MXPA00005061A - Stabilised fabric softening compositions - Google Patents

Abstract

The present invention is a composition comprising a polyamino functional polymer, whereby said composition is stabilised by means of a crystal growth inhibitor.

Description

STABILIZED FABRIC SOFTENING COMPOSITIONS FIELD OF THE INVENTION The present invention relates to a composition for the care of fabrics comprising a polyamino-functional polymer, by means of which effective stabilization of the composition is obtained.

BACKGROUND OF THE INVENTION The appearance of colored fabrics, for example, clothing, bedding, domestic fabrics such as table linen is one of the areas of interest to consumers. In fact, after the typical use of the fabrics by the consumer such as use, washing, rinsing and / or drying of the fabrics, a loss in the appearance of the fabrics, which is at least partially due to the loss of Color fidelity and color definition can take place. Said problem of color loss is more serious after multiple washing cycles. Therefore, an object of the invention is to provide a composition that provides improved color care to washed fabrics, especially after multiple washing cycles.

Recently, a new class of materials, mainly, amino-functional polymers, have found increasing use in the treatment of fabrics to be able to provide care to the color of the fabrics. However, it has been found that compositions comprising these amino-functional polymers tend to have storage stability problems. This problem can be characterized by a yellowish formation of the composition as well as bad odors on the treated fabrics. This problem is more severe when the product is formulated as a single product. In fact, when formulated in combination such as in a softening composition, the perfume present therein provides some coverage of bad odors resulting in more acceptable odors. On the contrary, for single products, the perfume, unless it is present at a very high level, does not sufficiently cover the bad smell. The high levels of perfume, however, increase the cost of formulation. In addition, high levels of perfume to cover the bad smell do not provide prolonged coverage of bad odors. In fact, the perfume will provide instant malodor coverage but after storage the perfume containing volatile ingredients will evaporate reducing the benefit of odor coverage. Likewise, the formulator of a composition for the care of fabrics faces the double problem of formulating a composition that provides fabric care without being negative for the stability of the composition.

Unexpectedly, the Applicant has found that the provision of a crystal growth inhibitor in compositions comprising modified amino-functional polymers counteracts the problem.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a plot of the base volume added against time to maintain the pH of the reaction medium.

DETAILED DESCRIPTION OF THE INVENTION Amino-functional polymer An essential component of the invention is an amino-functional polymer. The amino-functional polymer advantageously provides care for the colors of the fabrics. The amino-functional polymers of the present invention are water soluble or dispersible polyamines. Typically, amino-functional polymers for use herein have a molecular weight between 200 and 106, preferably between 600 and 20,000, most preferably between 1000 and 10,000. These polyamines comprise base structures that can be linear or cyclic. The polyamine base structures may also comprise polyamine branching chains to a greater or lesser degree.

Preferably, the polyamine base structures described herein are modified such that at least one, preferably each nitrogen of the polyamine chain is described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof. . For the purposes of the present invention the term "modification" in regard to the chemical structure of the polyamines is defined as the replacement of a hydrogen atom -NH of base structure by an R 'unit (substitution), quatemizing a nitrogen of the base structure (quaternized) or oxidizing a nitrogen of the base structure to an N-oxide (oxidized). The terms "modification" and "substitution" are invariably used when referring to the process of replacing a hydrogen atom attached to a nitrogen of the base structure with a unit R '. The quaternization or oxidation may be carried out in some circumstances without substitution, but the substitution is preferably accompanied by oxidation or quaternization of at least one nitrogen of the base structure. The non-cyclic or linear polyamine base structures comprising the amino functional polymer have the general formula: [R'2N-R] n + 1 - [N-R] m- [N-R] n-NR The cyclic polyamine base structures comprising the amino functional polymer have the general formula: R R I _R'2N-R] n-k + 1 - [N-R] m- [N-R] n- [N-R] k-NR2 The above base structures, prior to the optional but preferred subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by "linker" units R. For the purpose of the present invention, the primary amine nitrogens comprising the structure of base or chain branching, once modified, are defined as "terminal" units V or Z. For example, when a portion of primary amine located at the end of the base structure of main polyamine or branching chain that has the structure: H2N - [R] - is modified according to the present invention, is then defined as a "terminal" unit V, or simply a unit V. However, for the purposes of the present invention, some or all of the primary amine portions they may remain unmodified subject to the restrictions described in more detail later herein. These unmodified primary amine portions, by virtue of their position in the base structure chain, remain as "terminal" units. Likewise, when a portion of primary amine, located at the end of the main polyamine base structure having the structure: -NH2 is modified in accordance with the present invention, is hereinafter defined as a "terminal" unit Z, or simply a unit Z. This unit may remain unmodified subject to the restrictions described in more detail hereinafter. Similarly, the secondary amine nitrogens comprising the base structure or branching chain, once modified, are defined as "base structure" units W. For example, when a secondary amine portion, the main constituent of the base structures and branching chains of the present invention, having the structure H - [NR] - is modified in accordance with the present invention, is hereinafter defined as a "base structure" unit W, or simply a unit W. However, for the purposes of the present invention, some or all of the secondary amine portions may be remain unchanged. These unmodified secondary amine portions, by virtue of their position in the base structure chain, remain as "base structure" units. In another similar form, the tertiary amine nitrogens comprising the base structure or branching chain, once modified, are further defined as "branching" Y units. For example, when a tertiary amine moiety, which is a point of chain branch or base structure of polyamine or other branching chains or rings, having the structure: - [N-R] - is modified according to the present invention, is hereinafter defined as a "branching" unit Y, or simply a unit Y. However, for the purposes of the present invention, some or all of the tertiary amine portions may remain unmodified . These unmodified tertiary amine portions, by virtue of their position in the base structure chain, remain as "branching" units. The R units associated with the nitrogens of unit V, W and Y that serve to connect the polyamine nitrogens will be described later. The modified final structure of the polaminas of the present invention can then be represented by the general formula: (n + 1) WmYnZ for the linear amino-functional polymer, and for the general formula (n-k + 1) WmYnY, kZ for the cyclic amino-functional polymer. For the case of the polyamines comprising rings, a unit Y 'of the formula: R - [N-R] - serves as a branch point for a base structure or a branch ring.

For each unit Y 'there exists a unit Y that has the formula: - [N-R] - which will form the connection point of the ring to the chain or branch of the main polymer. In the unique case in which the base structure is a complete ring, the polyamine base structure has the formula: R i [R2N-R] n - [N-R] m- [N-R] n-- therefore does not comprise any terminal unit Z and has the formula Vn-kWmYnY'k where k is the number of ring-forming branch units. Preferably, the polyamine base structures of the present invention do not comprise rings. In the case of non-cyclic polyamines, the ratio of index n to index m refers to the relative degree of branching. A completely unbranched linear modified polyamine according to the present invention has the formula: VWmZ that is, n is equal to 0. The greater the value of n (the smaller the ratio of m to n), the greater the degree of branching in the molecule. Typically, the value of m varies from a minimum value of 2 to 700, preferably 4 to 400, however, values greater than m are also preferred, especially when the value of the index n is very low or almost 0.

Each polyamine nitrogen, whether primary, secondary or tertiary, once modified in accordance with the present invention, is further defined as being a member of one of two general classes; simple replaced, quaternized or oxidized. Those unmodified polyamine nitrogen units are classified into units V, W, Y, Y 'or Z depending on whether they are primary, secondary or tertiary nitrogens. That is, the nitrogens of the unmodified primary amine are V or Z units, the nitrogens of the unmodified secondary amine are W units or Y 'units and the unmodified tertiary amine nitrogens are Y units for the purposes of present invention. Modified primary amine moieties are defined as "terminal" units V having one of three forms: a) simple substituted units having the structure: R- N- R- I R b) quatemized units that have the structure: where X is a suitable counter ion that provides charge equilibrium; and c) oxidized units having the structure: Modified secondary amine portions are defined as "base structure" units W having one of three forms: a) simple substituted units having the structure: -N-R- I R b) quaternized units that have the structure: -N- R - R where X is a suitable counter ion that provides charge balance; and c) oxidized units having the structure: Other portions of modified secondary amine are defined as units Y 'having one of three forms: a) simple substituted units having the structure: - N-R- I R b) quaternized units that have the structure: where X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: The modified tertiary amine moieties are defined as "branching" units and they have one of three forms: a) unmodified units that have the structure: - N-R - b) quaternized units that have the structure: where X is a suitable counterion that provides load balance; and c) oxidized units having the structure: O - t N - R - Certain portions of modified primary amine are defined as "terminal" Z units having one of three forms: a) simple substituted units having the structure: N-R I R b) quaternized units that have the structure: where X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: When any position on a nitrogen is substituted or not modified, it is understood that the hydrogen will replace R '. For example, a primary amine unit comprising an R 'unit in the form of a hydroxyethyl portion is a terminal unit V having the formula (HOCH2CH2) HN-.

For the purposes of the present invention, there are two types of chain terminator units, units V and Z. The "terminal" unit Z is derived from a terminal primary amino portion of the structure -NH2. The non-cyclic polyamine based structures according to the present invention only comprise one unit Z, while the cyclic polyamines can comprise no unit Z. The "terminal" unit Z can be substituted with any of the units R 'described in more detail after, except when the Z unit is modified to form an N-oxide. In case the unit Z is oxidized to an N-oxide, the nitrogen must be modified and therefore R 'can not be a hydrogen. The polyamines of the present invention comprise "linker" units R of base structure which serve to connect the nitrogen atoms of the base structure. The R units comprise units which for the purpose of the present invention are called "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C 2 -C 2 alkylene, C 4 -C alkylene, and C 3 -C 1 hydroxyalkylene? in which the hydroxyl portion can take any position on the R unit, except the carbon atoms directly connected to the nitrogens of the polyamine base structure; dihydroxyalkylene of C_j.-C? 2 wherein the hydroxyl portions can occupy any two of the carbon atoms of the chain of the R unit, except those carbon atoms directly connected to the nitrogens of the polyamine base structure; dialkylarylene of Cs-C 2 which for the purpose of the present invention are arylene portions having two alkyl substituent groups as part of the linker chain. For example, a dialkylarylene unit has the formula: although the unit need not be 1, 4-substituted, but may also be 1, 2 or 1, 3-substituted with C2-C-J2 alkylene, preferably ethylene, 1, 2-propylene and mixtures thereof, most preferably ethylene. The R "oxy" units comprise - (R1O) xR5 (OR) x-, CH2CH (OR2) CH2?) Z (R0) and R (OCH2CH (OR2) CH2) w- > CH2CH (OR2) CH2-, - (R'O)? R "- and mixtures thereof. Preferred R units are C2-C12 alkylene. C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, - (R10) XR1-, -CH2CH (OR2) CH2-, - (CH2CH (OH) CH2O) z (Rl O) and Ri (OCH2CH- (OH) CH2) w-, - (R1O) XR5 (OR1) X-, most preferred R units are C2-C12 alkylene. hydroxyalkylene of C3-C-12. C4-C dihydroxyalkylene < | 2, (R10) xR1-, - (R10) xR5 (OR1) x-, (CH 2 CH (OH) CH 2 O) z (R 1 O) y R 1 (OCH 2 CH- (OH) CH 2) w- And mixtures thereof, even more preferred R units are C 1 -C 2 alkylene, C 3 hydroxyalkylene and mixtures of the very much preferred are C2-C6 alkylene. The most preferred base structures of the present invention comprise at least 50% R units that are ethylene. The R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene. R2 is hydrogen, and - (R1O) xB, preferably hydrogen.

