of the present invention. Foam suppression may be particularly important in so-called "highly concentrated cleaning processes" and front-loading European-style washers as described in US Pat. No. 4,489,455 and US Pat. No. 4,489,574. .

Various materials can be used as foam inhibitors, and foam inhibitors are well known to those skilled in the art. See Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley Sons, Inc., 1979)]. One type of particularly useful foam inhibitor is a monocarboxylic fatty acid and its soluble salts. See US Pat. No. 2,954,347, issued September 27, 1960, Wayne St. John]. Monocarboxylic fatty acids and salts thereof used as antifoams typically have a hydrocarbyl chain of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium salts, potassium salts and lithium salts and ammonium salts and alkanolamnonium salts.

The detergent composition of the present invention may also comprise a nonsurfactant foam inhibitor. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters such as fatty acid triglycerides, fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones such as stearone and the like. Other foam inhibitors include N-alkylated amino triazines formed as products of cyanuric chloride and 2 or 3 moles of primary or secondary amines having 1 to 24 carbon atoms (e.g., trialkylmelamine to hexaalkylmelamine or dialkyldiamine chlortri). Azine to tetraalkyldiamine chlortriazine), propylene oxide and monostearyl phosphate (e.g. monostearyl alcohol phosphate esters) and monostearyl dialkali metals (e.g. K, Na and Li) phosphate and phosphate esters . Hydrocarbons such as paraffin and haloparaffins can be used in liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, with an injection point of about −40 to about 50 ° C. and a minimum boiling point of at least about 110 ° C. (atmospheric pressure). It is also known to use wax hydrocarbons, preferably having a melting point of about 100 ° C. or less. Hydrocarbons make up the preferred type of foam inhibitor for detergent compositions. Hydrocarbon foam inhibitors are described, for example, in US Pat. No. 4,265,779, issued May 5, 1981, Gandolfo et al. Thus, hydrocarbons include aliphatic, cycloaliphatic, aromatic, and saturated or unsaturated heterocyclic hydrocarbons having about 12 to about 70 carbon atoms. The term "paraffin" as used in this antifoaming discussion is believed to include mixtures of pure paraffins with cyclic hydrocarbons.

Preferred categories of non-surfactant foam inhibitors include silicone foam inhibitors. This category includes the use of polyorganosiloxane oils (e.g. polydimethylsiloxanes), polyorganosiloxane oils or resin dispersants or emulsifiers, and mixtures of polyorganosiloxanes with silica particles (where polyorganosiloxanes are Adsorbed or fused). Silicone foam inhibitors are well known in the art and are described, for example, in US Pat. No. 4,265,779, issued May 5, 1981, Gandolfo et al., European Patent Application No. 89307851.9, published February 7, 1990. , Starch MS.

Other silicone foam inhibitors are disclosed in U.S. Patent No. 3,455,839, which relates to compositions and methods for the incorporation of small amounts of polydimethylsiloxane emulsions to deflate aqueous solutions.

Mixtures of silicon with silanized silica are described, for example, in DOS 2,124,526. Silicone antifoams and foam control agents in granular detergent compositions are disclosed in US Pat. No. 3,933,672, Bartolotta et al. And US Pat. No. 4,652,392, Baginski et al., Issued March 24, 1987.

Exemplary silicone-based foam inhibitors for use in the present invention are essentially

(i) a polydimethylsiloxane emulsion having a viscosity at about 25 ° C. of about 20 to about 1,500 cs,

(ii) (i) 100 parts by weight of about 5 to about 50 parts by weight, (CH _{3) 3} SiO _1/2 units to SiO ₂ units of from about 0.6: 1 to about 1.2: 1 (CH _{3) 3} SiO _{1 /} Siloxane resin composed of ₂ units and SiO ₂ units, and

(iii) (i) an antifoaming foam control agent comprising about 1 to about 20 parts by weight of solid silica gel per 100 parts by weight.

In preferred silicone foam inhibitors for use in the present invention, the solvent in the continuous phase consists of a specific polyethylene glycol or polyethylene-polypropylene glycol copolymer or a mixture thereof (preferably) or consists of propylene glycol. The primary silicone foam inhibitor is branched / crosslinked and is preferably not straight chain.

