CZ20017A3 - Fabric treating preparation and use thereof - Google Patents

Abstract

The present invention is a fabric care composition comprising a nitrogen containing compound selected from a polyamino-functional polymer, a dye fixing agent, and mixtures thereof, and a scum reducing agent selected from a water-soluble cationic surface active agent; a polyoxyalkylene alkyl amine surface active agent, and mixtures thereof, whereby the composition exhibit reduced or even no scum formation on fabric and/or washing machine parts compared to compositions which do not comprise the scum reducing agent.

Description

Fabric and use care product ^{from the} use of the fabric.

Technical field

The present invention relates to fabric care compositions and more preferably to a method and composition that reduces or even does not coat the fabric and / or parts of the washing machine while still providing color treatment for fabric treated with the composition.

BACKGROUND OF THE INVENTION

The appearance of dyed fabrics, such as clothing, bedding, household fabrics, such as table linen, is one of the areas of concern to consumers. Of course, typical consumer uses of fabrics, such as wearing, washing, soaking and / or drying fabrics, deteriorate the appearance of the fabric resulting from loss of color saturation and hue. This problem of color saturation becomes more acute after several washes.

The present invention provides a compound that provides improved color care on washed fabrics, especially after several washes. Dye-fixing compositions as described in EP 462 806 are suitable compositions for this purpose. Indeed, these compositions treat fabric colors because they bind loosely attached dyes to the fabric.

New classes of materials, namely aminofunctional polymers, can still be used. Indeed, they have recently been found to be more used in fabric processing because of providing fabric color care.

However, the problem now associated with compositions comprising such dye fixing agents and / or an aminofunctional polymer is the resulting coating that is formed on the treated fabric and / or parts of the washing machine.

So far, it has not been theoretically verified that the coating is formed from interactions of nitrogen-containing compounds, for example aminofunctional polymers and / or dye fixing agents, with an anionic group, such as anionic detergents obtained from laundry detergents, especially after several washes. This interaction results in an insoluble, sticky precipitate on the fabric and / or parts of the washing machine.

The author of the fabric care composition is faced with the double challenge of providing such a composition which reduces or even does not coat, but without being detrimental to the color of the treated fabrics.

The inventor has now surprisingly found that adding a coating reducing agent selected from water-soluble cationic surfactant, polyoxyalkylene alkyl amine surfactant, and mixtures thereof, to compositions comprising a nitrogen-containing compound selected from an aminofunctional polymer, a dye fixing agent, it overcomes this problem.

SUMMARY OF THE INVENTION

The present invention relates to a fabric care composition comprising

(i) a nitrogen-containing compound selected from a polyaminofunctional polymer, a dye fixing agent and mixtures thereof; and (ii) a coating reducing agent selected from a water-soluble cationic surfactant, a polyoxyalkylene alkyl amine surfactant, and mixtures thereof, when the single nitrogen-containing compound is a polyaminofunctional polymer, the polymer is present in an amount greater than 1% by weight.

In another aspect of the present invention, a surfactant is used herein in a composition comprising a nitrogen-containing compound selected from a polyaminofunctional polymer, a dye fixing agent and mixtures thereof to reduce or prevent coating on fabrics or parts of the washing machine that have come into contact with the device.

According to a further aspect of the present invention there is provided a fabric care composition with effective and sustained properties that treats color.

An essential component of the invention is a nitrogen-containing compound selected from an aminofunctional polymer, a dye fixing agent, and mixtures thereof.

Polyaminofunctional polymer

The polyaminofunctional polymer preferably cares for fabric colors.

The polyaminofunctional polymers of the present invention are water-soluble or dispersible polyamines. Typically, polyaminofunkční polymers for use herein have a molecular weight between 200 and 10 ^6, preferably between 600 and 20,000, most preferably between 1000 and 10 000. These polyamines comprise backbones that can be either linear or cyclic. The polyamine backbone may also include polyamines branching to a higher or lower degree. More preferably, the polyamine backbones described in the present invention are modified in such a way that at least one, more preferably, but each nitrogen of the polyamine chain is then substituted, quaternized, oxidized or modified by combinations of the reactions below.

For the purposes of the present invention, the term "modification" relating to the chemical structure of polyamines is defined as the replacement of the skeleton hydrogen atom -NH by the unit R '(substitution), by quartemization of nitrogen on the skeleton (quaternized) or by oxidation of nitrogen on the skeleton to N-oxide (oxidized) ). The terms "modification" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to a nitrogen on a R 'skeleton by a unit. Quaternization or oxidation may be interchangeable and may be without substitution, but substitution is more conveniently accompanied by oxidation or quaternization of at least one nitrogen on the scaffold.

Linear or non-cyclic polyamine backbones that include an amino-functional polymer have the general formula:

I [R 2 N-RW 1 - [NR] _m - [NR] _n -NR 1

Cyclic polyamine backbones that include an amino-functional polymer have the general formula:

R * | R [RAN-RJirk + t - [NR] _m - [NR] _n - (N-R) _k -NRi

The aforementioned skeletons preferably before, but suitably after the subsequent modification, contain primary, secondary and tertiary nitrogen amine groups linked by R "linking" units.

For the purposes of the present invention, primary nitrogen amines comprising a single modified skeleton or branched chain and are defined as a V or Z "terminating" unit. For example, when a primary amino group located at the end of a polyamine backbone or branched chain having a general structure

H ₂ N- [RJ] is modified according to the present invention, then it is defined as a V "terminating" unit or only a V unit. Although, for the purposes of the present invention, some or all of the primary amino groups may remain an unmodified subject with the limitations further described herein below. These unmodified primary amino groups, based on their position in the scaffold chain, continue to be "terminating" units. Similarly, when the primary amino group is located at the end of the main polyamine skeleton having the general structure

-NH ₂ C is modified according to the present invention, then it is defined as a Z "terminating" unit or only a Z unit. This unit may remain an unmodified subject by the limitations further described herein below.

Similarly, secondary nitrogen amino groups comprising a single modified backbone or branched chain are defined as W "backbone" units. For example, when a secondary amino group, an important component of the skeletons and branched chains of the present invention, has a general structure

H - [N-R] is modified according to the present invention, then it is defined as a W "skeleton" unit or only a W unit. Although, for the purposes of the present invention, some or all of the secondary amino groups may remain unmodified. These unmodified secondary amino groups, based on their position in the scaffold chain, continue to be "terminating" units.

In a similar way, tertiary nitrogen containing amino groups comprising a single modified skeleton or branched chain are defined as Y "branched" units. For example, when a tertiary amino group that is a branching point of either a polyamine backbone or other branched chains or rings having a general structure

I - [N-RJ] is modified according to the present invention, then it is defined as a Y "branched" unit or only a Y unit. Although, for the purposes of the present invention, some or all of the tertiary amino groups may remain unmodified. These unmodified tertiary amino groups, based on their position in the scaffold chain, continue to be "branched" units. The R units associated with the V, W and Y nitrogen units that serve to join the polyamine nitrogen are described below in the present invention.

Thus, the final modified structure of the polyamines of the present invention may be represented by the general formula

V (n + 1) W _m Y _n Z for a linear polymer with an amino functional group and a general formula

V (n-k + 1) W _m Y _n Y'kZ for an amino-functional cyclic polymer. In the case of polyamines comprising the rings, the Y 'unit of the general formula: - - - - - - - - - -

I R - [N-RJ— serves as a branch point for a skeleton or branched ring. For each Y 'unit, Y is a unit having the general formula

I - [N-R] Which creates the point of attachment of the ring to the main polymer chain or branch. In an isolated case where the skeleton is a complete ring, the polyamine skeleton has the general formula

R ', (RzN - R] _n - [N - R] _m - (N-R] _n - hence not including any Z terminating unit and having the general formula

V _n . _k W _m Y _n Y ' _k where k is the number of circles forming branched units. More preferably, the polyamine backbones of the present invention do not include any rings.

In the case of non-cyclic polyamines, the ratio of the index n to the index m is related to the relative degree of branching. The completely unbranched linear modified polyamine of the present invention has the general formula in _{w m} z where n is 0. A higher value of n (lower ratio m kn) causes a higher degree of branching in the molecule. Typically, the value for m ranges from a minimum value of 2 to 700, more preferably from 4 to 400, the largest values of m, especially when the value indexes very small or near zero, are also suitable.

Each polyamine nitrogen, in each case primary, secondary or tertiary, once modified according to the present invention, is further defined as an existing member of one of three general classes; monosubstituted, quaternized or oxidized. These polyamine nitrogen unmodified units are classified as V, W, Y, Y 'or Z units depending on their primary, secondary or tertiary nitrogen. Unmodified primary nitrogen amino groups are V or Z units, unmodified secondary nitrogen amino groups are W units or Y 'units, and unmodified tertiary nitrogen amino groups are Y units for the purposes of the present invention.

Modified primary amino groups are defined as V-terminating units and have one of three forms:

(a) units substituted by the same substituent shall have the general structure:

R — N — R—

AND

R '

(b) quaternized units shall have the general structure:

R 'xR ¹ —N — R—

AND

R 'wherein X is a suitable counter ion providing charge balance; and

(c) oxidized units having the general structure:

O f

R <-N-R—

AND

R ’

Modified secondary amino groups are defined as W "skeleton" units and have one of three forms:

(a) units substituted by the same substituent shall have the general structure:

-N-R—

AND

R ’i

(b) quaternized units shall have the general structure:

R’x —- N-R—

AND

R 'wherein X is a suitable counter ion providing charge balance; and

(c) the oxidized units shall have the general structure:

O f

—N-R—

AND

R '

Other modified secondary amino groups are defined as Y 'units and have one of three forms:

(a) units substituted by the same substituent shall have the general structure:

-N-R—

AND

R

(b) quaternized units shall have the general structure:

R 'χ — N-R—

I R wherein X is a suitable counter ion providing charge balance; and

(c) the oxidized units shall have the general structure:

O f —N-R—

AND

R

Modified tertiary amino groups are defined as Y "branched" units and have one of three forms:

(a) the unmodified units shall have the general structure:

—N-R—

AND

(b) quartemised units shall have the general structure:

R’x '—N-R— t

wherein X is a suitable counter ion providing charge balance; and

(c) the oxidized units shall have the general structure:

O f

—N-R—

Some modified primary amino groups are defined as Z 'terminating' units and have one of three forms:

(a) units substituted by the same substituent shall have the general structure:

-N-R ’

AND

R '

AND

(b) quaternized units shall have the general structure:

R’χ-N-R '

AND

R '

«

wherein X is a suitable counter ion providing charge balance; and

(c) the oxidized units shall have the general structure:

—N — R '

R ’

When any position on the nitrogen is unsubstituted or unmodified, it is meant that the hydrogen will be substituted for R '. For example, the primary amine unit comprising one R 'unit in the form of a hydroxyethyl group is a V terminating unit having the general formula (HOCH ₂ CH ₂ ) H N -.

For the purposes of the present invention there are two types of chain terminating units, V and Z units. The "terminating" unit is derived from the terminating primary amino group having the structure -NH ₂ . The non-cyclic polyamine backbones of the present invention comprise only one Z unit, while the cyclic polyamines need not include any Z units. The Z "terminating" unit may be substituted with any of the R 'units described below in this invention, except for the Z unit modified in the form of the N-oxide. In the case where the Z unit of the nitrogen is oxidized to the N-oxide, the nitrogen must be modified and thus R 'cannot be hydrogen.

The polyamines of the present invention include a skeleton of R "linking" units that serve to join nitrogen atoms to the skeleton. R units include units that for the purposes of the present invention are referred to as "hydrocarbyl R" units and "oxy R" units. "Hydrocarbyl" R units are C 2 to C 12 alkylene, C 4 to C 12 alkenylene, C 3 to C 12 hydroxyalkylene, wherein the hydroxyl group can occupy a position on the R unit of the chain, in addition to the carbon atoms directly linked to the polyamine nitrogen skeleton; C4 to C12 dihydroxyalkylene wherein the hydroxyl groups can occupy any two carbon atoms of the R unit of the chain, in addition to the carbon atoms directly linked to the polyamine backbone of the nitrogen; C8 to C12 dialkylarylene which for the purposes of the present invention are arylene groups having two alkyl substituted groups as part of the linker chain. For example, a dialkylarylene unit has the general formula (CH ₂ ) ₂ ch ₂ - or (CH ₂ ) ₄ (ch ₂ ) ₂ although the unit may not be 1,4-substituted, but may also be 1,2 or 1,3 substituted by C2 to C2. C12 alkylene, more preferably ethylene, 1,2-propylene and mixtures thereof, more preferably ethylene. "Oxy" R units include - (R ¹⁰ ) x R ⁵ (OR ¹ ) x -, (CH ₂ CH (OR ² ) CH ² O) z (R ¹⁰ ) y R ¹ (OCH ² CH (OR ² ) CH 2) _w -, -CH ₂ CH (OR ² ) CH ² -, - (R'O) xR'-, and mixtures thereof. Suitable R units are selected from the group consisting of C 2 to C 12 alkylene, C 3 to C 12 hydroxyalkylene, C 4 to C 12 dihydroxyalkylene, C 8 to C 12 dialkylarylene, - (R 6xR ¹ -, -CH ² CH (OR ² ) CH ² -, - (CH ² CH (OH) ) CH2O) z (R ¹ O) yR ¹ (OCH2CH- (OH) CH2) _w -, - (R ^I O) ^{xR5 (OR1)} x-, more preferable R units are C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, - (R ¹ jxr -, - (R ^ RR ^OR1), -, - (CH2CH (OH) CH2O) z ^(R! O) ^y! (OCH2CH- (OH) CH ₂ ) _w - and mixtures thereof, even more preferred R units are C 2 to C 12 alkylene, C 3 hydroxyalkylene and mixtures thereof, most preferably C 2 to C 6 alkylene The most suitable skeletons of the present invention include at least 50% R units that are ethylene.