R3 is CiC-is alkyl, C7-C2 arylalkylene, C7-C2 aryl substituted alkyl, C6-C12 aryl, and mixtures thereof, preferably C1-C12 alkyl, C7-C arylaylene. 2, most preferably CiC 2 alkyl, still most preferably methyl. The units R3 serve as part of the units R 'described below. R 4 is C 1 -C 12 alkylene, C -C 2 alkenylene, C 8 -Ci 2 arylalkylene, C 6 -C 0 arylene, preferably C 1 -C 6 alkylene, C 8 -C 2 arylalkylene, most preferably C 2 alkylene. -C8, still very preferably ethylene or butylene. R 5 is C 1 -C 2 alkylene, C 3 -C 2 hydroxyalkylene, C 4 -C 12 dihydroxyalkylene, C 8 -C 12 dialkylarylene, -C (O) -, -C (0) NHR 6 NHC (0) - , -C (0) (R4) rC (0) -, -R1 (OR1) -, CH2CH (OH) CH2O (R1O) and R1OCH2CH (OH) CH2-, C (O) (R4) rC (O) -, - CH2CH (OH) CH2-, R5 is preferably ethylene, -C (O) -, C (O) NHR6NHC (O) -, -R1 (OR1) -, -CH2CH (OH) CH2-, -CH2CH (OH) CH2O (R1O) and R1OCH2CH- (OH) CH2-, most preferably -CH2CH (OH) CH2-. R6 is C2-C2 alkylene or C6-C2 arylene. The preferred R "oxy" units are further defined in terms of the units R ^, R2 and R5. The preferred R "oxy" units comprise the preferred R1, R2 and R5. Preferred polyamine soil release agents of the present invention comprise at least 50% of R ^ units which are ethylene. The R- units! , R2 and R ^ are combined with the R "oxy" units to produce the preferred R "oxy" units in the following manner. i) Substituting the most preferred R5 for (CH2CH2?) XR5 (OCH2CH2) x- (CH2CH2?) XCH2CHOHCH2- (OCH2CH2) x- is produced. ii) Substituting preferred R1 and R2 for (CH CH (OR2) CH2O) z- (R1?) And R1 (CH2CH (OR2) CH2) w- is produced - (CH2CH (OH) CH2O) z- (CH2CH2O) and CH2CH2O (CH2CH (OH) CH2) w-. iii) Substituting preferred R2 for -CH2CH (OR) CH2- produces -CH2CH (OH) CH2-. The R 'units are selected from the group consisting of hydrogen, C?-C22 alkyl, C3-C22 alkenyl, C ar22 arylalkyl, C2-C22 hydroxyalkyl, - (CH2) pCO2M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, - (CH2) pP03M, - (R10) mB, -C (0) R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C22 alkylene, - (R10) mB, -C (0) R3, - (CH2) PC02M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, most preferably C22 alkylene, - (R1O) xB, -C (O) R3, - (CH2) pCO2M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, most preferably C al-C22 alkylene, - (R10) xB, and -C (0) R3. When a modification or substitution is not made on a nitrogen then the hydrogen atom will remain as the portion representing R '. An extremely preferred unit R 'is (R1O) xB.

The units R 'do not comprise a hydrogen atom when the units V, W or Z are oxidized, that is, the nitrogens are N-oxides. For example, the chain of the base structure or branching chains does not comprise units of the following structure: Additionally, the R 'units do not comprise carbonyl moieties directly attached to a nitrogen atom when the units V, W and Z are oxidized, that is, the nitrogens are N-oxides. According to the present invention, the portion -C (O) R3 of the unit R 'is not bound to a nitrogen modified by N-oxide, that is, there are no N-oxide amides having the structure: 0 combinations thereof. B is hydrogen, CrCe alkyl, - (CH2) qSO3M, - (CH2) pCO2M, - (CH2) q- (CHSO3M) CH2SO3M, - (CH2) q (CHSO2M) CH2SO3M, - (CH2) pPO3M, -PO3M, preferably hydrogen, - (CH2) qSO3M, - (CH2) q (CHSO3M) CH2SO3M, - (CH2) q (CHSO2M) CH2SO3M, most preferably hydrogen or - (CH2) qSO3M. M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the charge equilibrium. For example, a sodium cation also satisfies - (CH2) PC02M, and - (CH2) qS03M, thus resulting in portions - (CH2) pC? 2Na, and - (CH2) qS03Na. More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge equilibrium. However, more than one anionic group can be balanced in charge by a divalent cation, or more than one monovalent cation will be necessary to satisfy the loading requirements of a polyanionic radical. For example, a - (CH2) pPO3M portion substituted with sodium atoms has the formula - (CH2) pP03Na3. Divalent cations such as calcium (Ca2 +) or magnesium (Mg2 +) may be substituted or combined with other water-soluble monovalent cations. The preferred cations are sodium and potassium, most preferably sodium. X is a water-soluble anion such as chlorine (CI "), bromine (Br") and iodine (I ") or X can be any negatively charged radicals such as sulfate (SO42") and methosulfate (CH3SO3"). The formula has the following values: p has the value of 1 to 6, q has the value of 0 to 6, r has the value of 0 or 1, w has the value of 0 or 1, x has the value of 1 to 100 and has the value from 0 to 100, z has the value 0 or 1, m has the value from 2 to 700, preferably from 4 to 400, n has the value from 0 to 350, preferably from 0 to 200; n has the value of at least 5. Preferably, x has a value that is on the scale of 1 to 20, preferably 1 to 10.

Preferred amino-functional polymers of the present invention comprise polyamine base structures wherein less than 50% of the R groups comprise R "oxy" units, preferably less than %, most preferably less than 5%, still most preferably the R units do not comprise R "oxy" units. More preferred amino-functional polymers that do not comprise R "oxy" units comprise polyamine base structures wherein less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3 or fewer carbon atoms and are the preferred "hydrocarbyl" R units. This is when the R units of the base structure are C2-C12 alkylene, the C2-C3 alkylene is preferred, and most preferably ethylene. The amino-functional polymers of the present invention comprise homogeneous or non-homogeneous polyamine base structures, wherein 100% or less of the -NH units are modified. For the purpose of the present invention, the term "homogeneous polyamine base structure" is defined as a polyamine base structure having R units that are the same (ie, all are ethylene). However, this definition of equality does not exclude polyamines comprising other foreign units that comprise the polymer base structure that are present thanks to an artifact of the chosen method of chemical synthesis. For example, it is known to those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polyethylene imines, therefore a polyethylene imine sample comprising a hydroxyethyl portion resulting from the polymerization of an "initiator" would be considered comprising a homogeneous polyamine base structure for the purposes of the present invention. A base structure comprising all the ethylene units R where no branching Y units are present is a homogeneous base structure. A polyamine base structure comprising all the ethylene units R is a homogeneous base structure 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 base structure" refers to polyamine base structures that are a mixed material of various lengths of unit R and types of unit R. For example, an inhomogeneous base structure 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" units R is not necessary to provide a non-homogeneous base structure. Preferred amino-functional polymers of the present invention comprise homogeneous polyamine base structures that are totally or partially substituted by polyethyleneoxy moieties, total or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides and mixtures thereof. However, not all amine nitrogens in the base structure should be modified in the same way, the selection of modification should be made based on the specific needs of the formulator. The degree of ethoxylation is also determined by the specific requirements of the formulator. Preferred polyamines comprising the base structure of the compounds of the present invention are generally polyalkylene imines (PAI's), preferably polyethylene imines (PEI's), or PEI's connected in portions having longer R units than PAI's or PEI's progenitors. Preferred amine polymer base structures comprise R units which are C2 alkylene (ethylene) units, also known as polyethylene imines (PEI's). The preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4: 1, however the PEI's having a m to n ratio of 2: 1 are preferred. The preferred base structures, before modification, have the general formula: R i "I I [R2NCH2CH2] n - [NCH2CH2] m- [NCH2CH2] n- NR2 where R ', m and n are the same as previously defined. Preferred PEIs will have a molecular weight of more than 200 daltons. The relative proportions of primary, secondary and tertiary amine units in the polyamine base structure, especially in the case of PEI, will vary, depending on the manner of preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine base structure chain represents a potential site for substitution, quaternization or subsequent oxidation. These polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine base structures are presented in the U.S. patent. 2,182,306 Ulrich et al., Issued December 5, 1939; patent of E.U.A. 3,033,746, Mayle et al., Issued May 8, 1962; patent of E.U.A. 2,208,095, Esselmann et al., Issued July 16, 1940; patent of E.U.A. 2,806,839, Crowther, issued September 17, 1957; and patent of E.U.A. 2,553,696, Wilson, issued May 21, 1951; all incorporated herein by way of reference. Examples of amino-functional polymers comprising PEI's are illustrated in formulas I-IV: Formula I illustrates an amino-functional polymer comprising a base structure of PEI in which all substitutable nitrogens are modified by replacement of the hydrogen with a polyoxyalkylenoxy unit, - (CH 2 CH 2 O) H, having the formula: Formula I This is an example of an amino-functional polymer that is completely modified by a type of portion. Formula II illustrates an amino-functional polymer comprising a PEI base structure in which all substitutable nitrogens are modified by replacing hydrogen with a polyoxyalkylenoxy unit, - (CH2CH2O) 2H, then the molecule is modified by subsequent oxidation of all the primary oxidizable nitrogens and secondary to N-oxides, said polymer has the formula: Formula II Formula III illustrates an amino-functional polymer comprising a PEI base structure in which all of the nitrogen atoms of the base structure are substituted and some amine units of the base structure are quaternized. The substituents are polyoxyalkylenoxy units, - (CH CH O) 7H, or methyl groups. The modified PEI has the formula: Formula Formula IV illustrates an amino-functional polymer comprising a base structure of PEI in which the nitrogens of the base structure are modified by substitution (ie, by - (CH2CH2?) 3H or methyl), quaternized, oxidized to N-oxides or combinations thereof. The resulting polymer has the formula: Formula IV In the previous examples, not all the nitrogens of a unit class comprise the same modification. The present invention allows the formulator to have a portion of the nitrogens of the ethoxylated secondary amine while having the other nitrogens of the secondary amine oxidized to N-oxides. This also applies to the nitrogens of the primary amine, since the formulator may choose to modify all or a portion of the nitrogens of the primary amine with one or more substituents before oxidation or quaternization. Any possible combination of R 'groups can be substituted on the nitrogens of the primary or secondary amine, except for the restrictions described hereinabove.