To further illustrate this, typical laundry liquid detergent compositions with controlled foaming optionally contain from about 0.001% to about 1% by weight, preferably from about 0.01% to about 0.7% by weight of the above silicone foam inhibitor. From about 0.05% to about 0.5% by weight, which comprises polyorganosiloxane (a), silicone compound (b) made from resinous siloxane or silicone resin, finely divided filler (c), and mixed ingredients (a), (b) Water-insoluble emulsion (1) of a primary antifoaming agent which is a mixture of c) and a catalyst (d) which promotes the reaction of component (c) to form silanolate; One or more nonionic silicone surfactants (2); And copolymer (3) of polyethylene glycol or polyethylene-polypropylene glycol having a solubility in water of at least about 2% by weight at room temperature, and polypropylene glycol is absent. Similar amounts can be used for granular compositions, gels, and the like. See, for example, US Pat. No. 4,978,471, Starch, issued Dec. 18, 1990, and US Pat. No. 4,983,316, Starch, issued Jan. 8, 1991, US Pat. No. 5,288,431. , Huber et al., Issued February 22, 1994 and US Pat. Nos. 4,639,489 and US Pat. Nos. 4,749,740, Arizawa et al., Lines 46-46.

The silicone foam inhibitors of the present invention preferably comprise polyethylene glycol and polyethylene glycol / polypropylene glycol copolymers, all of which have an average molecular weight of less than about 1,000, preferably about 100 to 800. The solubility in water of the polyethylene glycol and polyethylene / polypropylene copolymers of the present invention at room temperature is at least about 2% by weight, preferably at least about 5% by weight.

Preferred solvents of the present invention are copolymers of polyethylene glycol and polyethylene glycol / polypropylene glycol having an average molecular weight of less than about 1,000, more preferably from about 100 to 800, most preferably from 200 to 400, preferably PPG 200 / PEG 300. A weight ratio of polyethylene glycol: polyethylene-polypropylene glycol of about 1: 1 to 1:10 is preferred, with a weight ratio of 1: 3 to 1: 6 being most preferred.

Preferred silicone foam inhibitors for use in the present invention do not contain polypropylene glycols having a molecular weight of 4,000 in particular. They also preferably do not contain block copolymers of propylene oxide with ethylene oxide such as PLURONIC L101.

Other foam inhibitors useful in the present invention include secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of the alcohols and silicone oils such as silicones (e.g., U.S. Patent 4,798,679, U.S. Patent 4,075,118, and European Patent 150,872). As described in the heading). Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having C ₁ -C ₁₆ chains. Preferred alcohols are 2-butyl octanol, available from Condea under the trade name ISOFOL 12. Secondary alcohol mixtures are commercially available under the trade name ISALCHEM 123, manufactured by Enichem. Mixed foam inhibitors typically comprise a mixture of alcohols and silicones in a weight ratio of 1: 5 to 5: 1.

In the case of detergent compositions used in automatic washing machines, the foam should not be so formed that it overflows in the washing machine. If a foam inhibitor is used, it is preferably present in an "foam inhibitor". "Anti-foam amount" means that the manufacturer of the composition can select an amount of foam control agent that can sufficiently control the foam to produce a low-foam laundry detergent for use in an automatic laundry washer.

Compositions of the present invention generally comprise from 0 to about 5% by weight foam inhibitor. When used as an antifoaming agent, monocarboxylic fatty acids and salts thereof are typically present in up to about 5% by weight of the detergent composition. Preferably, about 0.5 to about 3 weight percent of fatty monocarboxylate foam inhibitor is used. Silicone foam inhibitors are typically used at up to about 2.0% by weight of the detergent composition, although large amounts of silicone foam inhibitors can be used. This upper limit is practical in practice, mainly because small quantities are effective to minimize maintenance costs and effectively control the foam. Preferably about 0.01 to about 1 weight percent of the silicone foam inhibitor is used, more preferably about 0.25 to about 0.5 weight percent. As used herein, this weight percent value includes any silica that can be used in combination with the polyorganosiloxane and any binding materials that can be used. Monostearyl phosphate foam inhibitors are generally used in amounts of about 0.1 to about 2 weight percent of the compositions of the present invention. Hydrocarbon foam inhibitors are typically used in amounts of about 0.01 to about 5.0 weight percent, but can be used at higher concentrations. Alcohol foam inhibitors are typically used at about 0.2 to 3 weight percent of the processing composition.

Fabric softener

A variety of through-the-wash fabric softners, in particular fine smectite clays described in US Pat. No. 4,062,647, issued to Strom and Nirschl, issued December 13, 1977. clay, a smectite clay and other softeners known in the art, can typically be optionally used in a composition of the present invention at a concentration of about 0.5 to about 10 weight percent to provide fabric softener benefit simultaneously with fabric cleaning. Clay softeners are disclosed, for example, in US Pat. No. 4,375,416, Crisp et al., Issued March 1, 1983 and US Pat. No. 4,291,071, Harris et al., Issued September 22, 1981. As described above, the cationic softener and the amine may be mixed together.