The R ¹ units are C 2 -C 6 alkylene and mixtures thereof, more preferably ethylene.

R ² is hydrogen and - (R * O) _X B, more preferably hydrogen.

R ³ is C 1 to C 8 alkyl, C 7 to C 12 arylalkylene, C 7 to C 12 alkyl substituted aryl, C 6 to C 12 aryl and mixtures thereof, more preferably C 1 to C 12 alkyl, C 7 to C 12 arylalkylene, more preferably C 1 to C 12 alkyl, most preferably methyl. The R ³ units serve as part of the R 'units described below in the present invention.

R ⁴ is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 8 -C 12 arylalkylene, C 6 -C 10 arylene, more 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 ¹⁰ ) y R ¹⁰ OCH ₂ CH (OH) CH ₂ -, -C (O) (R ⁴ ) r C (O -, -CH ₂ CH (OH) CH ₂ -, R ⁵ is more preferably ethylene, -C (O) -, -C (O ¹ NH ⁶ NHC (O) -, -R 2 OR ¹ ) -, -CH ₂ CH (OH) CH ₂ -, -CH ₂ CH ₂ OH 1 CH ₂ O 2 O 4 OCH ₂ CH-COH ₃ CH ₂ -, more preferably -CH ₂ CH (OH) CH ₂ -.

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

Suitable "oxy" R units are further defined in terms of R ¹ , R ² and R ⁵ units. Suitable "oxy" R units include suitable R ¹ , R ² and R ⁵ units. Suitable cotton soil release agents of the present invention include at least 50% of the R ¹ units that are ethylene. Suitable R ¹ , R ² and R ⁵ units are combined with "oxy" R units to form suitable "oxy" R units in the present invention.

i) Substitution of more suitable R ⁵ in - (CH ₂ CH ₂ O) _X R ⁵ (OCH ₂ CH ₂ ) _X - provides

- (CH ₂ CH ₂ O) _x CH ₂ CHOHCH ₂ (OCH ₂ CH ₂ ) _x -.

ii) substitution of more suitable R ¹ and R ² - (CH2CH ^(OR2) CH2O) _z - (R ¹ O) y R ^I O (CH2 CH ^(OR2) _{CH2) w} - Provides - (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) Substitution of a more suitable R ² in -CH ₂ CH (OR ² ) CH ² - provides -CH ₂ CH (OH) CH ₂ -.

R 1 units are selected from the group consisting of hydrogen, C 1 to C 22 alkyl, C 3 to C 22 alkenyl, C 7 to C 22 arylalkyl, C 2 to C 22 hydroxylalkyl, - (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 ¹⁰ ) _m B, -C (O) R ³ , more preferably hydrogen, C 2 to C 22 hydroxyalkylene, benzyl, Cl to C22 alkylene, - (R * O) mB, -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 Cl-C22 alkylene, - (R JJB, -C (O) R ^3, - (CH2) pCO2 - (CH2) qSO3M, -CH (CH2CO2M) CO2M, most preferably Cl-C22 alkylene, - (ROjmB and - C (O) ^R3. When no nitrogen is formed to no modification or substitution then hydrogen atom will remain as the moiety representing R '. Most appropriate R' unit is (R * O) xB.

R 'units do not include a hydrogen atom when the V, W or Z units are oxidized such that the nitrogen is N-oxides. For example, a chain skeleton or branched chain does not include units of the following general structures:

O — N — R I H or

O f

H-n-R

I H

Additionally, R 'units do not include carbonyl groups directly linked to the nitrogen atom when the V, W or Z units are oxidized such that the nitrogen is N-oxides. According to the present invention, the R 'unit of the -C (O) R ³ group is not linked to the modified N-oxide nitrogen so that there are no N-oxide amides having the general structure

O f O - N - C - R 3

AND

R ’

O or R or NR is _{not O}

C = OR ¹

R3 or a combination thereof.

B is hydrogen, C1 to C6 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, more 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) _CH2 SO3 M, more preferably hydrogen or - (CH _{2) q} SO ₃ M.

M is hydrogen or a water-soluble cation in sufficient quantity to satisfy the charge balance. For example, the sodium cation also complies with the - (CH ₂ ) pCO ₂ M and - (CH ₂ ) pCbM, resulting in - (CH 2) _p CO ₂ Na and - (CH ₂ ) _q SO ₃ Na groups. More than one monovalent cation (sodium, potassium etc.) can be combined to meet the chemical equilibrium charge requirements, however, more than one anionic group can be equilibrated by a divalent cation, or more than one monovalent cation may be necessary to meet the charge requirements of a poly-anionic radical. (CH ₂ ) pPO ₃ M, a group substituted with a sodium atom has the general formula - (CH ₂ ) _p PO ₃ Na ₃ Divalent cations such as calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ) may be substituted or combined with other suitable monovalent moieties. Suitable cations are sodium and potassium, more preferably sodium.

X is a water-soluble anion such as chloride (CP), bromide (Br ') and iodide (Γ) or X may be some negatively charged radical such as sulfate (SC ^ ² ') and methosulfate (CH3SO3 ').

The indices of the formula have the following values: p has a value of 1 to 6, q has a value of 0 to 6; r is 0 or 1; w is 0 or 1, x is from 1 to 100; y is from 0 to 100; z is 0 or 1; m has a value from 2 to 700, more preferably from 4 to 400, n has a value from 0 to 350, more preferably from 0 to 200; m + n has a value of at least 5.

Suitably, x has a value ranging from 1 to 20, more preferably from 1 to 10.

Suitable amino-functional polymers of the present invention include polyamine backbones wherein less than 50% of the R groups comprise "oxy" R units, more preferably less than 20%, more preferably less than 5%, most preferably the R units do not include any "oxy" R units.

Most suitable amino-functional polymers that do not include any "oxy" R units include polyamine backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene and 1,3-propylene include 3 or fewer carbon atoms and suitable "hydrocarbyl" R units. Furthermore, when the scaffold R units are C 2 to C 12 alkylene, C 2 to C 3 alkylene is suitable, most preferably ethylene.

The amino-functional polymers of the present invention include modified homogeneous and inhomogeneous polyamine backbones wherein 100% or less of the -NH units are modified. For the purposes of the present invention, the term "homogeneous polyamine backbone" is defined as a polyamine backbone having R units that are the same (ie, all ethylene). However, this monotonicity of the definition does not exclude polyamines that include other outer units in the polymer backbone that are present as artifacts of a selected chemical synthesis method.

9 9 99 9

For example, it is known to trained chemists that ethanolamine can be used as an "initiator" in polyethyleneimine synthesis, thus a polyethyleneimine sample, contains one hydroxyethyl group derived from polymerization, the "initiator" can be included in a homogeneous polyamine skeleton for the purposes of the present invention. The polyamine skeleton comprising all ethylene R units where there are no branched Y units present is a homogeneous skeleton. The polyamine skeleton comprising all ethylene R units is a homogeneous skeleton regardless of the degree of branching or the number of cyclic branches present.

For the purposes of the present invention, the term "non-homogeneous polymer backbone" means polyamine backbones that are a combination of different R unit lengths and R unit types. For example, the inhomogeneous skeleton comprises R units that are a mixture of ethylene and 1,2-propylene units. For the purposes of the present invention, a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-homogeneous skeleton.

Suitable amino-functional polymers of the present invention include homogeneous polyamine backbones which are wholly or partially substituted with polyethyleneoxy groups, wholly or partially quaternized with amine nitrogen, wholly or partially oxidized to N-oxides, and mixtures thereof. Although not all of the skeletal amine nitrogen must be modified in the same way, the choice of modification is left to the specific needs of the inventor. The degree of ethoxylation is also determined by the specific requirements of the inventor.

Suitable polyamines that include a skeleton of the compounds of the present invention are generally polyalkylenimines (PAI's), more preferably polyethyleneimines (PEI's) or PEI's linked by groups having longer R units than the parent PAI's or PEI's.

Suitable amines of polymer backbones include R units, which are C2 alkylene (ethylene) units, also known as polyethyleneimines (PEI's). Suitable PEI's have at least moderate branching and this is an m kn ratio of less than 4: 1, but PEI's having a m kn ratio of 2: 1 are most suitable. Suitable skeletons have the general formula before modification:

I [RWCH ₂ CH ₂ ] _n - [NCH ₂ CH ₂ ] _m - [NCH ₂ CH ₂ ] _n -NR ' ₂ where R', m and n are the same as defined above in the present invention. Suitable PEI's will have a molecular weight of greater than 200 daltons.

The relative proportions of the primary, secondary and tertiary amine units in the polyamine backbone, especially in the case of PEI's, will vary depending on the method of preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine backbone of the chain represents a potential site for subsequent substitution, quaternization, or oxidation.

4 · 4 · 4 · 4 · 4 · 44 · 44

4 * ··· ·· • 4 ** 44 4 · 4 · * • * 444444

4 4 4 44 44 444

These polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium metabisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine skeletons are described in U.S. Patent 2,182,306 to Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., Issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., Issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and US Patent 2,553,696, Wilson, issued May 21, 1951; all of these documents are incorporated by reference.

Examples of amino-functional polymers including PEI's are illustrated in Formulas I-IV:

Formula I depicts an amino-functional polymer comprising a PEI skeleton wherein all substitutable nitrogen is modified by replacing hydrogen with a polyoxyalkyleneoxy unit, - (CH ₂ CH ₂ O) H, having the formula I (H ₂ OCH ₃ CH ₃ ) fcN [H (O _1, CH ₃ )] ) H] ₂

(B (OCH ₂ CH ₂ ) 1 N (CH ₂ CH ₃ ) h

H] 1 (CH, CH ₂ O) hk (NRCH ₃ CH ₂ O) H ₁₂ (I)

This is an example of an amino-functional polymer that is completely modified by one type of group.

Formula II depicts an amino-functional polymer comprising a PEI skeleton wherein all substitutable primary amine nitrogens are modified by replacing hydrogen with a polyoxyalkylenoxy unit, - (CH ₂ CH ₂ O) ₂ H, then the molecule is modified by subsequent oxidation of all oxidizable primary and secondary nitrogen to N oxides, said polymer having the general formula II

O | _— _

N [(CH, CH, O}, H] ₂ ] ' ^Z Q

O (CH, CH, O) ₂ H ¹⁰ O '

FKOCHjCHjJj

O f [H1OCHjCHjhhN o

[H (OCH ₂ CH 2) 2], N.

(HíOCHjCHjhhN

O (CH ₂ CH ₂ O) ₂ H

NRCH3CH3O4H3i

CXCH ₂ CH ₂ O) gi

Nf (CH, CH ₂ O) ₂ H] ₂

OfCHjCHjOLH

O ♦ N [(CH ₂ CH ₂ O), H], ^O ^ yKCHxCH ₃ OH ₁ H 3 O (II)

Formula III illustrates an amino-functional polymer comprising a PEI scaffold wherein all the scaffold hydrogen atoms are substituted and some scaffold amine units are quaternized. The substituents are polyoxyalkenoxy units, - (CH 2 CH 2 O) 7 H or methyl groups. The modified PEI has the general formula III

CH ₃ CH ₃

ROCH2CH3CHN [H2OCH3CH3N]

CH ₂ x x 2 (CH ₂ CH ₂ OH)

with (H 2 OCH 3 CH 3 HN 3)

CHj. CHj

CP i

CHj ₊ cr _n ^ \ ^ n (chj ₃ (III))

Formula IV illustrates an amino-functional polymer comprising a PEI scaffold, wherein the scaffold nitrogen is modified by substitution (i.e., - (ΟΙΕΟ-ΕΟ ^ Η or methyl), quaternization, oxidation to N-oxides or combinations thereof. H (OCH ₂ CH ₂ hJ ₂ N [H (OCH ₂ CH ₂ >, J ₂ N)

CH;

N (CH-> CH ₂ O) ₃ H o CH ₃

N (CH, CH, O) ₃ H. ⁺ cr

[H (OCH, CH ₂ ) ₃ }, N '3 ₊ cr

CHj (IV)

In the above examples, not all of the nitrogens of the same group include the same modifications. The present invention allows the inventor to prepare a portion of the secondary amine nitrogen ethoxylated while other secondary nitrogen amine groups are oxidized to the Noxides. This also applies to primary nitrogen amines in which the inventor can select for modification all or part of the primary nitrogen amines with one or more substituents prior to oxidation or quaternization. Selected combinations of R 'groups may be substituted on primary and secondary nitrogen amines, in addition to the limitations described hereinabove.

Commercially available amino-functional polymers suitable for use in the present invention are poly (ethyleneimine) with MW 1200, hydroxyethylated poly (ethyleneimine) from Polysciences, with MW 2000 and 80% hydroxyethylated poly (ethyleneimine) from Aldrich.

A typical amount of the amino-functional polymer used in the composition of the invention when used as exclusively nitrogen-containing compounds is greater than 1%, more preferably at most 50% by weight, more preferably from greater than 1% to 25% by weight and most preferably greater than 1% up to 10% active ingredient by weight of the composition.