The commercially available amino-functional polymer suitable for use herein is poly (ethyleneimine) with a MW 1200, hydroxyethylated poly (ethyleneimine) from Polysciences, with a MW 2000, and 80% hydroxyethylated poly (ethyleneimine) from Aldrich. A typical amount of amino-functional polymer that can be employed in the composition of the present invention is preferably up to 90% by weight, preferably from 0.01 to 50% by weight, most preferably from 0.1% to 20% by weight, and preferred from 0.5% to 15% by weight of the composition.

Crystal growth inhibitor A crystal growth inhibitor (CGI) is an essential component of the invention. By "crystal growth inhibitor" is meant a compound that reduces the rate of formation of inorganic microcrystals, thereby reducing the size and / or amount of said microcrystals on the surface of the fabrics. The CGl suitable for use herein can be defined by the following test procedure, called a test to measure the inhibition of crystal growth.

Test to measure the inhibition of crystal growth The ability of a compound to inhibit crystal growth can be obtained by evaluating the in vitro impact on the growth rate of inorganic microcrystals. For this purpose, a system developed by G. H. Nancollas in 1964, described in Nancollas, G. H. and Koutsoukos, P. G. "Calcium Phosphate Nucleation and Growth in solution" can be used. Proq. Crvstal Growth Charact. 3.77-102 (1980). This system consists of measuring the growth rate of calcium phosphate crystals seeded with hydroxyapatite ([Ca5 (PO) OH] or HAP) in the presence of CaCl2 and NaH2PO4. The growth of calcium phosphate releases protons that can be titrated with a strong base. The amount of base necessary to keep the pH constant over the crystal growth allows those skilled in the art to measure the rate of crystal growth directly as well as to determine the effects of the potential crystal growth rate inhibitors. A typical graph of said experiment is shown in Figure 1. The t-delay value defines the efficiency of a compound to inhibit the growth of calcium phosphate crystals; where the greater the t-delay, the better CGl. The following procedure can be used to build the graph of Figure 1 experimentally: Place 350 ml of distilled water (distilled twice), 35 ml of 2.1 M KCl, 50 ml of CaCl2 0.0175M and 50 ml of 0.01 M KH2PO in a reaction vessel. Insert a glass pH electrode and a standard calomel reference electrode connected to a self-titrator. Bubble gaseous nitrogen and stabilize the temperature of the reaction mixture at 37 ° C. When the temperature and pH stabilize, add the candidate CGl to the concentration to be tested (eg, 1.10"6M), titrate to a pH of 7.4 with 0.05M KOH, then sow the reaction mixture with 5 ml of Hydroxyapatite suspension [Ca5 (P0) OH] The hydroxyapatite suspension is prepared as follows: 100 g of hydroxyapatite powder Bio-Gel® HTP is dispersed in 1 liter of distilled water The pH of the resulting suspension is reduced to 2.5 by dropwise addition of 6N HCl The above is heated to boiling and refluxed by stirring for seven days in a 2L round bottom flask connected to a condenser.After cooling, at room temperature, the pH is adjusted to 12.0 by dropwise addition of 50% NaOH and the suspension is refluxed for another seven days as before.The suspension is allowed to stand for two days and the supernatant is sucked in. The flask is filled with 1.5L of distilled water, stirred vigorously, and let it rest again for two days. A total of seven rinses are performed as described above. The pH is adjusted to 7.0 by dropwise addition of 2N HCl while stirring vigorously. The resulting suspension is stored at 37 ° C for eleven months. The graph shown in Figure 1 is obtained by recording the amount of base added over time to maintain the pH of the reaction medium. The t-delay for a particular crystal growth inhibitor is determined graphically as described in Figure 1.

The crystal growth inhibitors to be used for the purpose of the invention have a t-delay of at least 10 minutes at a concentration of 1.10"6M, preferably at least 20 minutes, most preferably at least 50 minutes. Appropriate method to determine the crystal growth inhibition property of the selected component that is compared with the T-delay method is by visual qualification.The method is as indicated: A multi-cycle laundry test is performed over several cycles ( for example 10) repeated washing and drying in machine The conditions used are representative of the desired geographical region (for example, household washing machine used, detergent used, product use with added paint, water hardness, washed items, etc. At least two sections are run in parallel, including the composition of the invention and a separate reference section. To carry out the required number of washing cycles, the test garments (articles of clothing) are taken for comparison by qualified experts under controlled lighting conditions. The visual qualification is a better / worse comparison of the crystalline residue visible on the surface of the test garments, comparing the test section with the reference section. Woven cotton items in dark colors are the best suited to make this comparison.

In addition, crystal growth inhibitors differ from chelating agents because of their low binding affinity for copper defined by their Log K, ie ML / ML Log K at 25C, 0.1 ionic strength, CGl is less Of 15, preferably less than 12. Preferably, the CGl for use in the present invention is selected from the carboxylic compounds, organomonophosphonic acids, organodiphosphonic acids, and mixtures thereof.

Carboxylic Compounds Typical carboxylic compounds for use herein are the carboxylic compounds selected from glycolic acid, phytic acid, monomeric polycarboxylic acids, homo or copolymeric polycarboxylic acids or their salts wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by no more than two carbon atoms. When used in the salt form, alkali metals, such as sodium, potassium and lithium salts, or alkanolammonium are preferred. CGl organic detergents suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate CGl can generally be added to the composition in acid form, but it can also be added in the form of a neutralized salt. When used in salt form, alkali metals, such as sodium, potassium, and lithium or alkanolammonium salts are preferred. Included among the polycarboxylate CGIs is a variety of useful material categories. An important category of polycarboxylate CGIs comprises the ether polycarboxylates, including oxydisuccinate, as described in the U.S.A. 3,128,287 and patent of E.U.A. 3,635,830. See also CGI "TMS / TDS" of the US patent. 4,663,071. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patents. numbers 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful CGl include ether hydroxypolycarboxylates, polyacrylate polymers, maleic anhydride copolymers with ethylene or vinyl methyl ether, or acrylic acid, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the different alkali metals , ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and salts soluble of them.

The molecular weight for these polymers and copolymers is preferably less than 100,000, most preferably between 500 and 50,000. Commercially available polymers, suitable for use herein, which prevent the precipitation of salts of the regulatory component after dissolution of the composition in water are the polyacrylate polymers sold under the tradename Good-Rite® from Goodrich, Acrysol® from Rohm & Haas, Sokalan® by BASF, Norasol® by Norso Haas. The commercially available preferred polymers are the polyacrylate polymers, especially the Norasol® polyacrylate polymers and most preferably the polyacrylate polymers Norasol® 410N (PM 10,000) and the polyacrylate polymer modified with aminophosphonic groups Norasol® 440N (PM 4000) and their form corresponding acid Norasol® QR 784 (PM 4000) from Norso-Haas. The citrates, for example, citric acid and soluble salts thereof (particularly sodium salt), are suitable polycarboxylate CGI for use herein. Also suitable in the compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds presented in the US patent. 4,566,984. A CG1 of suitable succinic acid includes the succinic alkyl and C5-C2o alkenyl acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate GCIs include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred CGIs of this group, and are described in EP 0,200,263. Other suitable polycarboxylates are presented in the patent of E.U.A. No. 4,144,226 and in the patent of E.U.A. No. 3,308,067. See also patent of E.U.A. No. 3,723,322.

Organomonophosphonic acid Organomonophosphonic acid or one of its salts or complexes are also suitable for use as a CGI. Organomonophosphonic acid refers herein to an organomonophosphonic acid that does not contain nitrogen as part of its chemical structure. As a consequence, this definition excludes organo-aminophosphonates, which, however, can be included in compositions of the invention as heavy metal ion sequestrants. The organomonophosphonic acid may be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation. Preferably any salt / complex is soluble in water, with the salts / complexes of alkali metal and alkaline earth metal being especially preferred.

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

Organophosphonic acid Organodiphosphonic acid or one of its salts or complexes are also suitable for use herein as a CGI. By "organo diphosphonic acid" is meant herein an organodiphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition also excludes organo-aminophosphonates which, however, can be included in the compositions of the invention as heavy metal ion sequestrants. The organodiphosphonic acid component can be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation. Preferably, any salt / complex is soluble in water, the alkali metal and alkaline earth metal salts / complexes being preferred. The organodiphosphonic acid is preferably a diphosphonic acid of C -? - C4 and most preferably a diphosphonic acid of C2 selected from ethylene diphosphonic acid, a-hydroxy-2-phenylethyldiphosphonic acid, methylenediphosphonic acid, vinylidene 1,1-diphosphonic acid, 1,2-acid. 1, 1 diphosphonic dihydroxyethane and 1, 1 diphosphonic hydroxy-ethane acid and any salt thereof and mixtures thereof.

A preferred organodiphosphonic acid is hydroxy-1-diphosphonic acid (HEDP). Among the CGl classes described above, the preferred classes for use herein are the classes of organomonophosphonic acids and / or organodiphosphonic acids. For the proposed invention, when a CG1 is selected from carboxylic acid, organodiphosphonic acid, and mixtures thereof, the CGl is presented at a level of less than 1%, preferably 0.005% at 0. 5%, most preferably from 0.05% to 0.50%, still most preferably from 0.1% to 0.2% by weight of the composition. Typical levels for CGI components other than carboxylic acid, organodiphosphonic acid, and mixtures thereof, such as organomonophosphonic acid, are in an amount of less than 10%, most preferably from 0.005% to 0.50%, still most preferably 0.1% at 0.2% by weight of the composition. Preferably for the purpose of the invention, the stabilization of the polyamino-functional polymer-containing composition is better stabilized when a weight ratio of said CGI to said polymer is present from 0.005: 1 to 0.5: 1, preferably from 0.01: 1 to 0.1: 1. The composition of the invention can be used in the product only including pre- or post-wash additives. It can also be used and used in combination formulated compositions including laundry compositions as well as fabric softener compositions with added rinse and compositions with aggregate dryers (eg, sheets) that provide softness and / or antistatic benefits, and compositions with added rinse. The composition may comprise optional ingredients such as a dye fixing agent, a fabric softening compound and other optional ingredients.