Otitis inhibitor

The composition of the present invention may also comprise one or more materials effective to inhibit dye migration from one fabric to another during the cleaning process. Generally, such disinfection inhibitors include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone with N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures thereof do. When using such agents, they typically comprise from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2% by weight of the composition of the present invention.

More particularly, preferred polyamine N-oxide polymers for use in the present invention are units of the formula RA _x -P, wherein p may form part of the unit to which the NO group may be bonded or the NO group may be polymerized or Is a polymerizable unit that can be combined with both of these units, A is any one of the formulas -NC (O)-, -C (O) O-, -S-, -O- or -N =, and x is 0 or 1, and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or cycloaliphatic group or mixture thereof in which the nitrogen of the NO group may be bonded or the NO group may be part of these groups) . Preferred polyamine N-oxides are compounds in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolodine, piperidine and derivatives thereof.

NO group is a structural formula Groups wherein R ₁ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or cycloaliphatic groups or mixtures thereof, x, y and z are 0 or 1 and the nitrogen of the NO group is May be combined or form any part of the groups mentioned above). The pKa of the amine oxide units of the polyamine N-oxide is less than 10, preferably less than 7, more preferably less than 6.

Any polymer backbone can be used as long as the amine polymer formed is water soluble and has disinfection control properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylene, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random copolymers or block copolymers in which one monomer type is amine N-oxide and the other monomer type is N-oxide. Amine N-oxide polymers typically have a ratio of amine to amine N-oxide of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained upon polymerization of almost any degree. Typically, the average molecular weight is within 500 to 1,000,000, more preferably 1,000 to 500,000, most preferably 5,000 to 100,000. Such a group of preferred materials may be referred to as "PVNO".

The most preferred polyamine N-oxides useful in the detergent compositions of the present invention are poly (4-vinylpyridine-N-oxides) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4. Copolymers during the rollidone and N-vinylimidazole polymerizations (hereinafter referred to as the "PVPVI" group) are also preferred for use herein. Preferably, the average molecular weight of PVPVI is 5,000 to 1,000,000, more preferred. Preferably 5,000 to 200,000, most preferably 10,000 to 20,000. {Average molecular weight is determined by light scattering as described in Barth et al., Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization", which is hereby incorporated by reference in its entirety} PVPVI copolymer Is typically a molar ratio of N-vinylimidazole to N-vinylpyrrolidone 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1 to be. These copolymers may be straight or branched chain.

The compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000. PVP is known to those skilled in the detergent field (see, for example, European Patent Application No. 262,897 and European Patent Application No. 256,696, incorporated herein by reference). Compositions containing PVP may also contain polyethylene glycol (“PEG”) having an average molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP (based on ppm) delivered in the wash solution is about 2: 1 to about 50: 1, more preferably about 3: 1 to about 10: 1.

Detergent compositions of the present invention may also contain from about 0.005 to 5% by weight of certain types of hydrophilic fluorescent brighteners, which may optionally provide anti-inflammatory activity. When using the compositions of the present invention, they preferably comprise about 0.01 to 1% by weight of the fluorescent brightener.

Hydrophilic fluorescent brightener useful in the present invention is a structural formula Compounds wherein R ₁ is anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, and R ₂ is N-2-bis-hydroxyethyl, N-2-hydroxyethyl -N-methylamino, morpholino, chloro and amino, M is a salt forming cation (eg sodium or potassium).

In the above formula, where R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation (e.g. sodium), the brightener is 4,4'-bis [(4-anilino -6- (N-2-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenesulfonic acid and disodium salt. This particular class of brighteners is marketed under the tradename Tinopal-UNPA-GX by Ciba Geigy Corporation. Tinopal-UNPA-GX is a preferred hydrophilic fluorescent brightener useful in the detergent composition of the present invention.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation (e.g. sodium), the brightener is 4,4'-bis [ (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbendisulfonic acid disodium salt. This particular class of brighteners is commercially available from Ciba Geigy Corporation under the tradename Tinopal 5BM-GX.