Dye fixing agent

Dye fixing agents or "fixing agents" are well known, commercially available materials that are designed to improve the appearance of dyed fabrics by minimizing dye loss from fabrics as a result of washing. Components that are plasticizer materials or that are described herein as amino-functional polymers are not included in this definition.

Many dye fixing agents are cationic and are based on various quaternized or otherwise cationically charged nitrogenous organic compounds. Cationic fixatives

are available under different trade names from several suppliers. Representative examples include: Cartafix CB from Clariant, CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) from Crosfield; INDOSOL E-50 (February 27, 1984, Ref. No. 60,083,584; polyethylene amine based) from Sandoz; SANDOFIX TPS, which is also available from Sandoz and is a suitable polycationic fixative for use in the present invention and SANDOFIX SWE (cationic resin compound), REWIN SRF-0 and REWIN DWR from CHT-Beitlich GMBH, Tinofix® ECO, Tinofix® FRD and Solfin® available from Ciba-Geigy.

Other cationic dye fixing agents are described in &quot; After treatments for improving the fastness of dyes on textile fibers &quot; by Christopher C. Cook (REV. PROG. COLORATION Vol. 12, 1982). Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid diamine condensates such as hydrogen chloride, acetate, methosulfate and benzyl hydrochloride oleyldiethyl aminoethylamide, oleylmethyldiethylenediamine methosulfate, monostearyl ethylene diaminotrimethylammonium methosulfate and oxidized tertiary amine products; polymeric alkyldiamine derivatives, polyamine cyanuride chloride condensates, and aminated glycerol dichlorohydrins.

Suitable dye fixing agents are dye fixing agents by reaction with cellulose.

By "dye fixing agent by reaction with cellulose", it is meant that the agent reacts with cellulose fibers under hot cleaning. Reagents suitable for use in the present invention may be defined by the following test procedure, called the Cellulose Reactivity Measurement Test.

Cellulose reactivity test

Two portions of red fabric (e.g., 10 x 10 cm knitted cotton pieces stained with Direct Red 80) are soaked for 20 minutes in an aqueous solution of 1% (w / w) of the candidate for cellulose-reactive dye fixing agent. The pH of the solution is that obtained at this concentration.

The bandage is then dried. One of the dried bandages, as well as the non-soaked bandage (control 1), is passed 10 times through the ironing mandrel set to the ironing temperature of the linen fabric.

Control Bandage 2 is also used in this measurement test, which is a non-wetted and non-iron bandage.

the bandages are washed separately in washing machines under typical conditions with a commercial detergent used at the recommended dose for 1/2 hour at 60 ° C, followed by 4 rinses with 200 ml cold water and then directly dried.

Washing stability is then measured on the bandages by determining their so-called delta-E value against a new, unclean bandage. Delta-E values are defined, for example, in ASTM D2244.

’* · · · ♦ · + ♦

Delta E is the calculated color difference as described in ASTM D2244, ie the magnitude and vector between two psychophysical color stimuli defined by triple pulse values or color coordinates and luminance factor, calculated using a specific set of color difference equations defined in CIE 1976 CIELAB v the opposite color spot, the Hunter opposite color spot, the Friele-Mac Adam-Chickering color spot, or some equivalent color spot.

The lower the delta E is obtained, the better the wash stability of the formulation.

If the color fastness of the ironed and soaked bandage is better than the non-ironed soaked bandages and also better than control 1 and 2, then the dye-fixing agent and the cellulose-reactive agent are suitable for the purpose of the invention.

Typical dye fixing agents by reaction with cellulose are products containing a reactive group of reactive dye classes selected from halo-triazine products, vinyl sulfone compounds, epichlorohydrin derivatives, hydroxyethylene urea derivatives, condensation products of formaldehyde, polycarboxylates, glyoxal and glutaraldehyde derivatives, and mixtures thereof.

Other functional reactions for cellulose can be found in Textile processing and properties. Elsevier (1997) of Tyrone L. Vigo on pages 120 to 121 allows the use of specific electrophilic groups with affinity for cellulose.

Suitable hydroxyethylene urea derivatives include dimethyloldihydroxy ethylene, urea and dimethyl glyoxal urea.

Suitable formaldehyde condensation products include formaldehyde-derived condensation products and groups selected from amino, imino, phenol, urea, cyanamide, and aromatic groups. Commercially available compounds common to this class are Sandofix WE 56 from Clariant, Zetex E from Zeneca and Levogen BF from Bayer.

Suitable polycarboxylate derivatives include butanetetracarboxylic acid derivatives, citric acid derivatives, polyacrylates and derivatives thereof.

The most suitable dye fixing agents by reaction with cellulose is one of a class of hydroxyethylene urea derivatives commercially available under the tradename Indosol CR from Clariant. Still other most suitable dye fixing agents by reaction with cellulose are commercially available under the trade names Rewin DWR and Rewin WBS from CE1T R. Beitlich.

Co-discovered dye fixing agents, suitable agents for use in the present invention are cationic, especially polycationic dye fixing agents.

A typical amount of dye fixing agent used in the composition of the invention is more preferably from 1% to 50% by weight, more preferably from 1% to 25% by weight, most preferably from 1.5% to 10% by weight of the composition.

• 4 ····

When both dye fixing agent and polyamino functional polymer are used, the total amount of these components is typically at most 90% by weight, more preferably at most 50% by weight, more preferably from 1% to 25% by weight, most preferably from 1% to 10%. % of active substance by weight of the mixture.

Water-soluble cationic surfactant.

By "water-soluble humectant", it is meant that the humectant comprises substantially pure, isotropic solutions when 0.2 weight percent is dissolved in water at 25 ° C.

Any type of water-soluble cationic surfactant can be used to provide coating reducing properties. Although some water-soluble cationic surfactants and mixtures thereof are preferable. Therefore, it is preferred that the cationic detergent be an active molecule, on a surface with a linear or branched hydrophobic end and a positively charged hydrophilic head group, more preferably a cationic detergent, and for use in the present invention it is a quaternary ammonium salt of the formula:

[R'N ⁺ R3] X · wherein R ¹ is a C 10 to C 22 hydrocarbon group, more preferably a C 12 to C 18 alkyl group or a corresponding ester linkage interrupted by a short alkylene (C 1 -C 4) group between an ester linkage and N having a similar hydrocarbon group, e.g. a choline fatty acid ester, more preferably a C12 to C14 (coco) choline ester and / or a C16 to C18 tallow choline ester. The hydrocarbon group may be interrupted by other groups such as COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO. Each R is C 1 to C 4 alkyl or substituted (for example, hydroxy) alkyl or hydrogen, more preferably methyl and the opposite ion X ', ie, a compatible anion, for example, chloride, bromide, methyl, which softens the surface, etc.

The long chain R1 group, a long single chain detergent, typically comprises an alkylene group having from 10 to 22 carbon atoms, more preferably from 12 to about 16 carbon atoms, more preferably from 12 to 18 carbon atoms. This R1 group may be attached to a cationic nitrogen atom through a group containing one or more esters, amides, ethers, amines, etc., more preferably via an ester linker, which may be desirable to increase hydrophilicity, biodegradability etc. Such linking groups are more preferably a range of about three carbon atoms and a nitrogen atom. A suitable cationic detergent of this type is N, N-dimethyl-N- (2-hydroxyethyl) -N-dodecyl / tetradecyl ammonium bromide.

When the corresponding non-quaternary amines are used, any acid (preferably a mineral or polycarboxylic acid) that is added to maintain stable ester groups will also stabilize the protonated amine in the compositions.

Typically described such cationic detergents suitable for use in the present invention are choline ester detergents of the general formula:

• 99 · · · · · · · · · · · · · · · · · · · · · · · · · · ·

r n r ₂ 0- * 5 (CH) _n O Jb i ₊ h- (X) _u - (CH ₂ ) _m - (¥) - (CH 2 -N-R 3 M) - - and

R ₄ wherein R 1 is C 10 to C 22 linear or branched alkyl, alkenyl or alkaryl chain or M. N ⁺ (R ₆ R ₇ R ₈ ) (CH ₂ ) _s ; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH, and NHCOO, wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R ₂ , R 3, R ₄ , R 6, R 7 and R 8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl and hydroxyalkenyl groups having from 1 to 4 carbon atoms and alkaryl groups; and R5 is independently H or C1 to C3 alkyl; wherein the values of m, n, sat independently lie in the range of 0 to 8, the value of b lies in the range of 0 to 20 and the values of a, u and v are each independently 0 or 1 with the proviso that at least one of ; and wherein M is the opposite anion.

More preferably, M is selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, more preferably methyl sulfate, chloride, bromide or iodide. Very suitable water-soluble choline ester detergents are esters having the general formula:

O CHo

II L

R ₁ - CO - (CH ₂ ) _m -N ⁺ - CH ₃ (Jh ₃

M 'wherein m is from 1 to 4, more preferably 2 or 3, and wherein R 1 is C 1 to C 19 linear or branched alkyl chain.

Particularly suitable choline esters of this type include stearoyl choline ester quaternary methylammonium halides (R ¹ = C 17 alkyl), palmitoyl choline ester quaternary methylammonium halides (R ¹ = C 15 alkyl), myristoyl choline ester quaternary

• ·· 99 99 · ♦ 9 · • • • 9 9 9 • · · 9 * 9 · • 999 • · • • • · · 9 9 «· • · • · 999 99 fc · ·· ·· ·

methylammonium halides ^(R1 = C13 alkyl), lauroyl choline ester quaternary methylammonium halides (R ¹ = C 1 alkyl), cocoyl choline ester quaternary methylammonium halides (R ¹ = CII to CL3 alkyl), tallowyl choline ester quaternary methylammonium (R ¹ = (C1-C17 alkyl) and mixtures thereof.

Particularly preferred choline esters of this type are selected from myristoyl choline ester of quaternary methylammonium halides, lauroyl choline ester of methylammonium halides, cocoyl choline ester of quaternary methylammonium halides, and mixtures thereof.

Particularly suitable choline esters mentioned above can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol in the presence of an acid catalyst. The reaction product is then quaternized with methyl halide, more preferably in the presence of a solvent such as ethanol, water, propylene glycol, or more preferably a fatty alcohol ethoxylate such as a C10 to C18 fatty alcohol ethoxylate having an ethoxylation degree of from 3 to 50 ethoxy groups per mole forming the desired cationic. substance. They can also be prepared by direct esterification of a higher fatty acid of the desired chain length together with 2-halo-ethanol in the presence of an acidic catalyst. The reaction product is then quaternized with trimethylamine, forming the desired cationic substance.

Polyoxyalkylene alkyl amine surfactant

The polyoxyalkylene alkyl amine surfactant is also another essential component of the present composition. In fact, through this component, the formation of the coating is reduced or even prevented.

More preferably, polyoxyalkylene alkyl amine nonionic detergents suitable for use in the present invention have the general formula:

R - A, - N - [(R'O) _x (R ² O) y R ³ ] m (R ⁴ ) n wherein R is selected from C 7 to C 21 linear alkyl, C 7 to C 21 branched alkyl, C 7 to C 21 linear alkenyl, C7 to C21 branched alkenyl, and mixtures thereof. The nonionic detergents of the present invention are derived from synthetic or naturally occurring raw materials, more preferably naturally occurring raw materials, therefore, said nonionic detergents include acyl units having the general formula:

O

II

R — C

wherein said acyl unit is derived from a triglyceride source selected from the group consisting of tallow, partially hydrogenated tallow, lard, coconut oil, partially hydrogenated coconut oil, palm kernel oil, hydrogenated palm kernel oil, canola oil, partially hydrogenated canola oil, safflower oil, partially hydrogenated safflower oil, peanut oil, partly hydrogenated peanut oil, sunflower oil, partly hydrogenated sunflower oil, corn oil, partly hydrogenated corn oil, soybean oil, partly hydrogenated soybean oil, tall oil, partly hydrogenated tall oil , rice bran oil, partially hydrogenated rice bran oil and mixtures thereof. Other suitable triglyceride sources for the acyl unit are synthetic triglyceride raw materials, for example, triglycerides that are prepared by a chemical reaction or rarely by another process derived from a natural source. Suitable raw materials for said acyl units are tallow, partially hydrogenated tallow, coconut oil, partially hydrogenated coconut oil, canola oil, partially hydrogenated canola oil, synthetic triglycerides and mixtures thereof. A suitable source of triglycerides is tri-oleyl triglycerides.

R ¹ is ethylene; R ² is selected from C 3 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; More preferably, R ² is 1,2-propylene. Non-cationic detergents that comprise a mixture of R ¹ and R ² units, more preferably comprise from about 4 to 12 ethylene units in combination with about 1 to 4 1,2-propylene units. The units may be alternated or grouped together in any combination suitable for the inventor. More preferably, the ratio of R units to R units is from about 4: 1 to 8: 1. More preferably, the R ² units (e.g., 1,2-propylene) are attached to a nitrogen atom followed by balancing a chain comprising from 4 to 8 ethylene units.

R ³ is selected from hydrogen, C 1 to C 4 linear alkyl, C 3 to C 4 branched alkyl, and mixtures thereof; more preferably hydrogen or methyl, more preferably hydrogen.

R ⁴ is selected from hydrogen, C 1 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; more preferably hydrogen. When the index m is 2, the index n must be equal to 0 and the R ⁴ unit is absent and is instead replaced by the - [(R ¹⁰ ) x (R ²⁰ ) y R ³ ] generic unit.