Dye binding agent The composition of the invention may optionally comprise a dye binding agent. Dye fixing agents, or "fixatives", are well known, and are commercially available materials that are designed to improve the appearance of dyed fabrics by minimizing the loss of dye from fabrics due to washing. Within this definition, the components that are fabric softeners or those described above as amino-functional polymers are not included. Many dye fixing agents are cationic, and are based on various quaternized compounds or cationically charged organic nitrogen compounds. Cationic fixatives are available under various trade names from different suppliers. Representative examples include CROSCOLOR PMF (July 1981, code No. 7894) and CROSCOLOR NOFF (January 1988, code No. 8544) from Crosfield; INDOSOL E-50 (February 27, 1984, reference no 6008.35.84, based on polyethyleneamine) from Sandoz; SANDOFIX TPS, which is also available from Sandoz and is a preferred polycationic fixative for use herein and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWIN SRF-O 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 "Aftertreatments for improving the fastness of dyes on textile fibers" by Christopher C. Cook (REV PROG. COLORATION Vol. 12, 1982). Dye binding agents suitable for use in the present invention are ammonium compounds such as diamine-fatty acid condensates for example hydrochloride, acetate, methosulphate and benzyl hydrochloride of oleyldiethyl aminoethylamide, oleylmethyldietilenediamine methosulfate, mono-stearylethylenediaminotrimethylammonium methosulfate and oxidized products of tertiary amines; derivatives of polymeric alkyldiamines, condensates of polyamine-cyanuric chloride and glycerol aminated dichlorohydrins. A typical amount of the dye fixing agent that will be employed in the composition of the invention is preferable up to 90% by weight, preferably up to 50% by weight, most preferably from 0.001% to 10% by weight, still very preferably 0.5% to 5% by weight of the composition. The composition of the invention can also be formulated as a fabric softening composition. Also, when formulated as a softening composition, it will comprise a fabric softening compound.

Fabric Softening Compound The typical fabric softening compound incorporation levels in the softening composition are from 1% to 80% by weight, preferably from 5% to 75%, most preferably from 15% to 70% and still more preferably from 19% to 65%, by weight of the composition. The fabric softening compound is preferably selected from a cationic, non-ionic, amphoteric or anionic fabric softening component. Typical cationic softening components are the quaternary ammonium compounds or amine precursors thereof as defined hereinafter.

A) Quaternary ammonium fabric softening active compound (1) The preferred quaternary ammonium fabric softening active compound has the formula: or the formula: where Q is a carbonyl unit having the formula: ooo R2 OO R2 II II II II I -o-c- -c- -o-C- 'NI-C ?? - -c- each R unit is independently hydrogen, C? -C6 alkyl, hydroxyalkyl of C? -C6 and mixtures thereof, preferably methyl or hydroxyalkyl; each R1 unit is independently linear or branched C-n-C22 alkyl, linear or branched Cn-C22 alkenyl and mixtures thereof; R 2 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and mixtures thereof; X is an anion that is compatible with active fabric softener and auxiliary ingredients; the index m is from 1 to 4, preferably 2; the index n is from 1 to 4, preferably 2. An example of a fabric softening active that is preferred is a mixture of quaternized amines having the formula: wherein R is preferably methyl; R1 is a linear or branched alkyl or alkenyl chain comprising at least 1 1 carbon atoms, preference for at least 15 atoms. In the above fabric softener example, the -O2CR1 unit represents a fatty acyl unit that is typically derived from a triglyceride source. The source of triglycerides is preferably derived from tallow, partially hydrogenated tallow, lard, partially hydrogenated butter, vegetable and / or partially hydrogenated vegetable , such as canola safflower peanut sunflower corn, soybean wood rice bran etcetera and mixtures thereof. The fabric softening actives which are preferred in the present invention are the diester and / or diamide quaternary ammonium compounds (DEQA), the diesters and diamides having the formula: wherein R, R1, X and n are the same as those defined hereinabove for formulas (1) and (2), and Q has the formula: These preferred fabric softening actives are formed from the reaction of an amine with a fatty acyl unit to form an amine intermediate having the formula: R- -N- - (CH2) n-Q-R1 wherein R is preferably methyl, Q and R 'are as defined above; followed by quaternization until the final softening active. Non-limiting examples of the preferred amines that are used to form the fabric softening actives of DEQA according to the present invention include methyl-bis (2-hydroxyethyl) amine having the formula: methyl-bis (2-hydroxypropyl) amine having the formula: methyl- (3-aminopropyl) (2-hydroxyethyl) amine having the formula: methyl-bis (2-aminoethyl) amine having the formula: triethanolamine that has the formula: di (2-aminoethyl) ethanolamine having the formula: The above X (_) counter ion can be any anion compatible with softener, preferably the anion of a strong acid, for example, chloride, bromide, methylisulfate, etiisulfate, sulfate, nitrate and the like, most preferably chloride or methylisulfate. The anion can also, but is less preferred, carry a double charge in which case XH represents half of a group. Tallow and cane are convenient and inexpensive sources of fatty acyl units which are suitable for use in the present invention as R7 units. The following are non-limiting examples of quaternary amino compounds suitable for use in the compositions of the present invention. The term "seboyl" as used hereinbefore indicates that unit R1 is derived from a source of tallow triglycerides and is a mixture of fatty acyl units. Also, the use of the term canolyl refers to a mixture of fatty acyl units derived from canola TABLE I Fabric softening assets N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride; N, N-di (canolyl-oxy-ethyl) -N, N-dimethylammonium chloride; N, N-di (tallowyl-oxy-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-tallowoyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N-di (2-canolyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium chloride; N, N-di (2-canolyloxyethylcarbonylloxyethyl) -N, N-dimethylammonium chloride; N- (2-tallowoyloxy-2-ethyl) -N- (2-tallowoyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N- (2-canolyloxy-2-ethyl) -N- (2-cyanoyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N, N-tri (seborl-oxy-ethyl) -N-methylammonium chloride; N, N, N-tri (canolyl-oxy-ethyl) -N-methylammonium chloride; N- (2-tallowoyloxy-2-oxoethyl) -N- (tallowyl) -N, N-dimethylammonium chloride; N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N, N-dimethylammonium chloride; Chloride of 1,2-diploboyloxy-3-N, N, N-trimethylammoniopropane; 1, 2-Decanoyloxy-3-N, N, N-trimethylammonopropane Chloride and mixtures of the above assets. Other examples of quaternary ammonium softening compounds are methylbis (tallowamidoethyl) (2-hydroxyethyl) ammonium methylisulfate and methylbis methylisulfate (hydrogenated tallow amidoethyl) (2-hydroxyethyl) ammonium methylisulfate; these materials are available from Witco Chemical Company under the tradenames Varisoft® 222 and Varisoft® 110, respectively. N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride is particularly preferred, where the tallow chains are at least partially unsaturated. The level of unsaturation contained within tallow, canola or other acyl fatty acid chain can be measured by the corresponding iodine (IV) value of the fatty acid, which in the present case should preferably be in the range of 5 to 100, distinguishing two categories of compounds that have an IV of less than or more than 25. In fact, for compounds that have the formula: tallow fatty acid derivatives, when the Iodine Value is from 5 to 25, preferably 15 to 20, it has been found that a weight ratio of the cis / trans isomer of more than about 30/70, preferably more than about 50 / 50 and most preferably more than about 70/30, provides optimum concentration ability. For compounds of this type made from tallow fatty acids having an Iodine Value of more than 25, the ratio of cis to trans isomers has been found to be less critical, unless very high concentrations are required. Other suitable examples of fabric softening actives are derived from fatty acyl groups in which the terms "seboyl" and "canolyl" in the above examples are replaced by the terms "cocoyl, palmetto, lauryl, oleyl, ricinoleyl, stearyl, palmityl" , which correspond to the source of triglycerides from which the fatty acyl units are derived. These alternative fatty acyl sources can comprise chains either completely saturated, or preferably at least partially unsaturated. As described hereinabove, the R units are preferably methyl, however, suitable fabric softening actives are described by replacing the term "methyl" in the above examples of Table II with the "ethyl, ethoxy, propyl, propoxy" units , Sopropyl, butyl, isobutyl and t-butyl ". The counter on X in the examples of Table II can be suitably replaced by bromide, methylisulfate, formate, sulfate, nitrate and mixtures thereof. In fact, the X anion is present simply as a counter ion of the positively charged quaternary amino compounds. The scope of this invention is not considered limited to any particular anion. For the above ester fabric softening agents, the pH of the compositions herein is an important parameter of the present invention. In fact, it influences the stability of the quaternary ammonium compounds or amine precursors, especially under conditions of prolonged storage. The pH, as defined in the present context, is measured in the concentrated compositions at 20 ° C. Although these compositions can operate at a pH of less than about 6.0, for optimal hydrolytic stability of these compositions, the concentrated pH, measured under the conditions mentioned above, should preferably be in the range of about 2.0 to 5, preferably in the range of 2.5 to 4.5, preferably around 2.5 to about 3.5 . The pH of the compositions herein can be regulated by the addition of a Bronsted acid. Examples of suitable acids include inorganic mineral acids, carboxylic acids, in particular low molecular weight (C 1 -C 5) carboxylic acids and alkylsulfonic acids. Suitable inorganic acids include HCl, H2SO4, HNO3 and H3PO4. Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulphonic acids. The acids that are preferred are citric, hydrochloric, phosphoric, formic, methylsulphonic and benzoic acids. As used herein, when the diester is specified, it will include the monoester which is normally present in the manufacture. For smoothing, under laundry conditions of low or no detergency, the percentage of monoester should be as low as possible, preferably not more than about 2.5%. However, under conditions of high detergency, some monoester is preferred. The general ratios of diester to monoester are from about 100: 1 to about 2: 1, preferably about 50: 1 to about 5: 1, most preferably about 13: 1 to about 8: 1. Under conditions of high detergency, the di / monoester ratio is preferably about 11: 1. The level of monoester present can be controlled in the manufacture of the softening compound. Mixtures of the active compounds of the formula (1) and (2) can also be prepared. 2) Other quaternary ammonium fabric softening compounds suitable for use herein are cationic nitrogen salts having two or more C8-C22 long chain aliphatic and acyclic hydrocarbon groups, or one such group and an arylalkyl group which can be used alone or as part of a mixture are selected from the group consisting of: (i) acyclic quaternary ammonium salts having the formula: wherein R 4 is an acyclic and aliphatic C 8 -C 22 hydrocarbon group, R 5 is an alkyl or hydroxyalkyl group of C 1 -C 4, R 8 is selected from the group consisting of groups R 4 and R 5, and A- is an anion as defined above; (I) diamino alkoxylated quaternary ammonium salts having the formula: wherein n is equal to 1 to about 5, and R1, R2, R5 and A "are as defined above; (ii) mixtures thereof Examples of the cationic nitrogen salts of the above class are the well-known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methylisulfate, di (hydrogenated tallow) dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. di (hydrogenated tallow) dimethylammonium and ditallowdimethylammonium chloride Examples of commercially available diakyldimethylammonium salts useful in the present invention are di (hydrogenated tallow) dimethylammonium chloride (trade name Adogen® 442), ditallowdimethylammonium chloride (trade name Adogen®, Praepagen ® 3445), distearyldimethylammonium chloride (trade name Arosurf® TA-100), all available from Witco Chemical Com The dibenzyldimethylammonium chloride is sold under the tradename Kemamine Q-2802C by Humko Chemical Division of Witco Chemical Corporation. Dimethylstearylbenzylammonium chloride is sold under the trade names Varisoft® SDC by Witco Chemical Company and Ammonyx® 490 by Onyx Chemical Company.