In the above formula, when R ₁ is anilino, R ₂ is morpholino and M is a cation (e.g. sodium), the brightener is 4,4'-bis [(4-anilino-6-morpholino) -s-triazin-2-yl) amino] -2,2'-stilbenesulfonic acid, sodium salt. This particular class of brighteners is commercially available from Ciba Geigy Corporation under the tradename Tinopal AMS-GX.

The particular class of fluorescent brighteners selected for use in the present invention provides particularly effective desalting property benefits when used in admixture with the selected polymeric disinfecting inhibitors described below. Mixing of such selected polymeric materials (e.g. PVNO and / or PVPVI) with such selected fluorescent brighteners (e.g. Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) is used alone. In the case of an aqueous wash solution, it provides significantly better anti-inflammatory properties than the anti-inflammatory properties of either of these two detergent composition components. Without wishing to be bound by theory, it is believed that these brighteners work in this way because they have a high affinity for the fabric in the wash solution and are deposited relatively quickly on these fabrics. The degree to which the brightener is deposited on the fabric in the wash solution can be defined by a parameter called an "exhaustion coefficient". The adsorption coefficient is generally referred to as the ratio of the brightener material (a) deposited on the fabric to the initial brightener concentration (b) in the wash liquor. Brighteners with relatively high adsorption coefficients are most suitable for inhibiting dye migration in the context of the present invention.

Of course, it is contemplated that compounds of the conventional fluorescent brightener type may be optionally used in the compositions of the present invention to provide conventional fabric "whitening" benefits rather than pure disinfection inhibitory effects. Such uses are common and are well known in detergent compositions.

Preparation of Polyamines

Example 1

Ethoxylation of Poly (ethyleneimine) with an Average Molecular Weight of 1,800

A thermometer ^{(Therm-O-Watch TM,} I 2 R), purging tube's (sparging tube) and a three-necked are 250㎖ which is equipped with a mechanical stirrer, round bottom flask connected to a client sensor head (Claisen head), climate control Poly (ethyleneimine) MW 1800 (Polysciences, 50.0 g, 0.028 mol) is added. Ethylene oxide gas (Liquid Carbonics) is added through a sputtering tube under argon at about 140 ° C. with very rapid stirring until a weight increase of 52 g (corresponding to 1.2 ethoxy units) is obtained. 50 g of this yellow gelled material portion is stored. Potassium hydroxide pellets (Baker, 0.30 g, 0.0053 mol) are added to the residual material. After dissolving potassium hydroxide, ethylene oxide is added as mentioned above until a weight increase of 60 g (corresponding to a total of 4.2 ethoxy units) is obtained. Store 53 g of this brown viscous liquid portion. Ethylene oxide is added to the remaining material as mentioned above to yield 94.9 g of a dark brown liquid until a weight gain of 35.9 g (corresponding to a total of 7.1 ethoxy units) is obtained. Theoretical amounts of methanesulfonic acid are added to neutralize potassium hydroxide in the latter two samples.

Example 2

PEI 1800 E ₇ 4th grade

Polyethyleneimine having a molecular weight of 1,800 was added to a 500 ml Erlenmeyer flask equipped with a magnetic stir bar, and nitrogen (PEI 1800, E ₇ ) (207.3 g, 0.590 mol of nitrogen, as in Example 1). Preformed) and acetonitrile (120 g) to further denature by ethoxylation with about 7 ethyleneoxy moieties. Dimethyl sulfate (28.3 g, 0.224 mol) is added to the rapidly stirred solution at once, capped and stirred overnight at room temperature. Acetonitrile is removed by rotary evaporator at about 60 ° C. and further solvent is removed using a Kugelrohr apparatus at about 80 ° C. to obtain 220 g of partially quaternized material which is preferred as a dark brown viscous liquid. ¹³ C-NMR (D ₂ O) spectra obtained on a sample of the reaction product indicate no carbon resonance at about 58 ppm corresponding to dimethyl sulfate. Since the methylene adjacent to the non-quaternized nitrogen shifted about 3.0 ppm, the ¹ H-NMR (D ₂ O) spectrum showed that the resonance partially shifted at about 2.5 ppm. This is consistent with the desired quaternization of about 38% nitrogen.