A is (R 5) | (R ¹⁰ ) _x (R ²⁰ ) _y R ³

R ⁵ is selected from - [(R'O) x (R ²⁰ ) yJ unit, C 1 -C 16 linear alkyl, C 1 -C 16 branched alkyl, C 1 -C 16 linear alkenyl, C 1 -C 16 branched alkenyl, and mixtures thereof, more preferably is selected from C3 linear alkyl, C3 branched alkyl, C3 linear alkenyl, C3 branched alkenyl, and mixtures thereof.

Index m is 1 or 2, index n is 0 or 1, such that when m is 1, n is 1; and when m is 2, n is 0; preferably m is equal to 2 and n is equal to 0, resulting in two - [(R ¹ O) x (R ² O) y R ³⁾ R ^4, and units will be missed. The index x is from 0 to about 50, more preferably from about 1 to 25, more preferably from about 3 to 10. The index y is from 0 to about 10, more preferably 0, though, when the index y is not equal to 0, y is from 1 to about Preferably, all alkyleneoxy units are ethyleneoxy units. Those trained in the field of ethoxylated polyalkylene alkylamine surfactants will recognize that the values for the indexes x and y are average values and the true values may exceed the value several times depending on the amine alkoxylate process used.

Index q is 0 or 1.

Polyoxyalkylene alkylamines are available under various trade names from several suppliers. Representative examples include: Ethomeen, Ethoduomeen from Akzo Chemicals and / or Secomine from Stepan.

Polyoxyalkylene alkylamine surfactants are typically present in amounts of from 0.001% to 20% by weight, more preferably from 0.5% to 12% by weight, more preferably from 1% to 8% by weight of the composition.

More preferred coating reducing agents described herein are water-soluble cationic surfactants.

To further improve the performance of the coating reducing agent, it has been found desirable that the coating reducing agent have a weight ratio of coating reducing agent to dye fixing agent of from 0.05: 1 to 5: 1, more preferably from 0.1: 1 to 2.5: 1, most preferably from 0.5: 1 to 1: 1.

When a mixture of a polyaminofunctional polymer and a coating fixative is used, it is desirable that the coating reduction composition have a ratio of the weight of the coating reducing agent to the total amount of polyaminofunctional polymer and dye fixing agents from 0.05: 1 to 2: 1, more preferably 0, 1: 1 to 1: 1.

In addition to the coating reducing agents described above, it has been found that the use of a water-insoluble cationic surfactant commonly known as a fabric softening compound also provides the necessary coating reduction.

Fabric softening compound

Typical amounts included in the fabric softening compound in the composition are from 1% to 80%, more preferably from 5% to 75%, more preferably from 15% to 70% and even more preferably from 19% to 65% by weight of the composition.

Typical cationic softening components are quaternary ammonium compounds or amine precursors thereof, as defined below in the present invention.

A) Quaternary ammonium active fabric softening compound (1) Suitable quaternary ammonium active fabric softening compounds have the general formula:

+

N - (CH ₂ ) _n -Q-R 1 • m.

or general formula:

when Q is a carbones 1 unit having the general formula:

(2)

O

II —-o — c — o—

R 2 O r 2

Each R unit is independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl and mixtures thereof, more preferably methyl or hydroxyalkyl; each R ¹ unit is independently linear or branched C 1 -C 22 alkyl, linear or branched C 1 -C 22 alkenyl and mixtures thereof, R is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and mixtures thereof; X is an anion which is compatible with the fabric softening active ingredients and added ingredients; the index m is from 1 to 4, more preferably 2; the index n is from 1 to 4, more preferably 2.

An example of a suitable fabric softening active ingredient is a mixture of quaternized amines having the general formula:

X R · · 99 99 · 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 99 methyl; R ¹ is a linear or branched alkyl or alkenyl chain comprising at least 11 atoms, more preferably at least 15 atoms. In the above examples of fabric softening agents, the -O2CR ¹ unit represents an acyl fatty acid that is typically derived from a triglyceride source. The triglyceride source is more preferably derived from tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and / or partially hydrogenated vegetable oils such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil bean, tall oil, rice bran oil, etc., and mixtures thereof.

More preferred active softening agents of the present invention are diester and / or quaternary ammonium compound diester (DEQA), diesters and diamides having the general formula:

+

N - (CH 3 -n-Q-RI)

X 'wherein R, R ¹ , Xan are the same as defined above in the present invention for formulas (1) and (2) and Q has the formula:

These suitable fabric softening active ingredients are formed by reacting an amine with an acyl fatty acid to form an amine intermediate having the general formula:

wherein R more preferably methyl, Q and R ¹ are those defined above in the present invention; followed by quaternization to form the final fabric softening active agent.

Non-limiting examples of suitable amines that are used to form the DEQA fabric softener active of the present invention include methyl bis (2-hydroxyethyl) amine of the formula:

methyl bis (2-hydroxypropyl) amine having the general formula:

methyl (3-aminopropyl) (2-hydroxyethyl) amine having the general formula:

methyl bis (2-aminoethyl) amine having the general formula:

triethanolamine having the general formula:

di (2-aminoethyl) ethanolamine having the general formula:

The opposite ion X uvedený above may be any compatible anion, more preferably the strong acid anion, for example chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, nitrate and the like, more preferably chloride or methyl sulfate. The anion can also, but less suitably, carry a double charge, and in this case, X ^(_) represents a half group.

• · · ·

Tallow and canola oil are suitable and not very expensive sources of fatty acid acyls that are suitable for use in the present invention as R ¹ units. The following are non-limiting examples of quaternary ammonium compounds suitable for use in the composition of the present invention. The term "tallowyl" as used herein means an R ¹ unit derived from a tallow triglyceride source and is a mixture of fatty acyl units. Similarly, the term canoyl means a mixture of fatty acyl units derived from oil canola.

Table II

Active fabric softening agents

N, N-di (tallowyloxy-ethyl) -N, N-dimethyl ammonium chloride;

N, N-di (canolyl-oxy-ethyl) -N, N-dimethyl ammonium chloride;

N, N-di (tallowyloxy-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride;

N, N-di (canolyl-oxy-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride;

N, N-di (2-tallowyloxy-2-oxo-ethyl) -N, N-dimethyl ammonium chloride;

N, N-di (2-canolyloxy-2-oxo-ethyl) -N, N-dimethyl ammonium chloride;

N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N-dimethyl ammonium chloride;

N, N-di (2-canolyloxyethylcarbonyloxyethyl) -N, N-dimethyl ammonium chloride; N- (2-tallowyloxy-2-ethyl) -N- (2-tallowyloxy-2-oxo-ethyl) -N, N-dimethyl ammonium chloride;

N- (2-canolyloxy-2-ethyl) -N- (2-canolyloxy-2-oxo-ethyl) -N, N-dimethyl ammonium chloride; N, N, N-tri (tallowyloxy-ethyl) -N-methyl ammonium chloride;

N, N, N-tri (canolyl-oxy-ethyl) -N-methyl ammonium chloride;

N- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl) -N, N-dimethyl ammonium chloride;

N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N, N-dimethyl ammonium chloride;

1,2-ditallowyloxy-3-N, N, N-trimethylamoniopropane chloride;

1,2-canolyloxy-3-N, N, N-trimethylammonium propane chloride;

and mixtures of the above active ingredients.

Other examples of quaternary ammonium softening compounds are methylbis (tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate and methylbis (hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methylsulfate; these materials are available from Witco Chemical Company under the trade names Varisoft® 222 and Varisoft® 110, respectively.

Particularly suitable is N, N-di (tallowyloxy-ethyl) -N, N-dimethyl ammonium chloride, wherein the tallow chains are at least partially unsaturated.

The level of unsaturation contained in tallow, canola, or other fatty acyl units of the chain can be measured by the iodine value corresponding to the fatty acid that would be present. More preferably, in the present case, it should be in the range of 5 to 100, by providing a category of compounds that are significant having an iodine value of less than or greater than 25.

Indeed, for a compound having the general formula:

X 'derived from tallow fatty acids, when the iodine value is from 5 to 25, more preferably from 15 to 20, the weight ratio of the cis / trans isomer has been found to be greater than about 30/70, more preferably greater than about 50/50, and more preferably than about 70/30, provides optimum concentration.

Compounds of this type made from tallow fatty acids having an iodine value greater than 25 have been found to be less critical in the cis-to-trans-form ratio if very high concentrations are needed.

Other suitable examples of fabric softening active ingredients are derived from fatty acyl groups wherein the terms "tallowyl" and "canolyl" in the above examples are replaced by the terms "cocoyl, palmoyl, lauryl, oleyl, ricinoleyl, stearyl, palmityl" corresponding to triglyceride sources. from which the acyl units are derived. These alternative fatty acid sources may include either fully saturated or more preferably at least partially unsaturated chains.

As described above, the R units are more preferably methyl, although the fabric softening active ingredients are described above by replacing the term "methyl" in the above examples in Table II with the units "ethyl, ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t- butyl".

The opposite ion X, which is exemplified in Table II, may be more conveniently replaced by bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof. In fact, anion X is only present as the counter ion positively charged with the quaternary ammonium compound. The scope of the invention is not intended to limit any particular anion.

For the preceding esters of fabric softening agents, the pH of the compositions of the present invention is an interesting parameter of the present invention. Indeed, this affects the stability of the quaternary amines or amine precursor compounds, especially under extended storage conditions.

The pH as defined in the present context is measured in pure formulations at a temperature of 20 ° C. While these compounds are effective at a pH of less than about 6.0, they are optimal for optimum pH of 44.0. 4 · 4 the hydrolytic stability of these compositions has been a pure pH measured under the above conditions and must suitably be in the range of about 2.0 to 5, more preferably in the range of 2.5 to 4.5, more preferably in the range of about 2.5 to 3, 5. The pH of these compounds in the present invention can be controlled by the addition of Bronsted acid.

Examples of suitable acids include inorganic mineral acids, carboxylic acids, especially (C1 to C5) low molecular weight carboxylic acids and alkylsulfonic acids. Suitable inorganic acids include HCl, H2SO4, HNO3 and HPO4. Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acids. More preferred are citric acid, hydrochloric acid, phosphoric acid, formic acid, methylsulfonic acid and benzoic acid.

As used herein, when a diester is specified, it will also include a monoester that is normally present in the article. For softening, the remainder of the detergent should not be present and under washing conditions the percentage of monoester should be as low as possible, preferably no more than about 2.5%, although some monoesters are suitable due to detergents. Total ratios of diesters to monoesters are from about 100: 1 to 2: 1, more preferably from about 50: 1 to 5: 1, more preferably from about 13: 1 to 8: 1. Under the most suitable conditions, the di / mononester ratio is more preferably about 11: 1. The amount of monoesters present can be controlled in the manufacture of the softening compound.

Mixtures of the active formulas (1) and (2) can also be prepared.

2) Still other suitable quaternary fabric softening compounds for use in the present invention are cationic nitrogen salts having two carbon atoms or more of a long chain of acyclic aliphatic C8 to C22 hydrocarbon groups or one of said groups and an arylalkyl group which can be used either alone or as part of a mixture selected from the group consisting of:

(i) acyclic quaternary ammonium salts having the general formula:

+

AND'

wherein R ⁴ is an acyclic aliphatic C 8 -C 22 hydrocarbon group, R ⁵ is a C 1 -C 4 saturated alkyl or hydroxyalkyl group, R ⁸ is selected from the group consisting of R ⁴ and R ⁵ groups, and A is an anion as defined above;

(ii) a diaminoalkoxylated quaternary ammonium salt having the general formula:

About R5 o

II I II

R 1 -C-NH-R 2 -N-R 2 -NH-C-R (CH ₂ CH ₂ O) n H

And wherein n is from 1 to 5 and R1, R2, R5 and A are as defined above;

(iii) mixtures thereof.

Examples of the abovementioned classes of cationic nitrogen salts are the well-known dialkyldimethylammonium chloride, such as ditallowdimethylammonium chloride, ditallowdimethylammonium chloride, di (hydrogenated tallowimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride). in the present invention, di (hydrogenated tallowimethylammonium chloride (trademark Adogen® 442), ditallowdimethylammonium chloride (trademark Adogen® 470, Praepagen® 3445), distearyldimethylammonium chloride (trademark Arosurf® TA-100) are all available from Witco Chemical Company Dibehenyldimethylene. Chloride is sold under the trademark Kemamine Q-2802C by Humko Chemical Division of Witco Chemical Corporation. Van under the trade name Varisoft SDC by Witco Chemical Company and Ammonyx® 490 Onyx Chemical Company.

B) Amino active fabric softening compounds

Amino active fabric softening compounds suitable for use in the present invention, which may be in the form of an amine or in the form of a cation, are selected from:

(i) higher fatty acid reaction products with a co-amine selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines, and mixtures thereof. These reaction products are mixtures of several compounds in view of the many functional structures of polyamines.

A more preferred component (i) is a nitrogen compound selected from the group consisting of reaction product mixtures or some selected mixture components.

One suitable compound (i) is a compound selected from the group consisting of substituted imidazoline compounds having the general formula:

• »· · · · · · · · · · · · · · · · · · · · · · · · · · · ·

R8-NH-C — R?

II O

Wherein R is an acyclic aliphatic C1 to C21 hydrocarbon group and R is a bivalent C1 to C3 alkylene group.