B) Amine Fabric Softening Active Compound Amine fabric softening compounds suitable for use herein, which may be in the form of amine or cationic form, are selected from: i) reaction products of higher fatty acids with a polyamine selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof. These reaction products are mixtures of several compounds in view of the multifunctional structure of the polyamines. The component i) that is preferred is a nitrogen compound selected from the group consisting of the reaction product mixtures or of some selected components of the mixtures. A component i) that is preferred is a compound selected from the group consisting of substituted imidazoline compounds having the formula: wherein R7 is an acyclic and aliphatic C15-C21 hydrocarbon group and R8 is an alkylene group of divalent C-? -C3.

The materials of component i) are commercially available as: Mazamide® 6, sold by Mazer Chemicals or Ceranine® HC, sold by Sandoz Colors & Chemicals; stearic hydroxyethyl imidazoline sold under the trade names of Alkazine® ST by Alkaril Chemicals Inc., or Schercozoline® S by Scher Chemicals, Inc .; N, N "-diseboalcoildiethylene triamine; 1-tallowyldoxy-2-tallowamidazole (wherein in the above structure R1 is an aliphatic C15-C- | 7 hydrocarbon group and R8 is a divalent ethylene group) Certain of the components i) may also be dispersed first in a Bronsted acid dispersion auxiliary having a pKa value of no more than about 4, as long as the pH of the final composition is not greater than about 6. Some Preferred dispersion aids are hydrochloric acid, phosphoric acid or methylsulfonic acid, both N, N "-diseboalkylidenetrimamine and l-tallow (amidoethyl) -2-seboimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methylene-1-tallowamidoethyl-2-tallowamidazolinium methylisulfate (see "Cationic Surface Active Agents as Fabrics Softeners", RR Egan, Journal of the American Oil Chemicals' Society, January 1978, page Nos. 118-121). N, N "-diseboalcoildiethylenetriamine and 1-tallowamidoethyl-2-seboimidazole can be obtained from the Witco Chemical Company as experimental chemicals.Methyl-1-tallowamidoethyl-2-tallowamidazolinium methylisulfate is sold by Witco Chemical Company under the trade name Varisoft® 475. ii) softener that has the formula: wherein each R 2 is an alkylene group of d-6, preferably an ethylene group; and G is an oxygen atom a group -NR-; and each R, R1, R2 and R5 has the definitions given above and A "has the definitions given above for X". An example of compound ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride, wherein R1 is an acyclic and aliphatic C-? 5-C? 7 hydrocarbon, R2 is an ethylene group, G is an NH group, R5 is a methyl group and A "is a chloride anion. i) softener that has the formula: wherein R, R > 1, D R2 and A "are as defined above.

An example of compound iii) is the compound having the formula: wherein R1 is derived from oleic acid. The additional fabric softening agents useful herein are described in the U.S.A. No. 4,661, 269, issued April 28, 1987, in the names of Toan Trinh, Errol H. Wahl, Donald M. Swartley and Ronald L. Hemingway; U.S. Patent 4,439,335, Burns, issued March 27, 1984; and in the patents of E.U.A. Nos. 3,861, 870, Edwards and Diehl; 4,308,151, Cambre; 3,886,075, Bernardino; 4,233,164, Davis; 4,401, 578, Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016, Rudkin, Clint and Young; European patent application no. of publication 472,178, by Yamamura et al., All these documents being incorporated herein by way of reference. Of course, the term "softening active" may also encompass mixed softening active agents. Among the classes of softening compounds that are preferred described hereinbefore are the diester or diamide quaternary ammonium ammonium fabric softening active compound (DEQA).

The fabric softening compositions formulated in combination may contain, in addition to the components previously described herein, one or more of the following ingredients.

Optional ingredients (A) Liquid vehicle An optional but preferred ingredient is a liquid vehicle. The liquid vehicle used in the present compositions is preferably at least mainly water due to its low cost, relative availability, safety and environmental compatibility. The level of water in the liquid vehicle is preferably at least about 50%, more preferably at least about 60%, by weight of the vehicle. Useful as the liquid carrier are low molecular weight organic water and solvent mixtures, for example, about 200, for example, lower alcohols such as ethanol, propanol, sodium propane or butanol. Low molecular weight alcohols include monohydric, dihydric (glycol, etc.), trihydric (glycerol, etc.) and higher polyhydric (polyols) alcohols.

(B) Additional solvents The compositions of the present invention may comprise one or more solvents that provide increased formulation ease.

These easy-to-formulate solvents are all described in WO 97/03169. This is particularly the case when formulating liquid compositions and clear fabric softeners. When employed, the formulation ease solvent system preferably comprises less than about 40%, preferably about 10% to about 35%, most preferably about 12% to about 25%, and even more preferably about 14% to about 20%, by weight of the composition. The formulation ease solvent is selected to minimize the impact of solvent odor on the composition, and to provide a low viscosity to the final composition. For example, isopropyl alcohol is not very effective and has a strong odor. N-propyl alcohol is more effective, but it also has a distinctive odor. Various butyl alcohols also have odors but can be used for effective clarity / stability, especially when used as part of a formulation ease solvent system to minimize odor. Alcohols are also selected for optimum stability at low temperatures, ie they are capable of forming compositions that are liquid with low acceptable viscosities and translucent, preferably clear, up to 4.4 ° C, and are capable of recovering after storage to -6.7 ° C. The suitability of any major solvent for the formulation of the liquid, concentrated, preferably clear fabric softening compositions of the present with the necessary stability is surprisingly selective. Suitable solvents can be selected based on their octanol / water (P) separation coefficient as defined in WO 97/03169. The easy formulation solvents of the present are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62 and most preferably from about 0.40 to about 0.60, said ease of formulation solvent being preferably at least a little asymmetric, and preferably having a melting point or solidification that allows it to be liquid at or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes. The most asymmetric solvents appear to be very desirable, while highly symmetrical solvents, such as 1,7-heptanediol or 1,4-bis (hydroxymethyl) cyclohexane, which have a center of symmetry, appear to be unable to provide the essential clear compositions when used alone, even though their ClogP values are on the preferred scale. The most preferred easy-to-formulate solvents can be identified by the appearance of the softener vesicles, as observed by cryogenic electron microscopy of the compositions that have been diluted to the concentration used in the rinse. These diluted compositions appear to have fabric softener dispersions that exhibit a more unilamellar appearance than conventional fabric softener compositions. The more unilaminar the appearance, the better the compositions seem to act. These compositions provide surprisingly good fabric softening compared to similar compositions prepared in the conventional manner with the same fabric softening active. The easy-to-formulate solvents that can be used are described and listed below, which have ClogP values that are within the necessary scale. These include mono-oles, diols of C6, and diols of C7, isomers of octanediol, derivatives of butanediol, isomers of trimethylpentanediol, isomers of ethylmethylpentanediol, isomers of propylpentanediol, isomers of dimethylhexanediol, isomers of ethylhexanediol, isomers of methylheptanediol, isomers of octanediol , isanomers of nonanodiol, alkylglyceryl ethers, di (hydroxyalkyl) ethers and arylglyceryl ethers, aromatic glyceryl ethers, acrylic diols and derivatives, alkoxylated derivatives of C3-diol, aromatic diols and unsaturated diols. Particularly preferred formulation ease solvents include hexanediols such as 1,2-hexanediol; and C8 diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.

(C) Scattering Capability Auxiliary Relatively concentrated compositions can be prepared containing saturated and unsaturated diester quaternary ammonium compounds that are stable without the addition of concentration aids. However, the compositions of the present invention may require organic and / or inorganic concentration aids to obtain still higher concentrations and / or to satisfy higher stability standards, depending on the other ingredients. These concentration aids which typically can be viscosity modifiers may be required, or preferred, to ensure stability under extreme conditions when particular levels of softening active are used. The surfactant concentration aids are typically selected from the group consisting of (1) individual long chain alkyl cationic surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof. These auxiliaries are described in WO 94/20597, specifically on page 14, line 12 to page 20, row 12, which is incorporated herein by reference. When said dispersion capacity auxiliaries are present, the total level is from 2% to 25%, preferably from 3% to 17%, most preferably from 4% to 15% and still more preferably from 5% to 13% by weight of the composition. These materials may be added as part of the raw material of the active softener, (I), for example, the individual long chain alkyl cationic surfactant and / or the fatty acid which are reactants used to form the biodegradable fabric softening active as the one described above, or are added as a separate component. The total dispersion capacity auxiliary level includes any quantity that may be present as part of the component (I). Inorganic viscosity control / dispersing ability agents that can also act as or enhance the effect of surfactant concentration aids, include ionizable, water soluble salts that can also be optionally incorporated into the compositions of the present invention. A wide variety of ionizable salts can be used. Examples of suitable salts are the halides of group IA and HA of metals of the Periodic Table of the Elements, for example, calcium chloride, magnesium chloride, sodium chloride, potassium bromide and lithium chloride. Ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and then to obtain the desired viscosity. The amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the wishes of the formulator. Typical levels of the salts used to control the viscosity of the composition are from about 20 to about 20,000 parts per million (ppm), preferably from about 20 to about 11,000 ppm, by weight of the composition. Alkylene polyammonium salts may be incorporated into the composition to give viscosity control in addition to, or in place of, the above water-soluble ionizable salts. In addition, these agents can act as scavengers, forming pairs of ions with the anionic detergent of the main wash, in the rinse and on the fabrics, and can improve the yield of softness. These agents can stabilize the viscosity on a broader temperature scale, 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 are present at a level of from 0% to 2%, preferably from 0.01% to 0.2%, most preferably from 0.035% to 0.1% for antioxidants, and more preferably from 0.01% to 0.2% for reducing agents. These ensure adequate odor stability under long-term storage conditions of the compositions and compounds stored in molten form. The use of antioxidant stabilizers and reducing agent are especially critical for low aroma products (low perfume). Examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate and propylgalate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox® S-1.; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propylgalate and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox®-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BTH; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1 / GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C8-C22) of gallic acid, for example, dodecylgalate; Irganox® 1010; Irganox® 1030; Irganox® B 1171; Irganox® 1425; Irganox® 3114; Irganox® 3125 and mixtures thereof; preferably Irganox® 3125; Irganox® 1425, Irganox® 3114 and mixtures thereof; most preferably Irganox® 3125 alone. The chemical names and CAS numbers for some of the above stabilizers are listed in the following Table II.