Example 3

PEI 1800 E ₇ Formulation of Amine Oxide

To a 500 ml Erlenmeyer flask equipped with a magnetic stir bar, polyethyleneimine having a molecular weight of 1,800 was added, nitrogen (PEI 1800, E ₇ ) (209 g, 0.595 mol of nitrogen, prepared as in Example 1) and hydrogen peroxide ( 120 g of a 30 wt% solution in water, 1.06 g) is ethoxylated into about 7 ethoxy groups. The flask is capped and after initial exotherm, the solution is stirred overnight at room temperature. The ¹ H-NMR (D ₂ O) spectrum obtained on the sample of the reaction mixture shows complete conversion. Resonance in the methylene moiety adjacent to the unoxidized nitrogen indicates that it has moved from its original position at about 2.5 ppm to about 3.5 ppm. About 5 g of 0.5% Pd on alumina pellets is added to the reaction solution, and the solution is left at room temperature for about 3 days. The solution was tested with indicator paper and found to be negative for peroxides. The material obtained is suitably stored as 51.1% by weight active solution in water.

Example 4

Quaternary PEI 1800 E ₇ Formulation of Amine Oxide

Polyethyleneimine having a molecular weight of 1,800 was added to a 500 ml Erlenmeyer flask equipped with a magnetic stir bar, and further modified by ethoxylation with about 7 ethyleneoxy residues to nitrogen (PEI 1800, E ₇ ). Then dimethyl sulfate (130 g, about 0.20 mol of oxidizing nitrogen, prepared as in Example II), hydrogen peroxide (48 g of 30 wt% solution in water, 0.423 mol) and water (about 50 g) to about 38%. Rapidly denature further. The flask is capped and after initial exotherm, the solution is stirred overnight at room temperature. The ¹ H-NMR (D ₂ O) spectrum obtained from the sample from the reaction mixture showed that the resonance belonging to the previously observed methylene peak at 2.5 to 3.0 ppm for the material with methylene having a chemical shift of about 3.7 ppm was completely converted. Indicates. About 5 g of 0.5% Pd on alumina pellets is added to the reaction solution, and the solution is left at room temperature for about 3 days. The solution was tested with indicator paper and found to be negative for peroxides. The desired material having about 38% quaternized nitrogen and 62% nitrogen oxidized to amine oxide is suitably stored as 44.9% by weight active solution in water.

Example 5

PEI 1200 E ₇ Manufacture

Ethoxylation is carried out in a two gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and ethylene oxide is introduced as a liquid. The net cylinder of about 20 lb of ethylene oxide (ARC) is set to position the cylinder on a scale where the weight change of the cylinder can be observed and to pump the ethylene oxide into the autoclave as a liquid phase.

750 g of polyethyleneimine (PEI) moiety [with a described average molecular weight of 1,200 equal to about 0.625 mole of polymer and 17.4 mole of nitrogen functionality] is added to the autoclave. The autoclave is then sealed and purged with air (by applying vacuum to -28 "Hg, pressurized to 250 psia with nitrogen and then evacuated to atmospheric pressure). The oatclave contents are brought to 130 ° C. while applying a vacuum. After about 1 hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 ° C. The ethylene oxide is then released for several hours while closely monitoring the autoclave pressure, temperature and ethylene oxide flow rate. Added to the autoclave over an extended turn off and cooling the ethylene oxide pump to limit any temperature increase resulting from the exothermic reaction, maintaining the temperature at 100 to 110 ° C. while gradually increasing the overall pressure during the reaction path. 750 g total ethylene oxide (nearly 1 mole of ethylene oxide for PEI nitrogen functional groups) Equivalent) After charging the autoclave, the temperature is raised to 110 ° C. and the autoclave is stirred for an additional hour, at which time a vacuum is applied to remove any remaining unreacted ethylene oxide.

The autoclave is then cooled to about 50 ° C. and vacuum is continued while introducing 376 g of 25% sodium methoxide (1.74 mole, 10% catalyst based on PEI nitrogen functionality) in methanol solution. The methoxide solution is aspirated into the autoclave under vacuum and the oatclave thermostat anchor point is increased to 130 ° C. Use the device to observe the power consumption with a shaker. Observe the shaker power with temperature and pressure. As methanol is removed from the autoclave, the shaker power and temperature values increase slowly, the viscosity of the mixture increases and is stable for about 1 hour, indicating that most of the methanol is removed. The mixture is further heated and shaken under vacuum for a further 30 minutes.

The vacuum is removed and the autoclave is cooled to 105 ° C. with nitrogen charged to 250 psia and vented to ambient pressure. The autoclave is charged with nitrogen to 200 psia. Ethylene oxide is incrementally added back to the autoclave before closely monitoring the autoclave pressure, temperature and ethylene oxide flow rate while maintaining the temperature between 100 and 110 ° C. and limiting any temperature increase due to the exothermic reaction. After adding 4,500 g of ethylene oxide (7 mole total ethylene oxide to 1 mole of PEI nitrogen functional group) is added over several hours, the temperature is increased to 110 ° C. and the mixture is stirred for additional time.