Substances (i) are commercially available as: Mazamide® 6, sold by Mazer Chemical or Ceranine® HC, sold by Sandoz &Chemicals; stearic hydroxyethylimidazoline sold under the trade name Alkazine® ST Alkaril Chemicals, Inc. or Schercozoline® S Scher Chemicals, Inc .; N, N-ditallowalkoyldiethylenetriamine; 1-tallowamidoethyl-2-tallowimidazoline (wherein in the preceding structure R ^{1 is an} aliphatic C 15 to C ¹⁷ hydrocarbon group and R ⁸ is a bivalent ethylene group).

Some of the components (i) may also be first dispersed in a Bronsted acid to aid dispersion and having a pKa of not more than about 4, indicating that the pH of the resulting composition is not greater than about 6. Some suitable dispersing compounds are hydrochloric acid , phosphoric acid or methylsulfonic acid.

Both Ν, Ν '- ditallowalkoyldiethylenetriamine and l-tallow (amidoethyl) -2-tallowimidazole are reaction products of tallow fatty acids and diethylenetriamine and are precursors of fabric-softening cationic agents, which is methyl-1-thallowamidoethyl-2-tallowimidazolinium methylsulfate. "Cationic Surface Active Agents as Fabric Softeners" RR Egan, Journal of the American Oil Chemicals Society, January 1978, pages 118-121). Ν, Ν '- Ditallowalkoyldiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazole can be obtained from the Witco Company as an experimental chemical.

1-tallow (amidoethyl) -2-tallowimidazolinium methyl sulfate is sold by Witco Chemical Company under the trade name Varisoft® 475.

(ii) the emollients have the general formula:

r ‘

wherein each R ² is Cl to C6 alkylene group, preferably an ethylene group; and G is an oxygen atom

5 or an -NR- group; and each R, R, R and R has the definition above and A 'has the definition above for X'.

An example of compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride, wherein R ¹ is an acyclic aliphatic C 5 to C 17 hydrocarbon group, R is an ethylene group, G is an NH group, R ⁵ is a methyl group, and A is a chloride anion (iii) substances have the general formula:

2 @

where R, R ^! R ² and A 1 are as defined above.

An example of compound (iii) is a compound having the general formula:

• · · · · · · · · ·

2®

R ’

R ¹

wherein R ¹ is derived from oleic acid.

Additional fabric softening agents useful in the present invention are described in U.S. Patent No. 4,661,269, issued April 28, 1987 under the names Toan Trinh, Errol H. Wahl, Donald M. Swartley, and Ronald L. Hemingway; U.S. Patent No. 4,439,335, Bums, issued March 27, 1984; and in U.S. Patent Nos. 3,861,870 to Edwars and Diehl; 4,308,151, Cambre; 3,886,075, Bemardino; 4,233,164, Davis; 4,401,578, Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016 to Rudkin, Clint and Young; and European Patent Application Publication No. No. 472,178, Yamamura et al., All of said documents being incorporated herein by reference.

Of course, the term "active emollients" may include mixtures of active emollients.

A suitable number of classes of softening compounds described previously in this invention are diesters or diamido quaternary ammonium active fabric softening compounds (DEQA).

The above fabric care compositions may also contain one or more of the following ingredients in addition to the ingredients described herein.

Preferred components (A) a liquid carrier

Another preferred but more preferred component is a liquid carrier. The liquid carrier used in the present compositions is preferably at least primarily water because of its low cost, relative availability, safety and environmental compatibility. The amount of water in the liquid carrier is more preferably at least about 50%, more preferably at least about 60% by weight of the carrier. Mixtures of water and low molecular weight substances, for example < about 200, of an organic solvent such as lower alcohols such as ethanol, propanol, isopropanol or butanol are useful as liquid carriers. Low molecular alcohols include monohydroxy, dihydroxy (glycol, etc.), trihydroxy (glycerol, etc.) and higher polyhydroxy (polyols) alcohols.

(B) Solvents added

The compositions of the present invention may include one or more solvents that provide ease of processing. These effects of the administered solvents are described in WO 9 9 9 9 9 9 9

9 9 9 9 9 9 9 9 9

97/03169. This is particularly the case when liquid softening and cleaning agents are administered. When used, the processing facilitator system more preferably comprises less than 40%, more preferably from about 10% to 35%, more preferably from about 12% to 25%, and most preferably from about 14% to 20% by weight of the composition. The solvent that facilitates processing is selected to minimize the effect of odor in the composition and to provide a low viscosity in the final composition. For example, isopropyl alcohol is not very effective and has a strong odor. n-Propyl alcohol is more effective but also has a distinct odor. Some butyl alcohols also have odor, but can be used to increase clarity / stability, especially when used as part of a processing aid to minimize their odor. The alcohols are also selected for an optimally low stability temperature which allows them to form compositions that are liquid with an acceptable low viscosity and are translucent, more preferably pure from about 40 ° F (about 4.4 ° C) and are capable of recovering after storage at a temperature of about 20 ° F (about 6.7 ° C).

The suitability of some processing aids for the liquid, concentrated, more preferably pure, fabric softening composition used in the present invention with the necessary stability is surprisingly selective. Suitable solvents can be selected based on their octanol / water partition coefficient (P) as defined in WO 97/03169.

The processing aids in the present invention are selected from those having a ClogP of from about 0.15 to 0.64, more preferably from about 0.25 to 0.62, and more preferably from 0.40 to 0.60 of said processing aid, which is more preferably at least somewhere asymmetric and more preferably has a melting or freezing point so as to be liquid at or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for the same reasons. More asymmetric solvents appear to be highly desirable, while very symmetrical solvents, such as 1,7-heptanediol or 1,4-bis (hydroxymethyl) cyclohexane, which have a symmetry center, appear unsuitable to provide the necessary cleanliness of the compositions when used. on their own, even if they fall within an appropriate area due to their ClogP values.

The most suitable processing aids can be identified by forming cavities in the composition as observed by a cryogenic electron microscope when the composition is diluted to the concentration used in the rinse. These dilute compositions exhibit dispersion of the fabric softening agents and exhibit a more mono-laminar appearance than conventional fabric softening agents. The closer to the non-laminar appearance, the more it seems that the means are performing their activity. Surprisingly, these compositions provide good fabric softening compared to similar compositions prepared conventionally with the same fabric softening active agents.

• 4 4 4 «4 · 4 · 44

4 444444

44443 44 4 * 444

Suitable processing aids are described and listed below and have ClogP values that fall within the desired range. These include mono-oles, C6 diols, C7 diols, octanediol isomers, butanediol derivatives, isomers of trimethylpentanediol, isomers of methylmethylpentadiol, isomers of propylpentadiol, isomers of dimethylhexanediol, isomers of ethylhexanediol, isomers of methylheptanediol, nonionic isomers, ethers and aryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols and derivatives thereof, C3 to C7 alkoxylate derivatives of diols, aromatic diols and unsaturated diols. In particular, suitable processing aids include hexanediols such as 1,2-hexanediol and 2-ethyl-1,3-hexanediol and pentanediols such as 2,2,4-trimethyl-1,3-pentanediol.

(C) Dispersing excipients

Relatively enriching compositions containing both saturated and unsaturated diesters of the quaternary ammonium compounds can be prepared to be stable without the addition of concentrated excipients. However, the compositions of the present invention may require organic and / or inorganic enrichment aids, even at higher concentrations and / or higher standard stability depending on the other ingredients. These enrichment aids, which typically can alter the viscosity of the fabric, may be needed or may be suitable to provide stability under extreme conditions when special amounts of emollients are used. Surface enrichment agents are typically selected from the group consisting of (1) a single long alkyl chain of cationic detergents; (2) nonionic detergents; (3) amine oxides; (4) fatty acids; (5) mixtures thereof. These excipients are described in WO94 / 20597, in particular on page 14, line 12, which is incorporated by reference.

When said dispersing aids are present, the total amount thereof is from 2% to 25%, more preferably from 3% to 17%, more preferably from 4% to 15% and even more preferably from 5% to 13% by weight of the composition. These may either be added as part of the active softener (I), for example, to a fatty acid whose reactants are used to form a biodegradable fabric softener, as discussed above in the present invention, or may be added as separate components. The total amount of dispersing excipient includes any amount that may be present as part of component I.

Inorganic viscous / dispersing control agents which may also affect or enhance the effect of detergent enrichment aids, including water-soluble ionizable salts, which may also advantageously be incorporated into the composition of the present invention. 9 9 9 99 9999

9

9999 9999 9

9

9 9 9 9 999 of the invention. A wide variety of ionizable salts can be used. Examples of suitable salts are Group IA and IIA metal halides of the Periodic Table of the Elements, such as calcium chloride, magnesium chloride, sodium chloride, potassium bromide and lithium chloride. In particular, ionizable salts were used during the process of mixing the ingredients to form the composition of the invention and later to achieve the desired viscosity. The amount of ionizable salts used depends on the amount of active ingredients used in the composition and can be adjusted according to the requirements of the author. Typical amounts of salts used to control the viscosity of the composition are from about 20 to 20000 parts per million (ppm), more preferably from about 20 to 11000 ppm by weight of the composition.

Alkylene polyammonium salts can be incorporated into the composition to control viscosity when added to the water-soluble ionizable salts mentioned above. In addition, these agents may act as ionic vapor-cleaning cleaners with anionic detergents, leading to their removal from the main rinse and fabric wash and may improve fabric softness. These agents can stabilize the viscosity even over a wider temperature range, especially at low temperatures compared to inorganic electrolytes.

Specific examples of alkylene polyammonium salts include L-lysine monohydrochloride and

1,5-diammonium 2-methylpentane dihydrochloride.

(D) Stabilizers

Stabilizers may be present in the compositions of the present invention. The term "stabilizer" as used herein includes antioxidants and reducing agents. These agents may be present in an amount of from 0% to about 2%, more preferably from about 0.01% to 0.2%, more preferably from about 0.035% to 0.1% for antioxidants, and more preferably from about 0.01% up to 0.2% for reducing agents. These agents provide good stability (low level of odor) under long storage conditions for compositions and compounds stored in liquid form. The use of antioxidants and reducing agent stabilizers is particularly critical for low-perfume products.

Examples of antioxidants that may be added to the compositions of the invention include a mixture of ascorbic acid, ascorbic acid palmitate, propyl gallate, which are available from Eastmen Chemical Product, Inc, under the tradenames Tenox® PG and Tenox S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate and citric acid, available from Eastmen Chemical Product, Inc. under the tradename Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butyl hydroquinone, Eastmen Chemical Product, Inc., such as &quot;

Tenox TBHQ; natural tocopherols, Eastmen Chemical Product, Inc, such as TenoxGT-1 / GT-2; and butylated hydroxyanisole, Eastmen Chemical Product, Inc, such as BHA; long-chain gallic acid esters (C8-C22), for example dodecyl gallate; Irganox® 1010; Irganox® 1035; Irganox (R) B 1171; Irganox® 1425; Irganox® 3114; Irganox® 3125; and mixtures thereof; more preferably Irganox® 3125; Irganox® 1425; Irganox® 3114; and mixtures thereof; more preferably Irganox® 3125, which is used alone or is mixed with citric acid and / or other chelates such as isopropyl citrate, Dequest® 2010, which is available from Montaso and has the chemical name 1-hydroxyethylidene-1-diphosphonic acid (etidronic acid) acid) and Tiron®, available from Kodak, and has the chemical name 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt, EDDS and DTP A®, which are available from Aldrich and have the chemical name diethylenetriaminepentaacetic acid. The chemical names and CAS numbers for some of the above stabilizers are described in Table II below.

Table II

Antioxidant Prescriptions: CAS no. with Chemical name used in the National Code Irganox® 1010 6683-19-8 Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) methane Irganox® 1035 41484-35-9 Thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) Irganox® 1098 23128-74-7 Ν, Ν'-hexamethylene bis (3,5-di-tert-butyl-4hydroxyhydrocinnamamide) Irganox® B 1171 31570-04-4 23128-74-7 1: 1 mixture of Irgonax® 1098 and Irgafos® 168 Irganox® 1425 65140-91-2 Calcium bis (monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate) Irganox® 3114 65140-91-2 Calcium bis (monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate) Irganox® 3125 34137-09-2 3,5-Di-tert-butyl-4-hydroxyhydroxyhydrocinnamic acid tiester with 1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6- (1H, 3H, 5H) -tri-one Irgafos® 168 31570-04-6 Tris (2,4-di-tert-butylphenyl) phosphite

• 9 9 99 99

Q7 · 9 9 99

J! 9 9 9 9 9 99

999 99 9 9 99 · · 9

Examples of reductive agents include sodium borohydride, hypophosphoric acid, Irgafos® 168 and mixtures thereof.

(E) Stain Removal Agent

Stain removing agents are suitable for use in the fabric softening compositions of the present invention. Certain polymeric stain removal agents known to those skilled in the art of chemistry can be advantageously used in the compositions of the present invention. Polymeric stain removal agents are characterized by both hydrophilic segments and hydrophilization of the surface of hydrophobic fibers such as polyester and nylon and hydrophobic segments to deposit hydrophobic fibers and furthermore remove the adherents formed during washing and rinsing cycles and thus serve as absorbents hydrophilic segments. This may be detrimental to later processing and it is therefore preferable to use a stain removing agent in later washing procedures.

When stain-removing agents are used, they will generally comprise from about 0.01% to 10.0% by weight of the detergent compositions herein, typically from about 0.1% to 5%, more preferably from about 0.2% to 3%. , 0%.