TABLE II Antioxidant CAS-No. Chemical name used in the Federal Code of Regulations lrganox® 1010 6683-19-8 Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxy-hydroxynamate)) methane lrganox, ® ^ 1035 41484-35-9 Thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) Irganox® 1098 23128-74-7 (3,5-Di-tert-butyl-4-hydroxyhydrocinnamamide N, N ' - Hexamethylene Irganox "® ^ ^ 1171 31570-04-4 23128-74-7 Mix 1: 1 of Irganox® 1098 and lrgafos®168 Irganox, ® ^ 1425 65140-91-2 Bis (monoethyl (3,5-di- calcium tert-butyl-4-hydroxybenzyl) phosphonate lrganox "®w 3114 65140-91-2 Bis (calcium monoethyl (3,5-di-tert-butyl-4-hydroxy-benzyl) phosphonate lrganox .. ®ß '3125 34137-09-2 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid tri-ester with 1, 3,5-tris (2-hydroxyethyl) -S-triazine-2,4 , 6- (1 H, 3H, 5H) -trione lrgafos ® ^ 168 31570-04-4 Tris (2,4-di-tert-butyl-phenyl) phosphite Examples of effective reducing agents include sodium borohydride, acid hypophosphoric, Irgafos® 168 and mixtures thereof.

(E) Dirt releasing agent Dirt releasing agents are conveniently used in the compositions of the present invention. Any soil release agents known to those skilled in the art can be added to the compositions of the present invention. The polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, as hydrophobic segments to deposit on hydrophobic fibers and remain adhered to them throughout the cycle closure of washing and rinsing and, in this way, serve as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. If used, the soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%. . The following documents, all included herein by way of reference, disclose suitable soil release polymers for use in the present invention. The patent of E.U.A. No. 3,959,230 Hays, issued May 25, 1976; patent of E.U.A. No. 3,893,929 Basadur, issued July 8, 1975; patent of E.U.A. No. 4,000,093, Nicol et al., Issued December 28, 1976; patent of E.U.A. No. 4,702,857, Gosselink, issued October 27, 1987; patent of E.U.A. No. 4,968,451, Scheibel et al., Issued November 6; patent of E.U.A. No. 4,702,857, Gosselink, issued October 27, 1987; patent of E.U.A. No. 4,71 1, 730, Gosselink et al., Issued December 8, 1987; patent of E.U.A. No. 4,721, 580, Gosselink, issued January 26, 1988; patent of E.U.A. No. 4,877,896, Maldonado et al., Issued October 31, 1989; patent of E.U.A. No. 4,956,477, Gosselink et al., Issued September 11, 1990; patent of E.U.A. No. 5,415,807 Gosselink et al., Issued May 16, 1995; European patent application 0 219 048, published on April 22 by Kud, et al. Additional and suitable soil release agents are described in the US patent. No. 4,201, 824, Violland et al .; patent of E.U.A. No. 4,240,918 Lagasse et al .; patent of E.U.A. No. 4,525,524 Tung et al .; patent of E.U.A. No. 4,579,681, Ruppert et al .; patent of E.U.A. No. 4,240,918; patent of E.U.A. No. 4,787,989; patent of E.U.A. No. 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 N.V., 1974, all incorporated herein by reference. Commercially available soil release agents include METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo KK, SOKALAN material type, eg, SOKALAN HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).

(F) Bactericides Examples of bactericides used in the compositions 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 Bronoprol®, and a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyI-4-isothiazolin-3-one sold by Rohm and Haas Company under the trade name Kathon 1 to 1, 000 ppm by weight of the agent.

(G) Perfume The present invention may contain a perfume. Suitable perfumes are described in U.S. Pat. 5,500,138, said patent being incorporated herein by way of reference. As used herein, the perfume includes a fragrant substance or mixture of substances that include natural fragrances (ie, obtained by the extraction of flowers, herbs, leaves, roots, barks, wood, petals or plants), artificial ( that is, a mixture of different natural oils or oil constituents) and synthetic (that is, produced synthetically). These materials are commonly accompanied by auxiliary materials, such as fasteners, extenders, stabilizers and solvents. T auxiliaries are also included within the meaning of "perfume", as used herein. Typically, perfumes are complex mixtures of a plurality of organic compounds. The scale of the natural raw substances can encompass not only the readily volatile but also moderately volatile and slightly volatile components and that of the synthetic ones can include representative of virtually all kinds of fragrance substances, as will be evident from the following illustrative compilation : natural products, such as absolute tree moss, basil oil, citrus fruit oils (such as bergamot oil, tangerine oil, etc.) absolute mastix, myrtle oil, palmarrosa oil, patchouli oil, oil of petigran of Paraguay, wood worm oil; alcohols, such as famesol, geraniol, linalool, nerol, phenylethyl alcohol, rodinol, cinnamic alcohol; aldehydes, such as citral, Helional ™, alphahexylcinnamaldehyde, hydroxycitronellal, Lilial ™ (p-tert-butyl-alpha-methyldihydrocinnamaldehyde), methiinonylacetaldehyde; ketones such as allylonone, alfayonone, betayonone, isoraldein (isomethyl-alpha-yonone), metilyonone; esters, such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxide, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, ethyl acetate, linalyl, methyl dihydrojasmonate, styrallylacetate, vetyveryl acetate, etc., lactones, such as gamma-undecalactone, various components commonly used in perfumery, such as musk ketone, indole, p-menthane-8-thiol-3- ona and methyl-eugenol. Likewise, any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the fully formulated perfume (c). Such conventional fragrant acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as the benzaldehyde-based acetals or ketals, t comprising phenylethyl moieties, or more recently developed specialties such as t described in a U.S. patent. entitled "Acetáis and Ketals of Oxo-Tetralins and Oxo-Indanes", see patent of E.U. No. 5,084,440, issued January 28, 1992, assigned to Givaudan Corp. Of course, other recent synthetic specialties may be included in the perfume compositions for the fabric care composition of the invention. These include the enol ethers of oxo-tetralins and alkyl-substituted oxo-indanes such as t described in the U.S.A. 5,332,725, July 25, 1994, assigned to Givaudan; or Schiff bases such as t described in the patent of E.U.A. No. 5, 264,615, December 9, 1991, assigned to Givaudan. The perfumes useful in the compositions of the present invention are substantially free of halogenated materials and nitro-alkyls. The perfume may be present at a level of from 0% to 10%, preferably from 0.1% to 5% and most preferably 0.2% to 3%, by weight of the finished composition. The fabric softening compositions of the present invention provide an improved deposition of perfume on fabrics.

(H) Enzyme The compositions and methods herein may optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases. An enzyme that is preferred to be used herein is a cellulase enzyme. In fact, this type of enzyme will also provide a benefit of color care to the treated fabric. Cellulases useful herein include both bacterial and fungal cellulases, which preferably have an optimum pH of between 5 and 9.5. The patent of E.U.A. 4,435,307 describes suitable fungal cellulases of the strain DSM1800 of Humicola insolens or Humicola or a cellulase-producing fungus 212 belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk Dolabella Auricular Solander. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitable cellulases are also described in WO 91/17243 to Novo, WO 96/34092, WO 96/34945 and EP-A-0,739,982. In practical terms for current commercial preparations, typical amounts are 5 mg by weight, most preferably 0.1 mg to 3 mg, of active enzyme per gram of the detergent composition. In other words, the compositions herein will typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight of a commercial enzyme preparation. In particular cases in which the activity of the enzyme preparation can be defined in another way such as with cellulases, the corresponding activity units are preferred (eg, CEVU or Cellulase Equivalent Viscosity Units). For example, the compositions of the present invention may contain cellulase enzyme at a level equivalent to an activity of 0.5 to 1000 CEVU / gram of composition. The cellulase enzyme preparations that are used for the purpose of formulating the compositions of this invention typically have an activity between 1, 000 and 10,000 CEVU / gram in liquid form, and about 1, 000 CEVU / gram in solid form.

Other Optional Ingredients The present invention may include optional components conventionally used in textile treatment compositions, for example: brighteners, colorants; surfactants; anti-shrinkage agents; fabric tightening agents; stain reduction agents; germicides; micoticides; antioxidants such as butylated hydroxytoluene, anticorrosion agents, antifoaming agents and the like. The present invention may also include other compatible ingredients, including those described in WO 96/02625, WO 96/21714 and WO 96/21715, and dispersible polyolefin such as Velustrol® as presented in the co-pending application. PCT / US 97/01644, and the like. The present invention may also comprise optional chelating agents. The benefit provided by the use of the present invention is that the composition containing polyamino-functional polymer is stabilized by CGI. As a consequence, in one aspect of the invention, the use of a crystal growth inhibitor is provided to stabilize compositions comprising amino functional polymer.

As a consequence, the compositions of the invention provide better care to fabrics compared to compositions that do not have said stabilization means. Thus, in another aspect of the invention, a method is provided for providing care to the color fabrics comprising the steps of contacting the fabrics with a composition of the invention. The benefit of color care can be assessed either by observation or by determination of delta-denominated values. When visual assessment is used, a panel of qualifying experts compares visually, according to the panel score unit scales established (PSU), fabrics treated with and without the composition according to the present invention. A positive PSU value indicates better performance (PSU scale: 0 = no difference, 1 = it is believed that there is a dience, 2 = it is known that there is a dience, 3 = there is a big dience, 4 = there is too much dience). Another method to evaluate the benefit of color care of fabrics is the determination of the values called delta-E. The delta-E values are defined, for example, in ASTM D2244. Delta E is the computerized color dience as defined in ASTM D2244, ie the magnitude and direction of the dience between two psychophysical color stimuli defined by tristimulus values, or by chromaticity coordinates and illumination factor as computarized by a set Specific to dient color equations defined in the CIEL 1976 CIELAB opposite color space, the opposite color space of Hunter, the Friele-Mac Adam-Chickering color space or any equivalent color space.