The reaction mixture is then collected in a nitrogen purged vessel and transferred into a 22 L three-necked round bottom flask equipped with heating and shaking. 167 g (1.74 mole) of methanesulfonic acid are added to neutralize the strongly alkaline catalyst. The mixture is then heated to 130 ° C. and inert gas (argon or nitrogen) is passed through the reaction mixture and gas dispersion frit at about 100 cu.ft. Pass through to deodorize the reaction mixture.

The final reaction product is cooled slightly and collected in an organic vessel purged with nitrogen.

In another method of production, the product is neutralized and deodorized in the reactor prior to discharge.

Other preferred examples (eg PEI 1200 E15 and PEI 1200 E20) are prepared by the above-mentioned methods by adjusting the reaction time and the appropriate amount of ethylene oxide used in the reaction.

Example 6

PEI 1200 E ₇ 9.7% of Level 4

500 ml of Erlenmeyer flasks equipped with a magnetic stir bar with MW 1,200 polyethyleneimine (248.4 g, 0.707 mol of nitrogen, prepared as in Example 5) and acetonitrile (Baker, 200 ml] is added. Dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) is added all at once to the rapidly stirred solution, capped and stirred at room temperature overnight. Acetonitrile is evaporated on a rotary evaporator at about 60 ° C. and evaporated by Kugelor apparatus (Aldrich) at about 80 ° C. to give about 220 g of the desired material as a dark brown viscous liquid. ^{The 13} C-NMR (D ₂ O) spectrum shows no peak at about 58 ppm corresponding to dimethyl sulfate. ^{The 1} H-NMR (D ₂ O) spectrum shows that the peak shifts partially from 2.5 (methylene bound to unquaternized nitrogen) to about 3.0 ppm.

Example 7

PEI 600 E ₂₀ Manufacture

Ethoxylation is performed in a two gallon stirred stainless steel autoclave equipped with temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and introduction of ethylene oxide as a liquid. The cylinder is placed on a scale where a weight change can be observed, setting about 20 lb of net cylinder to pump the ethylene oxide (ARC) into the autoclave as a liquid phase.

250 g of polyethyleneimine (PEI) moiety (with a described average molecular weight of 600 equivalent to Nippon Shokubai, about 0.417 mole of polymer and 6.25 mole of nitrogen functionality) are added to the autoclave. The autoclave is then sealed and purged with air (by applying vacuum to -28 "Hg, pressurized to 250 psia with nitrogen and then evacuated to atmospheric pressure). After about 1 hour, the autoclave was charged with nitrogen up to about 250 psia while cooling the autoclave to about 105 ° C. The ethylene oxide was then several hours while closely monitoring the autoclave pressure, temperature and ethylene oxide flow rate. Added to the autoclave over an extended period of time by turning off the ethylene oxide pump and cooling to limit any temperature increase resulting from the exothermic reaction, maintaining the temperature at 100 to 110 ° C. while gradually increasing the overall pressure during the reaction path. A total of 275 grams of ethylene oxide was added (with 1 mole of ethylene oxide for PEI nitrogen functionality). Equivalent to) After charging the autoclave, the temperature is increased to 110 ° C. and the autoclave is stirred for an additional hour, at which time a vacuum is applied to remove any remaining unreacted ethylene oxide.

The autoclave is then cooled to about 50 ° C. and vacuum is continued while introducing 135 g of 25% sodium methoxide (0.625 mole, 10% catalyst based on PEI nitrogen functionality) in methanol solution. The methoxide solution is aspirated into the autoclave under vacuum and the oatclave thermostat anchor point is increased to 130 ° C. Use the device to observe the power consumption by the shaker. Observe the shaker power over temperature and pressure. As methanol was removed from the autoclave, the shaker power and temperature values increased slowly, the viscosity of the mixture increased, and was stable for about 1 hour, indicating that most of the methanol was removed. The mixture is further heated and shaken under vacuum for a further 30 minutes.

The vacuum is removed and the autoclave is cooled to 105 ° C. with nitrogen to 250 psia and vented to ambient pressure. The autoclave is charged with nitrogen to 200 psia. Ethylene oxide is incrementally added back to the autoclave before closely monitoring the autoclave pressure, temperature and ethylene oxide flow rate while maintaining the temperature between 100 and 110 ° C. and limiting any temperature increase due to the exothermic reaction. After about 5,225 g of ethylene oxide (total of 20 moles of ethylene oxide per 1 mole of PEI nitrogen functional group) are added over several hours, the temperature is increased to 110 ° C. and the mixture is stirred for an additional hour.