The following are all stain removal polymers suitable for use in the present invention, which are incorporated by reference. US 3,959,230 Hays, issued May 25, 1976; U.S. 3,893,929 Basadur, issued July 8, 1975; U.S. 4,000,093, Nicol et al., Issued December 28, 1976; U.S. Patent 4,702,857 Gosselink, issued October 27, 1987; U.S. 4,968,445 Scheibel et al., Issued November 6; US 4,702,857 Gosselink, issued October 27, 1987; US 4,711,730, Gosselink et al., Issued December 8, 1987; US 4,721,580 Gosselink, issued Jan. 26, 1988; US 4,877,896, Maldonado et al., Issued October 31, 1989; U.S. 4,956,447, Gosselink et al., Issued September 11, 1990; U.S. 5,415,807 Gosselink et al., Issued May 16, 1995; European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.

Other suitable stain removing agents are described in US 4,201,824, Violland et al .; US 4,240,918 Lagasse et al .; U.S. 4,525,524 Tung et al. ; U.S. 4,579,681 to Rupper et al .; U.S. 4,240,918; 4,787,989; U.S. 4,525,524; EP 279 134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2 335 044 to Unilever Ν. V., 1974, all of which are incorporated herein by reference.

Commercially available stain removing agents include METOLOSE SM 100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo KK, SOKALAN type material such as SOKOLAN HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).

9 9 9 9 9 9 99 99

9

9 99 9 9 9 99 9 9 (F) Bactericidal agents

Examples of bactericidal compositions used in the composition of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania under the trade name Bronopol® and a 5-chloro-2- mixture. methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one sold by the Rohm and Haas Company under the trade name Kathon 1 to 1000 ppm by weight of the agent.

(G) perfume

The present invention may include perfume. Suitable perfumes are described in US Patent 5,500,138, said patent being incorporated by reference herein.

As used in the present invention, a perfume comprises a fragrance substance or a mixture of substances including natural (i.e., obtained by extracting flowers, herbs, leaves, roots, bark, wood, flowers or plants), artificial (i.e., a mixture of various natural oils or a substantial portion of oils). ) and synthetic (i.e. synthetically produced) fragrance substances. Such materials are often accompanied by excipients such as fixatives, fillers, stabilizers and solvents. These excipients are often included within the meaning of "perfume" as used herein. Typically, perfumes are complexes of mixtures of a number of organic compounds.

Examples of perfume ingredients useful in perfumes in the composition of the present invention include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexylsalicylate; terpinol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol;

2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol;

3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate; tricyclodecenylacetate; anisaldehyde; 2-methyl-2- (para-isopropylphenyl) propionaldehyde; ethyl 3-methyl-3-phenyl glycidate; 4- (para-hydroxyphenyl) butan-2-one; 1- (2,6,6-trimethyl) 2-cyclohexen-1-yl) -2-bute-1-one, para-methoxyacetophenone, para-methoxy-alpha-phenylpropene, methyl 2-n-hexyl-3-oxo-cyclopentane carboxylate, gamma-undecalactone.

Other examples of fragrances include, but are not limited to, orange essential oil; lemon essential oil; grapefruit essential oil; bergamot oil; clove oil; gamma-dodecalactone; methyl 2- (2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methyl ether; methyl beta-naphthyl ketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha, alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; Schiff base 4- (4-hydroxy-4)

·· φ · 99 · 99

9999 8 • ··

99999

9 99

9 99

9

9

9999

9

999

methylpentyl) -3-cyclohexene-1-carboxaldehyde and methyl anthranilate; cyclic ethylene glycol diester of tridecanedioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; gamma methyl ionone; α-ionone; β-ionone; petitgrain; methylcedrylon; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; methyl ionone; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; isohexyl cyclohexyl carboxaldehyde; formyl tricyclodecane; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; ambroxan; dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan; cedrol; 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-ol; caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexyl acetate; patchouli; oliban gum; read; vetivert; balm balm; fir balm; and condensed products: hydroxycitronone and methyl anthranilate; hydroxycitronone and indole; phenyl acetaldehyde and indole; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxyaldehyde and geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronelyl acetate; dihydromyrcenone; dihydromyrcenyl acetate; tetrahydromyrcenol; terpine acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; styralyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate; vetiverol; 2-methyl-3- (p-tert-butylphenyl) -propanal; 4- (4-methyl-3-pentenyl) -3-cyclohexenecarbaldehyde; 4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal; n-dodecanal; 9-decen-1-ol; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile; citronelontrtril; cedryl acetal; 3-isocamylcyclohexanol; cedryl methyl ether; isolongifolanone; aubepine nitrile; aubepine; heliotrophin; eugenol; vanillin; diphenyloxide; hydroxycitronelal ionones; methyl ionone; isomethyl ionones; ironů; cis-3-hexenols and their esters; indan musk fragrances; tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones; macrolactone musk fragrances; ethylene brasylate.

The perfumes useful in the compositions of the present invention are substantially free of halogenated or nitro-muscular substances.

Suitable solvents, diluents or carriers for the perfumes mentioned above are, for example, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc. Quantity such substances, i.e., solvents, diluents or carriers, contained in the perfumes are preferably as small as possible to provide homogeneity of the perfume solution.

The perfume may be present in an amount of from 0% to 10%, more preferably from 0.1% to 5% and more preferably from 0.2% to 3% by weight of the final composition. The fabric softening compositions of the present invention provide improved perfume retention on the fabric.

The perfume ingredients may also be suitably added flavor release agents, such as perfumes or fragrances, as described in US 5,652,205 Hartman et al., Issued July 29, 1997, incorporated herein by reference.

(H) Enzyme

The compositions and processes of the invention may advantageously employ one or more enzymes such as lipase, protease, cellulase, amylase, and peroxidase. A more preferred enzyme for use in the present invention is a cellulase enzyme. Indeed, this type of enzyme will further provide color care to the processed fabric. The cellulases used in the present invention include both bacterial and fungal types, more preferably having a pH optimum between 5 and 9.5. US 4,435,307 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM 1800 or cellulase 212 producing fungi belonging to the genus Aeromonas and cellulase extracted from the pancreas of the marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-2 247 832. CEREZYME® and CELLUZYME® (Novo) are particularly useful. Under practical conditions for present commercial preparations, the typical amount of enzymes is up to 5 mg, more preferably typically from 0.0 mg to 3 mg of active enzyme per gram of detergent composition. In another aspect, the compositions will typically comprise from 0.001% to 5%, more preferably from 0.01% to 1% by weight of the commercial enzyme preparation. In particular cases, in which the activity of the enzyme preparation may be defined differently, as is the case with cellulase, the corresponding unit activities are more appropriate (for example, CÉVU or cellulase Equivalent Viscosity Units). For example, the compositions of the present invention may contain cellulase enzymes in an amount corresponding to an activity of from 0.5 to 1000 CEVU / gram of composition. The cellulase enzymatic compositions used to process the composition of the invention typically have an activity comprised between 1000 and 10,000 CEVU / g in liquid form, about 1000 CEVU / g in solid form.

(I) Crystalline growth inhibitory agent

The compositions of the present invention may further comprise a crystal growth inhibiting agent, more preferably an organodiphosphonic acid and / or an organomonophosphonic acid, and the like. More preferably from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the composition.

By organodiphosphonic acid in the present invention is meant an organodiphosphonic acid which does not contain nitrogen in its chemical structure. However, this definition includes organoaminophosphonates which may be included in the compositions of the invention as well as the heavy metal separation means.

The organodiphosphonic acid is more preferably Cl and C4 diphosphonic acid, more preferably C2 diphosphonic acid such as ethylene diphosphonic acid or more preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, in particular as salts of the complex.

Still useful in the present invention as an inhibitor of crystal growth is organic monophosphonic acid.

The organic monophosphonic acid or one of its salts or complexes is also suitable for use in the present invention as CGI.

By organomonophosphonic acid in the present invention is meant a nitrogen-free organomonophosphonic acid in its chemical structure. However, this definition includes organoaminophosphonates which may be included in the compositions of the invention as well as the heavy metal separation means.

The organomonophosphonic acid may be present in its acid form or in the form of one of its salts or complexes with a suitable opposite cation. More preferably, some salts / complexes are water-soluble and alkali and alkaline earth metal salts / complexes are particularly suitable.

A suitable monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer under the trade name Bayhibit.

Other preferred components

The present invention may include preferred ingredients conventionally useful in fabric processing compositions, for example: brighteners, colorants, detergents, anticoagulants, fabric enhancers, coating agents, bactericidal agents, antifungal agents, antioxidants such as butylated hydroxytoluene, anticorrosive agents, antifoams reagents and the like.

The present invention also encompasses other compatible components, including those described in WO96 / 02625, WO96 / 21714 and WO96 / 21 715, and disperse polyolefins such as Velustrol® as described in PCT / US 97/01 644 and so on. alike. The present invention may also contain preferred chelating agents such as ethylenediamine-N, N'-disuccinic acid, (S, S) isomer in the form of its sodium salts (EDDS) and crystal growth inhibitors such as glycolic acid and / or 1,1-hydroxyethane diphosphonic acid (HEDP).

Form of the device

The fabric care composition may take a variety of physical forms including a liquid, such as aqueous and non-aqueous compositions, and a solid form, such as solid portions of the mold.

Such compositions may be applied to a substrate, such as a dried product layer, useful as an additional rinse product or as a spray or foaming product.

Similarly, in another aspect of the invention, there is provided the use of surfactants, more preferably coating reducing agents, as described hereinabove. In a composition comprising a nitrogen-containing compound selected from a polyamino functional polymer, a dye fixing agent, and mixtures thereof to reduce or prevent the formation of coatings on fabrics or parts of the washing machine that have come into contact with the composition. In other words, compositions that contain a nitrogen compound as defined above in the present invention but do not contain coating reducing agents produce an increased amount of coating compared to the composition of the invention.

Process

The fabric softening compositions may conveniently be manufactured according to well known processes known to those skilled in the art. An example is given in EP-A-0 668 092.

The invention is illustrated by the following non-limiting examples in which all percentages are based on weight unless otherwise stated.

In the examples, component abbreviations have the following meanings:

DEQA DOEQA DTDMAC : Di- (tallowoxy-ethyl) dimethyl ammonium chloride : Di- (oleyloxyethyl) dimethylammonium methyl sulfate : Ditallow dimethylammonium chloride DHEQA : Di- (soft-allowyl-oxy-ethyl) hydroxyethyl methyl ammonium methyl sulfate Fatty acid Electrolyte : tallow fatty acid IV = 18: Calcium chloride

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

DTDMAMS : Ditallowdimethylammonium methylsulfate SDASA : 1: 2 ratio of stearyldimethylamine: three times compressed stearic acid Glykosperse S-20 : Polyethoxylated sorbitan monostearate available from Lonza Clay : Bentonite L-type Bentonite L sold by Southern Clay Products TAE25 : Tallow alcohol ethoxylated with 25 moles of ethylene oxide per molecule of alcohol PEG : Polyethylene glycol 4000 PEI 1800 Ei : Ethoxylated polyethyleneimine (MW 1800 in 50% active substance) PEI 1800 E ₃ : Ethoxylated polyethyleneimine (MW 1800 in 50% active substance), synthesized as in Synthesis Example 1 PEI 1800 E ₇ AO : Amine oxide ethoxylated with polyethyleneimine (MW 1800 in 50% active substance), synthesized as in Synthesis Example 4 PEI 1200 Ei : Ethoxylated polyethyleneimine (MW 1200 in 50% active substance), synthesized as in Synthesis Example 5 PEI 1200 E ₂ Ethoxylated polyethyleneimine (MW 1200 in 50% active substance), synthesized as in Synthesis Example 5 PEI 1200 E ₇ : Ethoxylated polyethyleneimine (MW 1200 in 50% active substance), synthesized as in Synthesis Example 5 PEI 1200 E ₇ AO: Amine ethoxylated with polyethyleneimine (MW 1800 at 50% active substance), synthesized as in Synthesis Example 5 and 4 Fixing agent 1: Cellulose dye fixing reagent available under the tradename Tinofix FRD from Ciba-Geigy Fixing Agent 1; Cellulose reactive dye fixing reagent available under the trade name Rewin DWR from CHT R. Beitlich Reducing agent: N, N-dimethyl-N- (2-hydroxyethyl) -N-dodecyl / tetradecylammonium coating 1 bromide Reducing agent: coating 2 C12 / C14 choline ester Reducing agent: Polyoxalkylene alkylamine, which is commercially available from Akzo under coating 3 trade name Ethomeen T / 15 Reducing agent: Polyoxalkylene alkylamine, which is commercially available from Stepan coating 4 under the trade name Secomine TA 15

• • • • •

Reducing agent: Polyoxalkylenalkylamine, which is commercially available from Akzo under the trade name Ethoduomeen T / 20: Linear C1-2 alkylbenzene sodium: Tallow alcohol sodium sulphate: C12 to C1-5 linear alkyl alkyl sulphate: C1 to C1 y branched sodium alkyl sulphate condensed with from moles of ethylene oxide : C14 to C15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide: C12 to C15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide: Sodium linear alkylcarboxylate derived from an 80/20 mixture of tallow oils and groundnut oils: C16 to C18 alkyl N- methylglucamide: C12 to C14 fatty acids: hydrated sodium aluminosilicate of general formula

Nai ₂ (AlO2SiO2) i2.27H ₂ O: Anhydrous citric acid: Anhydrous sodium carbonate with particle sizes between 200 pm and 900 pm: Amphoteric sodium silicate (SiO2: Na2O; ratio 2.0): anhydrous sodium sulfate: trisodium citrate dihydrate o 86.4% activity with particle sizes between 425 pm and 850 pm: 1: 4 maleic / citric acid copolymer with an average molecular weight of about 70,000 coatings 5