Applications The compositions of the invention are suitable for use in any domestic treatment step, i.e. as a pre- or post-treatment composition, as a wash additive, as a laundry composition, as a composition suitable for use in the home. rinse cycle of the wash cycle or applied on a dryer sheet. Obviously, for the purpose of the invention, various applications can be made such as treating the fabric with a pretreatment composition of the invention and also subsequently with a composition of the invention suitable for use in the rinse cycle and / or suitable for use as a sheet for dryer. The compositions of the invention may also be in the form of a spray, foam or aerosol which for example may be suitable for use while ironing, or applied to the surfaces of the drying machine. The invention is illustrated in the following non-limiting examples, in which all percentages are on an active weight basis, unless otherwise indicated. In the examples, the identifications of the abbreviated components have the following meanings: DEQA Di- (seboyl-oxy-ethyl) dimethylammonium chloride DOEQA Di- (oleyloxyethyl) dimethylammonium methylisulfate DTDMAC Disodbodimethylammonium chloride DHEQA Di- (tallow soft-oxy-ethyl) hydroxyethyl methylammonium methylisulfate Fatty acid Fatty tallow acid IV = 1 18 Electrolyte Calcium chloride DTDMAMS Disodbodimethylammonium methylsulphate SDASA 1: 2 ratio of stearyldimethylamine: triple-pressed stearic acid. Glicosperse S-20 Polyethoxylated sorbitan monostearate available from Lonza Clay Clay bentonite clay, Bentonite L, sold by Southern Clay Products TAE25 Ethoxylated tallow alcohol with 25 moles of ethylene oxide per mole of alcohol PEG Polyethylene glycol 4000 PEI 1800 E1 Ethoxylated polyethyleneimine ( MW 1800, 50% active) as synthesized in synthesis example 1 PEI 1800 E3 Ethoxylated polyethyleneimine (MW 1800, 50% active) as synthesized in synthesis example 1 PEÍ 1800 E7 AO Ethoxylated polyethyleneimine amine oxide (PM 1800, 50% active) as synthesized in the synthesis example 4 PEI 1200 E1: Ethoxylated polyethyleneimine (MN 1200, 50% active in water) as synthesized in the synthesis example 5 PEI 1200 E2: Ethoxylated polyethyleneimine (MN 1200, 50% active in water) as synthesized in synthesis example 5 PEI 1200 E4: Ethoxylated polyethyleneimine (MN 1200, active 50% in water) as synthesized in synthesis example 5 PEI 1200 E7: Ethoxylated polyethyleneimine (MN 1200, 50% active in water) as synthesized in synthesis example 5 PEI 1200 E7 AO: Ethoxylated polyethyleneimine of amine oxide (MN 1200, 50% active) as synthesized in synthesis example 5 Dye fixer 1: Cationic agent dye fixative (50% active) available under the trade name Tinofix Eco from Ciba-Geigy Dye fixative 2: Emulsified cationic dye fixative (30% active) available under the tradename Rewin SRF-0 from CHT-Beitlich NH4CI: Ammonium Chloride LAS: Linear alkyl of C12 TAS: Sodium alcohol sulfate C25AS: Linear sodium alkyl sulfate of C-? 2-C-i5 CxyEzS: Sodium alkylsulfate of C? XC? And branched and condensed with z moles of oxide of ethylene C45E7: A predominantly linear C14-C15 primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3: A primary alcohol of C12-C15 branched and condensed with an average of 3 moles of ethylene oxide Cationic ester: Ester mixture C12 / C14 Choline Soap: Linear Sodium Alkylcarboxylate Derived from an 80/20 Blend of Tallow and Coconut Oils TFAA: Alkyl-N-Methylglucamide from C? 6-C? 8 TPKFA: C12- Whole Cut Acid Fatty Acids C? Zeolite A: Hydrated sodium aluminosilicate of formula Na-? 2 (A102S.O2)? 2. 27H20 which has a primary particle size on the scale of 0.1 to 10 microns Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate with a particle size between 200μm and 900μm Silicate: Amorphous sodium silicate (Si0: Na20, ratio 2.0) Sulfate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate activity 86.4 % with a particle size distribution of between 425μm and 850μm MA / AA: Maleic / acrylic acid copolymer 1: 4, average molecular weight of approximately 70,000 CMC: Sodium carboxymethylcellulose Savinase: Proteolytic enzyme activity of 4KNPU / g Carezyme: Cellulite enzyme with an activity of 1000 CEVU / g Termamyl Activity amylolytic enzyme 60 KNU / g Lipolase Activity lipolytic enzyme 100 KLU / g all sold by NOVO Industries A / S and with an activity mentioned above, unless otherwise specified otherwise PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1 Anhydrous sodium perborate whitener of nominal formula NaB02.H202 TAED Tetraacetylethylenediamine DTPMP: Diethylenetriaminepenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060 Photoactivated bleach: Phthalocyanine of sulfonated zinc encapsulated in dextrin-soluble polymer Brightener: 4,4'-Bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) -estilben-2: 2'-disulfonate disodium Antifoam silicone: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as the dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1 HEDP: 1, 1-hydroxyethane diphosphonic acid PBT: 2-phosphonobutan-1, 2,4-tricarboxylic acid Polycarboxylic: Polycarboxylic compound sold by BASF under the trade name Sokalan CP 10 Glycolic : Glycolic Acid EXAMPLE OF SYNTHESIS 1 Preparation of PEÍ 1800 E » Step A) The ethoxylation is performed in a 2-gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for the introduction of ethylene oxide as a liquid. . A cylinder of -7.5 kg net of ethylene oxide (ARC) is installed to supply ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale to be able to monitor the changes in the weight of the cylinder. A 750 g portion of polyethylenimine (PEI) (Nippon Shokubai, Epomin SP-018 having a listed average molecular weight of 1800, equivalent to 0.417 moles of polymer and 17.4 moles of nitrogen) is added to the autoclave. The autoclave is then sealed and purged of air (applying vacuum to minus 711 mm Hg followed by pressurization with nitrogen at 17.57 kg / cm2, then ventilating at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while vacuum is applied. After about one hour, the autoclave is charged with nitrogen at about 17.57 kg / cm2 while the autoclave is cooled to about 105 ° C. Ethylene oxide is then added to the autoclave in increments over time while carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave. The ethylene oxide pump is turned off and cooling is applied to limit any increase in temperature that results from any reaction exotherms. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide have been charged into the autoclave (almost equivalent to one mole of ethylene oxide per function of PEI nitrogen), the temperature is increased to 110 ° C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide. Step B) The reaction mixture is then deodorized by passing approximately 2,831 cn.3 of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while stirring and heating the mixture to 130 °. C. The final reaction product is cooled slightly and collected in glass containers purged with nitrogen. In other preparations, neutralization and deodorization are achieved in the reactor before discharging the product. If a PEI 1800 E7 is desired, the next step of catalyst addition between Step A and B will be included. Vacuum is applied continuously while the autoclave is cooled to about 50 ° C by introducing 376 g of a sodium methoxide solution at 25 ° C. % in methanol (1.74 moles, to achieve a catalyst load of 10% based on the nitrogen functions of PEI). The methoxide solution is sucked into the autoclave under vacuum and then the programming point of the autoclave temperature controller is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The stirrer power and temperature values increase gradually as the methanol is removed from the autoclave, and the viscosity of the mix increases and stabilizes at about 1 hour indicating that most of the methanol has been removed. The mixture is heated and further stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged with nitrogen at 17.57 kg / cm2 and then ventilated at ambient pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Ethylene oxide is again added to the autoclave in increments as mentioned above, carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave, while maintaining the temperature between 100 and 110 ° C and limiting any increase in temperature due to the exotherm of the reaction. After achieving the addition of 4,500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of nitrogen function of PEI) for several hours, the temperature is increased to 110 ° C and the mixture Shake for an additional hour. The reaction mixture is then collected in nitrogen-purged containers and is eventually transferred to a 22-liter three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 moles). Other preferred examples can be prepared such as PEI 1800 E2, PEÍ 1800 E3, PEÍ 1800 E15 and PEÍ 1800 E20 by the above method adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

EXAMPLE OF SYNTHESIS 2 Quaternization at 4.7% of PEI 1800 E7 To a 500 ml Erlenmeyer flask equipped with a magnetic stir bar is added poly (ethyleneimine), MW 1800 ethoxylated to a degree of 7 (224 g, 0.637 moles nitrogen, prepared as in Synthesis Example 1) and acetonitrile (Baker, 150g, 3.65 moles). Dimethyl sulfate (Aldrich, 3.8 g, 0.030 mol) is added in a single dose to the rapidly stirring solution, which is then capped and stirred at room temperature overnight. The acetonitrile is evaporated on the rotary evaporator at ~60 ° C, followed by a Kugelrohr (Aldrich) apparatus at ~80 ° C to produce -220 g of the desired material as a viscous dark brown liquid. A spectrum of 13 C-NMR (D 2 O) shows the absence of a peak at -58 ppm corresponding to dimethyl sulfate. A spectrum of A 1 H-NMR (D20) shows the partial change of the peak at 2.5 ppm (methylenes bound to non-quaternized nitrogens) at -3.0 ppm.

EXAMPLE OF SYNTHESIS 3 Oxidation of PEI 1800 E7 quaternized to 4.7% To a 500 ml Erlenmeyer flask equipped with a magnetic stirring bar is added poly (ethyleneimine), PM1800 which has been ethoxylated to a degree of 7, and quaternized at -4.7% with dimethyl sulfate (121.7 g, -0.32 moles of nitrogen oxidizable, prepared as in synthesis example 2), hydrogen peroxide (Aldrich, 40 g of a 50% by weight water solution, 0.588 moles), and water (109.4 g). The flask is capped, and after an initial exotherm the solution is stirred at room temperature overnight. A spectrum of 1 H-NMR (D 20) shows the total change of the methylene peaks from 2.5-3.0 ppm to -3.5 ppm. To the solution is added -5 g of 0.5% Pd on alumina pellets and the solution is allowed to stand at room temperature for -3 days. The peroxide indicator paper shows that no peroxide remains in the system. The material is stored as a 46.5% solution in water.

EXAMPLE OF SYNTHESIS 4 Formation of amine oxide of PEI 1800 E7 To a 500 ml Erlenmeyer flask equipped with a magnetic stir bar is added polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI-1800, E) (209 g, 0.595 moles of nitrogen, prepared as in synthesis example 1), and hydrogen peroxide (120 g of a solution in water at 30% by weight, 1.06 mol). The flask is capped and after an initial exotherm the solution is stirred at room temperature overnight. The 1 H-NMR spectrum (D 20) obtained on a sample of the reaction mixture indicates complete conversion. The resonances belonging to the methylene protons adjacent to non-oxidized hydrogens have changed from the original position of -2.5 ppm to -3.5 ppm. To the reaction solution is added about 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for about 3 days. The solution is tested and found negative for peroxide by indicator paper. The material as obtained is stored appropriately as an active solution at 51.1% in water.

EXAMPLE OF SYNTHESIS 5 Preparation of PEI 1200 Ei Step A) The ethoxylation is carried out in a 2-gallon stirred stainless steel autoclave, equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for the introduction of ethylene oxide as a liquid. A cylinder of 7.5 kg net of ethylene oxide (ARC) is installed to supply ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale to be able to monitor the changes in the weight of the cylinder. A 750 g portion of polyethyleneimine is added to the autoclave (PEI) (having a listed average molecular weight of 1200, equivalents to 0.625 moles of polymer and 17.4 moles of nitrogen functions). The autoclave is then sealed and purged of air (applying vacuum to minus 711 mm Hg followed by application of pressure with nitrogen at 17.57 kg / cm2, then ventilating at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while vacuum is applied. After about one hour, the autoclave is charged with nitrogen at about 17.57 kg / cm2 while the autoclave is cooled to about 105 ° C. Ethylene oxide is then added to the autoclave in increments over time while carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave. The ethylene oxide pump is turned off and cooling is applied to limit any increase in temperature that results from any reaction exotherms. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been charged into the autoclave (almost equivalent to one mole of ethylene oxide per function of PEI nitrogen), the temperature is increased to 110 ° C and the autoclave is allowed to shake for an additional hour. At this point, vacuum is applied to remove any residual ethylene oxide that did not react. Step B) The reaction mixture is then deodorized by passing approximately 2,831 cn.3 of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while stirring and heating the mixture to 130 °. C. The final reaction product is cooled slightly and collected / in glass containers purged with nitrogen.