The reaction mixture is then collected in a nitrogen purged vessel and transferred into a 22 L three-necked round bottom flask equipped with heating and shaking. 60 g (0.625 mole) of methanesulfonic acid are added to neutralize the strongly alkaline catalyst. The mixture was then heated to 130 ° C. and inert gas (argon or nitrogen) was passed through the reaction mixture and gas dispersion frit to about 100 cu. ft. Pass through to deodorize the reaction mixture.

The final reaction product is cooled slightly and collected in an organic vessel purged with nitrogen.

In another method of production, the product is neutralized and deodorized in the reactor prior to discharge.

The following describes a high concentration liquid detergent composition according to the present invention:

1. E ₉ ethoxylated alcohol sold by Shell Oil Co.

2. Ethoxylated tetraethylenepentamine (PEI 189 E ₁₅ -E ₁₈ ) according to US Pat. No. 4,597,898 to Vander Meer, issued July 1, 1986.

3. Bleaching stability variant of BPN '(protease A-BSV) as known from European Patent Application No. 130,756 A of January 9, 1985.

4. Subtilisin 309 Loop Region 6 variant.

5. Novo marketed proteolytic enzymes.

6. Polyamine according to example 7 (PEI 600 E20).

7. Polyamine according to example 5 (PEI 1200 E20).

8. The remaining amount to be 100% is a small amount of a fluorescence brightener, a fragrance, a foam inhibitor, a contaminant dispersant, a chelating agent, a disinfectant inhibitor, additional water, and a filler including, for example, CaCO ₃ , talc, silicate, and the like. Additives.

1. E ₉ ethoxylated alcohol sold by Shell Oil Corporation.

2. Bleaching stability variant of BPN '(protease A-BSV) as known from European Patent Application No. 130,756 A of January 9, 1985.

3. Subtilisin 309 loop region 6 variant.

4. Proteolytic enzymes marketed by Novo.

5. Polyamine according to example 1 (PEI 1200 E7).

6. Polyamine according to example 7 (PEI 600 E20).

7. The remaining amount to be 100% is a small amount of fluorescent brightener, flavoring agent, antifoaming agent, contaminant dispersant, chelating agent, disinfectant inhibitor, additional water and fillers including, for example, CaCO ₃ , talc, silicates and the like. Additives.

1. E ₉ ethoxylated alcohol sold by Shell Oil Corporation.

2. Protease B variant of BPN 'with Tyr 217 replaced with Leu.

3. The subtilisin 309 variant, wherein the denatured amino acid sequence is a subtilisin 309 wild-type amino acid sequence, wherein the substitution occurs at one or more positions 194, 195, 196, 199 or 200.

4. Polyamine according to example 4.

5. Polyamine according to example 7.

6. The remaining amount to be 100% is a small amount of fluorescent brightener, fragrance, antifoam, contaminant dispersant, chelating agent, disinfectant inhibitor, additional water and fillers including, for example, CaCO ₃ , talc, silicates and the like. Additives.

1. E ₉ ethoxylated alcohol sold by Shell Oil Corporation.

2. Protease B variant of BPN 'with Tyr 217 replaced with Leu.

3. The subtilisin 309 variant, wherein the denatured amino acid sequence is a subtilisin 309 wild type amino acid sequence, wherein the substitution occurs at one or more positions 194, 195, 196, 199 or 200.

4. Polyamine according to example 7.

5. Polyamine according to Example 1.

6. The remaining amount to be 100% is a small amount of fluorescent brightener, fragrance, antifoam, contaminant dispersant, chelating agent, disinfectant inhibitor, additional water and fillers including, for example, CaCO ₃ , talc, silicates and the like. Additives.

1. C ₁₂ -C ₁₃ alkyl E ₉ ethoxylate sold by Shell Oil Corporation.

2. Bacillus amylolyquepathy subtilisin, as described in International Publication No. 95/10615, published April 20, 1995 by Genenker International.