LAS

TAS

C25AS

CxyEzS

C45E ₇

C25E ₃

Soap

TFAA

TPKFA

Zeolite A

Citric acid

Carbonate

Silicate

Sulfate

Citrate

MA / AA

CMC

Savinasa

Sodium carboxymethylcellulose Proteolytic enzyme of 4KNPU / g activity

Cellulytic enzyme with activity 1000 CEVU / g Amylolytic enzyme with activity 60 KNU / g

Lipolytic enzyme with an activity of 10OkLU / g

PB ₄

Carezym

Tetramyl

Lipolasa

They are all sold by NOVO Industries A / S and the activity of the above enzymes is specified above: Sodium perborate tetrahydrate of the general formula: &lt; tb &gt; ______________________________________ &lt; tb &gt; 9 · · 9 9 9 ♦ ♦ 9 9 9 9 9

NaBO2.3H2O.H2O2 PBt : Pure anhydrous sodium perborate of the formula NaBO2.H ₂ O ₂ TAED : tetraacetyl ethylenediamine DTPMP : diethylenetriaminpenta (methylene phosphonate), sold by Monsato under the trademark Dequest 2060 Photoactivated substance : sulfonated zinc phthalocyanine encapsulated in pure dextrin soluble polymer Gloss-forming additive : 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) aminostylbene-2: 2 '- disodium disulfonate Silicone defoaming agent Polydimethyldioxane antifoam with siloxane-oxyalkylene copolymer as a dispersant and a ratio of said antifoam to said dispersant from 10: 1 to 100: 1 HEDP : 1,1-hydroxyethane phosphonic acid Bayhibit AM : 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer TPTA N, N'-bis (3-aminopropyl) -1,3-propanediamine commercially available from Aldrich

DETAILED DESCRIPTION OF THE INVENTION

Synthesis Example 1- Preparation of PEI 1800 Ej

Step A) ethoxylation is carried out in a 2 gallon steel mixing autoclave connected to a device for controlling and measuring temperature, measuring pressure, generating vacuum and introducing inert gases, adding samples, and introducing liquid ethylene oxide. A 20 pound ethylene oxide bottle (ARC) is connected to a liquid ethylene oxide pump (pump) that is introduced into the autoclave from a bottle placed on a weighing device that monitors the weight changes of the bottle.

A 750 g amount of polyethyleneimine (PEI) (Nippon, Shokubai, Epomin SP-018 having an average molecular weight of 1800 and having 0.417 moles of polymer and 17.4 moles of functional nitrogen atoms) is added to the autoclave. The autoclave is now closed and the air has been removed (evacuated to minus 28 ”mercury, followed by pressurizing with nitrogen to 250 psia and then venting to atmospheric pressure). The contents of the autoclave were heated to 130 ° C under vacuum. After about 1 hour, the autoclave was filled with nitrogen to about 250 psia, while cooling the autoclave to a temperature of about 250 ° C. 105 ° C, then ethylene oxide was gradually added to the autoclave while measuring the autoclave pressure, temperature and ethylene oxide flow in the autoclave. The ethylene oxide supply pump is turned off and cooling is started when the temperature limit rises due to the exothermic reaction. The temperature is maintained between 100 ° C to 110 ° C, although the total pressure gradually rises during the reaction. After the total addition of 750 g of ethylene oxide to the autoclave (approximately equivalent to 1 mole of ethylene oxide per PEI nitrogen function), the temperature rose to 110 ° C and the autoclave content was stirred for an additional hour. At this point the autoclave was evacuated and the remainder of the unreacted ethylene oxide was removed.

Step B) The reaction mixture was odorless by bubbling about 100 cu. fit. of inert gas (argon or nitrogen) using a dispersed frit and through the reaction mixture while stirring and heating the mixture to 130 ° C. The final reaction product is cooled somewhat and stored in glass containers under nitrogen. Other preparations, such as neutralization and odor removal, are carried out in the reactor prior to product discharge.

If a PEI 1800 Εγ is required the next step in which the catalyst is added can be curved between steps A and B.

Vacuum is continuously applied until the autoclave is cooled to about 50 ° C, then 376 g of 25% sodium methoxide in methanol (1.74 mol, i.e. addition of 10% catalyst based on PEI functional nitrogen atoms) is added. The methanolate solution is sucked into the autoclave by vacuum and then the autoclave control unit raises the temperature to 130 ° C. The device is used to monitor the power input of the mixer. The mixer performance is monitored along with pressure and temperature. The mixer performance and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and is stabilized after about 1 hour, meaning that most of the methanol has been removed. The mixture is further heated and stirred under vacuum for an additional 30 minutes.

The vacuum is removed and the autoclave is cooled to 105 ° C, pressurized to 250 psia with nitrogen and then vented to room pressure. Nitrogen is pressurized into an autoclave of 200 psia. Gradually ethylene oxide is added to the autoclave as before, while the autoclave pressure, temperature, ethylene oxide flow ratio are closely monitored. The temperature is maintained between 100 ° C to 110 ° C, although the total temperature gradually rises during the exothermic reaction. After the addition of 4500 g of ethylene oxide, which is a total of 7 moles of ethylene oxide per mole of PEI nitrogen function, which is achieved within a few hours, the temperature rises to 110 ° C and the mixture is stirred for 1 hour.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

The reaction mixture is then cooled in nitrogen purged flasks and finally transferred to a 22 L three-necked round flask coupled with heating and stirring. The highly alkaline catalyst is neutralized by the addition of 167 g methanesulfonic acid (1.74 mol).

Other suitable examples such as PEI 1800 E ₂ , PEI 1800 E ₃ , PEI 1800 E ₅ , PEI 1800, E ₂₀ can be prepared by the above method while controlling the time and relative amount of ethylene oxide used in the reaction.

Synthesis example 2 - 4.7% quaternization of PEI 1800 E ₇

To a 500 mL Erlenmeyer flask coupled with a magnetic stirrer is added polyethyleneimine, MW 1800, which was ethoxylated to step 7 (224 g, 0.637 mol of nitrogen, prepared as in Synthesis Example 1) and acetonitrile (Beker, 150 g, 3.65 mol). . Dimethyl sulfate (Aldrich, 3.8 g, 0.030 mol) is added in one portion to a rapidly stirring solution, which is then stoppered and stirred at room temperature overnight. The acetonitrile is evaporated on a rotary evaporator at 6060 ° C, then using a Kugelrohr apparatus (Aldrich, -80 ° C) to give 20220 g of the desired material as a dark brown viscous liquid. ^{The 13} C NMR (D ₂ O) spectrum shows the absence of a peak at -58 ppm of the corresponding dimethyl sulfate. * H NMR (D ₂ O) spectrum shows a partial shifting of the peak at 2.5ppm (methylenes related to non-quaternary nitrogens) to ~ 3.0 ppm.

Synthesis example 3 - oxidation of 4.7% quaternized PEI 1800 E ₇

To a 500 ml Erlenmeyer flask coupled to a magnetic stirrer is added polyethyleneimine, MW 1800, which has been ethoxylated to degree 7 and ~ 4.7% of quaternized PEI with dimethyl sulfate (121.7 g, -0.32 moles of oxidizable nitrogen, prepared as in Synthesis Example 2), hydrogen peroxide (Aldrich, 40 g of a 50% by weight solution in water, 0.588 mol) and water (109.4 g). The flask is sealed and after initiation exothermic reaction the solution is stirred at room temperature overnight. * H NMR (D ₂ O) spectrum shows the total shifting of the methylene peaks from 2.5-3.0 ppm to -3.5 ppm. -5 g of 0.5% Pd on alumina pellets is added to the solution and the solution is allowed to stand for -3 days. The peroxide indicator paper indicates that no peroxide remained in the system. The material is stored as a 46.5% solution in water.

Synthesis example 4 - PEI 1800 E ₇ amine oxide formation

To a 500 ml Erlenmeyer flask coupled to a magnetic stirrer is added polyethyleneimine, MW 1800, which has been ethoxylated to a degree of about 7 ethoxy groups on nitrogen (PEI 1800 E ₇ ) (209 g, 0.595 mol of nitrogen prepared in Synthesis Example 1) and hydrogen peroxide (120 g, 30% (w / w) solution in water, 1.06 mol). The flask is sealed and after initiation exothermic reaction, the solution is stirred at room temperature overnight. ¹ H NMR (D ₂ O) obtained · 9 9 * A

99 9 9 ·

99999 9 · 9 · 9 sample from the reaction mixture shows complete conversion. Resonance describing proton shift of non-oxidized nitrogen was shifted from its original position at ~ 2.5 ppm to ~ 3.5 ppm. ~ 5 g of 0.5% Pd on alumina pellets is added to the solution and allowed to stand for ~ 3 days. The solution is tested and found to be peroxide-negative by means of indicator paper. The material obtained is conveniently stored as a 51.1% active solution in water.

Synthesis example 5 - formation of amine oxide PEI 1200 Ei

Step A) ethoxylation is carried out in a 2 gallon steel mixing autoclave connected to a device for controlling and measuring temperature, measuring pressure, generating vacuum and introducing inert gases, adding samples, and introducing liquid ethylene oxide. A 20-liter bottle of ethylene oxide (ARC) is connected to a liquid ethylene oxide pump (pump) that is introduced into the autoclave from a bottle placed on a weighing device that monitors the weight changes of the bottle.

A 750 g amount of polyethyleneimine (PEI) (having an average molecular weight of 1200 and having 0.625 moles of polymer and 17.4 moles of functional nitrogen atoms) is added to the autoclave. The autoclave is now closed and the air has been removed (evacuated to minus 28 ”mercury, followed by pressurizing with nitrogen to 250 psia and then venting to atmospheric pressure). The contents of the autoclave were heated to 130 ° C under vacuum. After about 1 hour, the autoclave was charged with nitrogen to about 250 psia while cooling the autoclave to about 105 ° C, then ethylene oxide was gradually added to the autoclave while measuring the autoclave pressure, temperature, and ethylene oxide flow in the autoclave. The ethylene oxide supply pump is turned off and cooling is started when the temperature limit rises due to the exothermic reaction. The temperature is maintained between 100 ° C to 110 ° C, although the total pressure gradually rises during the reaction. After the total addition of 750 g of ethylene oxide to the autoclave (approximately equivalent to 1 mole of ethylene oxide per PEI nitrogen function), the temperature rose to 110 ° C and the autoclave content was stirred for an additional hour. At this point the autoclave was evacuated and the remainder of the unreacted ethylene oxide was removed.

Step B) The reaction mixture was odorless by bubbling about 100 cu. ft. of inert gas (argon or nitrogen) using a dispersed frit and through the reaction mixture while stirring and heating the mixture to 130 ° C. The final reaction product is cooled somewhat and stored in glass containers under nitrogen. Other preparations, such as neutralization and odor removal, are carried out in the reactor prior to product discharge.

If a PEI 1800 E7 is required the following step in which the catalyst is added can be curved between steps A and B.

Vacuum is continuously applied until the autoclave is cooled to about 50 ° C, then 376 g of 25% sodium methoxide in methanol (1.74 mol, i.e. addition of 10% catalyst based on PEI functional nitrogen atoms) is added. The methanolate solution is sucked into the autoclave by vacuum and then the autoclave control unit raises the temperature to 130 ° C. The device is used to monitor the power input of the mixer. The mixer performance is monitored along with pressure and temperature. The mixer performance and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and is stabilized after about 1 hour, meaning that most of the methanol has been removed. The mixture is further heated and stirred under vacuum for an additional 30 minutes.

The vacuum is removed and the autoclave is cooled to 105 ° C, pressurized to 250 psia with nitrogen and then vented to room pressure. Nitrogen is pressurized into an autoclave of 200 psia. Gradually ethylene oxide is added to the autoclave as before, while the autoclave pressure, temperature, ethylene oxide flow ratio are closely monitored. The temperature is maintained between 100 ° C to 110 ° C, although the total temperature gradually rises during the exothermic reaction. After the addition of 4500 g of ethylene oxide, which is a total of 7 moles of ethylene oxide per mole of PEI nitrogen function, which is achieved within a few hours, the temperature rises to 110 ° C and the mixture is stirred for 1 hour.

The reaction mixture is then cooled in nitrogen purged flasks and finally transferred to a 22 L three-necked round flask coupled with heating and stirring. The highly alkaline catalyst is neutralized by the addition of 167 g methanesulfonic acid (1.74 mol).

Other suitable examples such as PEI 1800 _E2, PEI 1800 E3, PEI 1800 E15 PEI 1800 E ₂ may be prepared by the above method for controlling the time and the relative amount of ethylene oxide used in the reaction.

Synthesis example 6 - 9.7% quartemization of PEI 1800 E7

To a 500 mL Erlenmeyer flask coupled with a magnetic stirrer is added polyethyleneimine, MW 1200, which was ethoxylated to step 7 (248.4 g, 0.707 mole of nitrogen, prepared as in Synthesis Example 5) and acetonitrile (Beker, 150 g, 3.65). mol). Dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) is added all at once to a rapidly stirring solution, which is then stoppered and stirred at room temperature overnight. The acetonitrile is evaporated on a rotary evaporator at -60 ° C, then further in a Kugelrohr apparatus (Aldrch, -80 ° C) to give -220 g of the desired material as a dark brown viscous liquid. C NMR (D ₂ O) · D * * * * * * * NMR NMR NMR NMR NMR NMR NMR NMR NMR NMR

The SO spectrum showed the absence of a peak at -58 ppm of the corresponding dimethyl sulfate. * H NMR (D ₂ 0) spectrum shows a partial shifting of the peak at 2.5ppm (methylenes related to non-quaternary nitrogens) to ~ 3.0 ppm.