In other preparations, neutralization and deodorization are achieved in the rector before unloading the product. If a PEI 1200 E7 is desired, the next catalyst addition step will be included between Step A and B. Vacuum is applied continuously while the autoclave is cooled to approximately 50 ° C by introducing 376 g of a sodium methoxide solution at 25 ° C. % in methanol (1.74 moles, to achieve a catalyst loading of % based on the PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the programming point of the autoclave temperature controller is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The power and temperature values of the agitator increase gradually as the methanol is removed from the autoclave, and the viscosity of the mixture increases and stabilizes in about one hour indicating that most of the methanol has been removed. The mixture is heated and further stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged with nitrogen at 17.57 kg / cm2 and then ventilated at ambient pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Ethylene oxide is again added to the autoclave in increments as mentioned above, carefully monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave, while maintaining the temperature between 100 and 1 10 ° C and limiting any increase in temperature due to the exotherm of the reaction. After achieving the addition of 4,500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of nitrogen function of PEI) for several hours, the temperature is increased to 110 ° C and the mixture Shake for an additional hour. The reaction mixture is then collected in nitrogen purged containers and optionally transferred to a 22-liter, three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 moles). Other preferred examples such as PEI 1200 E2, PEI 1200 E3, PEI 1200 E15 and PEI 1200 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction. The amine oxide corresponding to the above ethoxylated PEI can also be prepared following synthesis example 4.

EXAMPLE OF SYNTHESIS 6 Quaternization at 9.7% of PEI 1200 E7 To a 500 ml Erlenmeyer flask equipped with a magnetic stir bar is added poly (ethyleneimine), MW 1200 ethoxylated to a degree of 7 (248.4 g, 0.707 mol nitrogen, prepared as in Synthesis Example 5) and acetonitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) is added in a single dose to the rapidly stirring solution, which is then capped and stirred at room temperature overnight. The acetonitrile is evaporated on the rotary evaporator at ~60 ° C, followed by a Kugelrohr (Aldrich) apparatus at ~80 ° C to produce -220 g of the desired material as a viscous dark brown liquid. A spectrum of 13 C-NMR (D 20) shows the absence of a peak at -58 ppm corresponding to dimethyl sulfate. A spectrum of 1 H-NMR (D 2 O) shows the partial change of the peak of 2.5 ppm (methylenes bound to non-quaternized nitrogens) at -3.0 ppm.

EXAMPLE OF SYNTHESIS 7 Oxidation at 4.7% of PEI 1800 E7 quaternized at 9.5% To a 500 ml Erlenmeyer flask equipped with a magnetic stir bar is added poly (ethyleneimine), PM1200 which has been ethoxylated to a degree of 7, and quaternized to -9.5% with dimethyl sulfate (144 g, -0.37 moles of nitrogen oxidizable, prepared as in the synthesis example 6), hydrogen peroxide (Aldrich, 35.4 g of a solution in water at 50% by weight, 0.52 moles), and water (100 g). The flask is capped, and after an initial exotherm the solution is stirred at room temperature overnight. A spectrum of 1 H-NMR (D 20) shows the total change of the methylene peaks from 2.5-3.0 ppm to -3.5 ppm. To the solution, sufficient sodium bisulfite is added as a solution in 40% water to reduce the level of residual peroxide to 1-5 ppm. The sodium sulfate that is formed causes an aqueous phase to be separated that contains salts, but nothing or few organic. The aqueous salt phase is removed and the desired oxidized polyethylene imine derivative is obtained and stored as a 52% solution in water.

EXAMPLE 1 The following compositions are in accordance with the present invention.

EXAMPLE 2 The following compositions for use as papers that are added to the dryer are according to the invention.

EXAMPLE 3 The following detergent formulations are in accordance with the present invention: EXAMPLE 4 The following liquid detergent formulation was prepared according to the present invention:

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A fabric care composition comprising a functional polyamine polymer and a crystal growth inhibitor, wherein said crystal growth inhibitor is selected from carboxylic acid, organodiphosphonic acid, and mixtures thereof, the growth inhibitor of crystal is presented in an amount of less than 1% by weight of the composition.

2. A composition according to claim 1, further characterized in that said polymer comprises a polyamine base structure corresponding to the formula: R i [R2N-R] n + 1 - [NR] m- [NR] n- NR having a polyamine formula V (n + i) WmYnZ or a polyamine base structure corresponding to the formula: R R I [R2N-R] n.k + 1 - [N-R] m- [N-R] n- [N-R] k-NR2 having a polyamine formula V (n-k +.) WmYnY'kZ, wherein k is less than or equal to n, said polyamine base structure has a molecular weight of more than 200 daltons, wherein i) the V units are terminal units that have the formula: OR- N- R- RN? -. ? R-- R- N t-R- I I R R R ii) units W are base structure units that have the formula: O - N- R - - N- R- - N- R- I I R R R iii) units Y are branching units that have the formula: O R X "-N- R- -N- R- - N-R- and iv) the units Y 'are branching point for a base structure or branching ring having the formula: v) Z units are terminal units that have the formula: wherein the base structure binding units R are selected from the group consisting of C2-Ci2 alkylene, C4-C12 alkylene, C3-C2 hydroxyalkylene, C4-C12 dihydroxyalkylene. dialkylarylene of C8-C12, - (R10) xR \ - (Rl?) xR5 (OR)? -, CH2CH (OR2) CH20) z (R0) and R (OCH2CH (OR2) CH2) w- > -C (0) (R4) rC (0) -, (CH2CH (OR2) CH2- and mixtures thereof, wherein R1 is selected from the group consisting of C2-C6 alkylene, and mixtures thereof: R2 is selected from the group consisting of hydrogen, - (R10) xB, and mixtures thereof, R 4 is selected from the group consisting of C 1 -C 12 alkylene, C 4 -C 2 alkenylene, C 8 -C 16 arylalkylene, C 6 -C arylene, and mixtures thereof. thereof, R 5 is selected from the group consisting of C 1 -C 2 alkylene, C 3 -C 2 hydroxyalkylene, C 4 -C 2 dihydroxyalkylene, C 8 -C 8 dialkylarylene, -C (O ) -, -C (0) NHR6NHC (0) -, -R1 (OR1) -, -C (0) (R4) rC (0) -, CH2CH (OH) CH2-, -CH2CH (OH) CH20 (R10 ) and R1OCH2CH (OH) CH2-, and mixtures thereof: R6 is selected from the group consisting of C2-C12 alkylene or C6-C-? 2 arylene, the R 'units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl> C7-C22 arylalkyl, C2-C2 hydroxyalkyl, - (CH2) pC02M, - (CH2) qS03M, -CH (CH2C02M) C02M, - (CH2) pP03M , - (R10) xB, -C (0) R3, and mixtures d e the same; B is selected from the group consisting of hydrogen, C? -C6 alkyl, - (CH2) qS03M, - (CH2) pC02M, - (CH2) q- (CHS? 3M) CH2S? 3M, - (CH2) q ( CHS02M) CH2S03M, - (CH2) PP03M, -P03M, and mixtures thereof; R3 is selected from the group consisting of C? -C? 8 alkyl, C7-C12 arylalkyl, C7-Ci2 aryl substituted alkyl, C6-C12 aryl, and mixtures thereof; M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the charge equilibrium; X is a water soluble anion; m has the value of 2 to 700; n has the value from 0 to 350; p has the value of 1 to 6, q has the value of 0 to 6; r has the value of 0 or 1; w has the value of 0 or 1; x has the value of 1 to 100; and has the value from 0 to 100; z has the value of 0 or 1.

3. A composition according to claim 2, further characterized in that the R 'units of the amino-functional polymer are selected from the group consisting of hydrogen, C3-C22 hydroxyalkyl, benzyl, C1-C22 alkyl, - (R10) xB, -C (0) R3, - (CH2) pC02-M +, - (CH2) qS03-M +, - CH (CH C02M) C02M and mixtures thereof, preferably the R 'units are selected from the group consisting of hydrogen, CrC22 alkyl, - (R1O) xB, -C (O) R3, and mixtures thereof, most preferably the R 'units are - (R10) xB.

4. A composition according to any of claims 2 or 3, further characterized in that x has a value on the scale from 1 to 20, preferably from about 1 to 10.

5. A composition according to any of the reinvidications 1-4, further characterized in that said polymer is present in an amount of up to 90% by weight, preferably from 0.01% to 50% active by weight, most preferably from 0.1% to 20% by weight and still most preferably 0.5% to 15% by weight of the composition.

6. - A composition according to any of claims 1-5, further characterized in that said crystal growth inhibitor is selected from carboxylic compounds, organomonophosphonic acid, organodiphosphonic acids and mixtures thereof; preferably it is an organodiphosphonic acid.

A composition according to claim 6, further characterized in that said organomonophosphonic acid is 2-phosphonobutane-1, 2,4-tricarboxylic acid.

8. A composition according to claim 6, further characterized in that said organodisophonic compound is hydroxy-ethane 1,1 diphosphonic acid.

9. A composition according to any of claims 1-7, further characterized in that said crystal growth inhibitor is present in an amount of about 0.005% to 0.50%, preferably of about 0.1% to 0.2% by weight of the composition.

10. A composition according to any of the claims 1-9, further characterized in that said composition additionally comprises a fabric softener.

11. A composition according to claim 10, further characterized in that said softener is a cationic fabric softener, preferably selected from l X "O) or the formula: (R) '.4-m - where Q is a carbonyl unit having the formula: O o o R2 O O R2 II II II I II II I -o-c-, -c-o-, -0-c-o-, -N-C- -C-N- each R unit is independently hydrogen, C 1 -C 6 alkyl, C 6 -C 6 hydroxyalkyl, and mixtures thereof, preferably methyl or hydroxyalkyl; each R1 unit is independently linear or branched CH-C22 alkyl, straight or branched C11-C22 alkenyl, and mixtures thereof; R 2 is hydrogen, C 4 alkyl, hydroxy C 1 -C 4 alkyl, and mixtures thereof; X is an anion that is compatible with fabric softener; the index m is around 1 to 4, preferably 2; the index n is around 1 to 4, preferably 2.

12. A composition according to any of claims 1-11, further characterized in that said composition additionally comprises a colorant fixing agent.

13. A composition according to any of claims 1-12, further characterized in that said composition is in liquid form.

14. The use of a crystal growth inhibitor to stabilize compositions comprising amino-functional polymer.

15. A method for providing care to the colored fabrics comprising the steps of contacting the fabrics with a composition according to any of the claims 1-13.