3. Derived from Fumi-Cola Ranoginosa and marketed by Novo.

4. Listed in International Patent Publication No. 9,510,603 A, which is marketed by Novo.

5. Polyamine according to example 7.

1. Polyamine of Example 7.

2. Polyamine of Example 1.

1. Polyamine of Example 7.

2. Polyamine of Example 1.

3. The polyamine of Example 5.

Claims (14)

Surfactants, Effective amount of HEDP and Formula with modified polyamine of Formula 1 Formula having a polyamine backbone or modified polyamine of formula (2) corresponding to wherein n is from 0 to 200 and m is from 4 to 400 A stabilizing amount of a water-soluble or water-dispersible modified polyamine comprising a polyamine backbone corresponding to where n is from 0 to 200, m is from 4 to 400, and k is less than or equal to n. Molecular weight of the polyamine backbone exceeds 200 daltons]. Formula 1 V _{(n + 1)} W _m Y _n Z Formula 2 V _{(n-k + 1)} W _m Y _n Y ' _k Z In Chemical Formulas 1 and 2 above, n is 0 to 200, m is 4 to 400, k is less than or equal to n, Iii) the V unit is Is a terminal unit of Ii) W unit is represented by Is the main chain unit of, Iii) Y unit is Is a side chain unit of, Iii) the Z unit is Is the terminal unit of Main chain bond R units include C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy-alkylene, C ₈ -C ₁₂ dialkyl Arylene,-(R ¹ O) _X R ¹ -,-(R ¹ O) _X R ⁵ (OR ¹ ) _X -,-(CH ₂ CH (OR ² ) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH (OR ² ) CH ₂ ) _W- , -C (O) (R ⁴ ) _r C (O)-, -CH ₂ CH (OR ² ) CH ₂ -and a combination thereof R ¹ is C ₂ -C ₃ alkylene and combinations thereof, R ² is hydrogen, — (R ¹ O) _X B and combinations thereof, R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and combinations thereof, R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene and combinations thereof, R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxy-alkylene, C ₄ -C ₁₂ dihydroxy Alkylene, C ₈ -C ₁₂ dialkylarylene, -C (O)-, -C (O) NHR ⁶ NHC (O)-, -R ¹ (OR ¹ )-, -C (O) (R ⁴ ) _r C (O)-, -CH ₂ CH (OH) CH _2- , -CH ₂ CH (OH) CH ₂ O (R ¹ O) _y R ¹ -OCH ₂ CH (OH) CH ₂ -and combinations thereof, R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene E unit is hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl,-(CH ₂ ) _p -CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) -CO ₂ M,-(CH ₂ ) _p PO ₃ M,-(R ¹ O) _X B, -C (O) R ³ And combinations thereof, provided that if any one of the E units bound to nitrogen is hydrogen, then nitrogen is also not N-oxide and B is hydrogen, C ₁ -C ₆ alkyl, — (CH ₂ ) _q -SO ₃ M,-(CH ₂ ) _P CO ₂ M,-(CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M,-(CH ₂ ) _q- (CHSO ₂ M) CH ₂ SO ₃ M ,-(CH ₂ ) _P PO ₃ M, -PO ₃ M and combinations thereof, M is hydrogen or an amount of water-soluble cation sufficient to satisfy the charge balance, X is a water-soluble anion, p is 1-6 , q is 0 to 6, r is 0 or 1, w is 0 or 1, x is 1 to 100, y is 0 to 100 and z is 0 or 1. The composition of claim 1 wherein the detersive surfactant comprises an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof. _{3. The} compound of claim 1, wherein R is C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene ,-(R ¹ O) _x R ¹ -,-(R ¹ O) _x R ⁵ (OR ¹ ) _x -,-(CH ₂ CH (OH) CH ₂ O) _z (R ¹ O) _y R ¹ ( OCH ₂ CH (OH) CH ₂ ) _w- , -CH ₂ CH (OR ² ) CH ₂ -and combinations thereof. The composition of claim 3, wherein R is C ₂ -C ₆ alkylene. The composition of claim 4, wherein R is C ₂ alkylene ethylene. The composition of claim 1 or 2, wherein E is (R ₁ O) _× B. The composition of claim 6, wherein R ₁ is C ₂ alkylene and B is hydrogen. 8. The composition of claim 7, wherein x is from 5 to 30. 8. The composition of claim 7, wherein prior to denaturation, the molecular weight of PEI is between 200 and 3,000 Daltons. The composition of claim 1 or 2 comprising 0.1 to 5% by weight of HEDP. The composition of claim 10 comprising 0.2 to 2% by weight of HEDP. The composition of claim 1 or 2 comprising 0.1 to 10% by weight of a polyamine. 13. The composition of claim 12 comprising from 0.2 to 5% by weight of polyamines. The composition of claim 1 or 2 comprising 30 to 40% by weight of water.