Synthesis example 7 - 4.7% oxidation 9.5% quaternized PEI 1800 Εγ

To a 500 ml Erlenmeyer flask coupled to a magnetic stirrer is added polyethyleneimine, MW 1200, which has been ethoxylated to step 7 and -9.5% quaternized PEI with dimethyl sulfate (144 g, -0.37 moles of oxidizable nitrogen, prepared as in the example) Synthesis 6), hydrogen peroxide (Aldrich, 35.4 g of a 50 wt.% solution in water, 0.52 mol) and water (100 g). The flask is sealed and after initiation exothermic reaction, the solution is stirred at room temperature overnight. The 1 H NMR (D ₂ O) spectrum shows the total shift of methylene peaks from 2.5 to 3.0 ppm to -3.5 ppm. Sufficient sodium metabisulfite is added to the solution as a 40% aqueous solution to reduce the amount of residual peroxide to 1-5 ppm. The sodium sulphate formed in the aqueous phase makes it possible to separate the aqueous phase with salts, but with little or no organic compounds. The aqueous salt phase is discarded and the desired oxidized polyethyleneimine derivative is recovered and stored as a 52% solution in water.

Example 1

The following compositions are in accordance with the present invention

Active substance (%) AND II III IV IN Dye Fix 1 5.0 5.0 5.0 5.0 10.0 PEI 1200 E - 10.0 20.0 5.0 20.0 DEQA - - - - - Bayhibit AM 1.0 0.2 1.0 1.0 1.0 NH ₄ Cl - - 0.2 0.2 0.5 CFP ₂ - - - 0.5 1.0 MgCl ₂ - - - - 4.0 Gloss forming agent 1 - - - - 0.2 Coating reducing agent 3 5 10 10 5 10 Water and minor substances to equalize up to 100

Example 2

The following compositions are in accordance with the present invention.

Component AND II III IV IN Coating reducing agent 1 1.0 - - 5.0 5.0 Coating reducing agent 2 - - - 2.5 2,0 Coating reducing agent 5 - 2,0 2,0 - - DEQA 2.6 18.0 19.0 - - TAE25 - 1.0 - - - Fatty acid 0.3 1.0 - - - Hydrochloric acid 0.02 0.02 0.02 - - PEG - 0.6 0.6 - - Perfume 1.0 1.0 1.0 0.1 0.1 Silicone defoaming agent 0.01 0.01 0.01 - - PEI1200 E ₄ 3 3 - 15 Dec - TPTA - - 5 - 10 Dye Fix 1 1.0 - 5.0 - 10 Dye Fix 2 - 3 - 5.0 - HEDP 0.2 - - 0.4 - Electrolyte (ppm) - 600 1200 - - Dye (ppm) 10 50 50 - - Water and minor substances to equalize up to 100

Component VI VII VIII IX Coating reducing agent 4 2.5 5.0 10 1.0 DTDMAC - - - 15 Dec DEQA 2.6 19.0 - - TAE25 0.3 - - - Fatty acid 0.3 - - - Hydrochloric acid 0.02 0.02 - 0.02 PEG - 0.6 - 0.6

· ♦ · * ♦ ♦ • ♦ * * * * * * * * * *

Perfume 1.0 1.0 0.1 1.0 Silicone defoaming agent 0.01 0.01 - 0.01 PEI 1800 E ₄ 3 3 10 3 Dye Fix 1 1 3.0 10 1 Dye Fix 2 2 - - 2 Electrolyte (ppm) - 600 - 600 Dye (ppm) 10 50 - 50 Water and minority substances to equalize c o 100

Example 3

The following compositions for use as a layer of added dryers are in accordance with the present invention

AND II III IV IN VI Coating reducing agent 4 10.0 5.0 2.5 1.0 5.0 0.1 DOEQA 40 25 - - - - DHEQA - - 20 May - - - DTDMAMS - - - 2 12 60 SDASA 30 30 20 May 30 20 May - Glykosperse S-20 - - 10 - - - Glycerol monostearate - - - 20 May 10 - Clay 4 4 3 4 4 - Perfume 0.7 1.1 0.7 1.6 2.6 1.4 PEI 1800 Ei - 5 - - - - PEI 1200 E ₄ - - 4 2.2 - - PEI 1800 E ₄ 2 - - - 5 7.0 Dye Fix 1 2 5 4 2.2 5 3 HEDP 0.2 - 0.5 - - 0.7 Glycolic acid - 0.2 - 0.2 - - Polycarboxylic acid - 0.2 - - 0.4 - Stearic acid to equalize up to 100

Example 4

The following detergents of formulas S and T are in accordance with the present invention:

WITH T Zeolite A 24.0 23.0 Sulphate 9.0 - MA / AA 4.0 4.0 LAS 8.0 8.0 TAS - 2,0 Silicate 3.0 3.0 CMC 1.0 0.4 Gloss-forming additive 0.2 - Soap 1.0 - DTPMP 0.4 0.4 C45E7 2.5 2,0 c ₂₅ e ₃ 2.5 2,0 Silicone defoaming agent 0.3 5.0 Perfume 0.3 0, Carbonate 13.0 16.0 Citrate - 5.0 PB4 18.0 - PB1 4.0 14.0 TAED 3.0 6.0 Photoactivated whitening bath 0.02% - Savinasa 1.0 1.0 Lipolasa 0.4 0.4 Termamyl 0.30 0.6 Carezym - 0.6 PEI 1800 E ₇ AO 1.0 - PEI 1800 E ₇ AO - 1.0 Dye Fix 1 2,0 1.0 Coating reducing agent 4 0.5 0.5 HEDP 0.2 - Glycolic acid - 0.2

Polycarboxylic acid - 0.2 Compensation (moisture and miscellaneous substances) up to 100

Example 5

The following liquid detergent composition of the present invention was prepared:

AT c ₂₅ as 13 c ₂₅ e ₂ p 2 TFAA 6 C12 to C14 alkyl dimethylhydroxyethyl ammonium chloride 1 Cationic ester 1.5 TPKFA 15 Dec Citric acid 1 Ethanol 2 1,2-propanediol 8 NaOH to raise the pH 7.5 DTPMP 1,2 Savinasa 0.5 Termamyl (300 KNU / g) 0.15 Boric acid 1.5 Bentonite type softening clay 4 Suspension clay SD ₃ 0.3 PEI 1200 E ₇ 1 Dye Fix 2 1 Coating reducing agent 5 0.2 Rest (moisture and miscellaneous substances) 100 ALIGN!

Claims (11)

PATENT CLAIMS CLAIMS 1. A fabric care composition comprising: (i) a nitrogen-containing compound selected from polyamino functional polymer, dye fixing agent and mixtures thereof; and (ii) a coating reducing agent selected from water-soluble cationic surfactant, polyoxyalkylene alkyl amine surfactant and mixtures thereof, provided that: when the single nitrogen-containing compound is a polyamino functional polymer, the polymer was present in an amount greater than 1% by weight. A composition according to claim 1, wherein said water-soluble cationic surfactant has the general formula: [R ^] N ⁺ R 3] X · wherein R ¹ is a C 10 to C 22 hydrocarbon group or the corresponding ester linkage interrupted by a short alkylene (C 1 -C 4) group between the ester linkage and N, each R is C 1 -C 4 alkyl or substituted alkyl; hydrogen and the opposite ion X 'is a compatible anion that softens the surface. A composition according to claim 2, wherein the water-soluble cationic detergent is obtained from N, N-dimethyl-N- (2-hydroxyethyl) -N-dodecyl / tetradecyl ammonium bromide, myristoyl choline ester of quaternary methylammonium halides, lauroyl quaternary methylammonium halide ester choline, quaternary methylammonium halide cocoyl choline ester and mixtures thereof. A composition according to any one of claims 1 to 3, wherein the polyoxyalkylene alkyl amine surfactant has the general formula: (R ⁴ ) n wherein R is selected from C 7 to C 21 linear alkyl, C 7 to C 21 branched alkyl, C 7 to C 21 1; 2 linear alkenyl, C7 to C21 branched alkenyl, and mixtures thereof; R is ethylene; R is «· · '''' 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Selected from C3 to C4 linear alkyl, C3 to C4 branched alkyl and mixtures thereof; R ⁴ is selected from hydrogen, C 1 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; And is - N - (R 5) - [(R 10) _x (R ²⁰ ) _y R ³ ] R ⁵ is selected from - [(R ¹⁰ ) x (R ²⁰ ) y] unit, C1 to C16 linear alkyl, C1 to C16 branched alkyl, C1 to C16 linear alkenyl, C1 to C16 branched alkenyl, and mixtures thereof; where m is 1 or 2, n is 0 or 1 such that when m is 1, n is 1; and when m is 2, n is 0; wherein the index x is from 0 to about 50, more preferably from about 1 to 25; wherein the index y is from 0 to about 10; where index q is 0 or 1. The composition of claim 4, wherein said index x is from 1 to 25. The composition of any one of claims 4 or 5, wherein said index m is 2 and n is 0. Composition according to any one of claims 1 to 6, characterized in that said polymer comprises a polyamine skeleton corresponding to the general formula: R '| [R2N-RW1 - [N-Rjm- [NR] _n -NR1 having a polyamine general formula V ( _{n +} i) W _m Y _n Z or a polyamine skeleton corresponding to the general formula: R 'IR [Rn-R] irk + i - [NR] _m - [N -R] _n - [N-Rjk-NR] having the polyamine formula V ( _n. K ₊ i) W _m Y _n Y \ Z, wherein k is less than or equal to n, said polyamine skeleton has a molecular weight greater than 200 daltons, wherein (i) The units are terminating units and have the general formula: rť57 R 'xR ¹ —N — R— AND R ' • 44 • 44 4 ·· 4 ···· • • 4 • 4 4 • 44 · 4 4 • 4 4 4 4 • 4 44 44 4 4 4 4 4 4 • 4 4 4 4 4 4 R-N-R I R 'or (ii) W units are skeletal units and have the general formula: N-R— I R 'or O t N-R R 'or iii) Y units are branching units and have the general formula: O t —N-R— I R -N-RI R or or iv) Y'units are branching points for skeleton or branching of the ring and have the general formula: or (v) Z 'units are terminal units and have the general formula: N-R 'I R 'or or; wherein the scaffolding R units are selected from the group consisting of C 2 to C 12 alkylene, C 4 to C 12 alkenylene, C 3 to C 12 hydroxyalkylene, C 4 to C 12 dihydroxyalkylene, C 8 to C 12 dialkylarylene, - (R'O) _x R'-, -CH ₂ CH ^(OR2) CH2-, - (CH2CH (OH) CH2O) z (R ¹ O) y R ¹ (OCH 2 CH (OH) CH2) w-, -C (O) (R ⁴⁾ r C (O) -, -CH ₂ CH (OR ² ) CH ² - and mixtures thereof; wherein the R ¹ units are selected from the group consisting of C 2 -C 6 alkylene and mixtures thereof; R is selected from the group consisting of hydrogen, - (R'O) XB, and mixtures thereof; R ⁴ is selected from the group consisting of C 1 to C 12 alkylene, C 4 to C 12 alkenylene, C 8 to C 12 arylalkylene, C 6 to C 10 arylene, and mixtures thereof; R ⁵ is selected from the group consisting of 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) -, 9 9 9 99 9,999 9 9 9 9 9,999 9999 9 -R (OR ¹ ) -, -CH 2 CH (OH) CH ² O (R ¹⁰ ) y R ^, OCH 2 CH (OH) CH 2 - and mixtures thereof; R ⁶ is selected from the group consisting of C 2 -C 12 alkylene or C 6 -C 12 arylene; R 1 units are selected from the group consisting of hydrogen, C 1 to C 22 alkyl, C 3 to C 22 alkenyl, C 7 to C 22 arylalkyl, C 2 to C 22 hydroxylalkyl, - (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, 13 - (RO) _X B, -C (O) R and mixtures thereof; B is selected from the group consisting of hydrogen, C1 to C6 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 mixtures thereof; R ³ is selected from the group consisting of C 1 to C 8 alkyl, C 7 to C 12 arylalkylene, C 7 to C 12 alkyl substituted aryl, C 6 to C 12 aryl and mixtures thereof; M is hydrogen or a water-soluble cation in sufficient quantity to satisfy the charge balance; X is a water-soluble anion; m has a value of from 2 to 700; n is from 0 to 350; p is from 1 to 6; q is from 0 to 6; r is 0 or 1; w is 0 or 1, x is from 1 to 100; y is from 0 to 100; z is 0 or 1. The composition of any one of claims 1 to 7, wherein said dye fixing agent is a reactive cellulose dye fixing agent. Composition according to any one of claims 1 to 8, characterized in that the nitrogen-containing compound is from 1% to 25% by weight, most preferably from 1% to 10% by weight of the active ingredient. Use of a surfactant in a composition comprising a nitrogen-containing compound selected from a polyamino functional polymer, a dye fixing agent and mixtures thereof to reduce the prevention of coating on fabric or washing machine parts contacted with the composition. The use of claim 9, wherein said surfactant is selected from a water-soluble cationic surfactant; polyoxyalkylene alkyl amine surfactant, water-soluble emollients and mixtures thereof.