CZ341295A3 - Composition of granulated detergent with packaging system - Google Patents

Abstract

The present invention relates to detergent compositions containing selected moisture-sensitive ingredients; it provides a combination between such compositions and a packaging system containing them, such a combination providing optimum protection against moisture to said selected ingredients, and thus excellent storage stability to the finished compositions.

Description

Technical Field> CS tn 2 C- * 7i

CO 'σ>

rc

-j zn

The invention relates to detergent compositions comprising selected moisture sensitive ingredients, providing a combination between such compositions and a packaging system comprising them, and this combination provides optimal moisture protection to said selected ingredients and thus excellent storage resistance of the resulting ingredients.

-¾ means.

BACKGROUND OF THE INVENTION

The problem of the negative effect of moisture on detergent ingredients during storage and in particular during extended storage has been known to detergent manufacturers for a long time. This effect is either due to the direct action of water on certain ingredients resulting in their decomposition and / or loss of activity, or corresponds to the action of degradation products on the moisture-sensitive components on other ingredients, which also leads to degradation and / or loss of activity. Numerous technologies have been designed and implemented that require the addition of special additives or modifications to existing additives to protect the resulting composition from moisture.

Relatively little attention has been paid to a packaging system containing detergent compositions in relation to the above problem.

SUMMARY OF THE INVENTION

The present invention is based on the discovery that the choice of a particular packaging system in combination with careful control of the moisture level in a composition can surprisingly solve the described shelf life problem for a number of particularly moisture sensitive ingredients identified herein.

Thus, the present invention provides a detergent composition comprising selected moisture sensitive ingredients and a controlled moisture level with a protective system with selected water vapor transmission rate characteristics.

Advantageously, laundry detergent dishes are also included.

Detergent

The term detergent composition herein is with detergent compositions, although automatic detergent compositions are washed

Equilibrium relative humidity reaps relative humidity, not greater

These compositions are characterized by equal to 30% by weight at 35 ° C.

For the purposes of the present invention, an equilibrium of 300g of product is placed in one liter containers of material and sealed with a lid immersed in containers adapted to allow insertion of the probe indoors for 24 hours at 35 ° C to maintain water vapor in the space above the products used (Hygrotest 6100, Registered Testoterm Ltd, Old Flour Hampshire London). While the vessel is held open to the lid and the water vapor pressure measurement is equal to two consecutive measurements, there is no change. The inflow to directly readable equilibrium relative humidity measures the relative humidity as follows: y made of impermeable y. The lid has a sealed opening, at the container. Container and contents are and constant temperature. To measure the pressure of a solid state hygrometer Miles, Oueen Street, Emsworth, at 35 ° C, the probe is inserted through the scale, as evidenced by converting the vapor pressure measurement st.

The compositions of the invention are prepared many relative humidity not higher than the critical value:

and methods to equilibrium and 30% at 35 ° C.

For example, certain components of the detergent deterge the internal moisture, such as the agglomerates of the surfactant dried component, are dried or mixed, the dried zeolite also being used in the active agents as a dry addition, in the environment or in the final powdering step.

The further spraying agent-containing compositions or spray-drying agents are preferably dried prior to the preparation of the spray-dried surface formulations of the agglomerates.

Other methods include drying the final product as described in DE 40 31 10.

Other methods result in a relative humidity balance of less than 25% at 35 ° C.

Selected moisture sensitive ingredients are described herein.

1 / Amides of polyhydroxy fatty acids

Polyhydroxy fatty acid amides are formed by reacting fatty acid esters and N-alkyl polyhydroxyamine. A preferred amine for use in the present invention is N- (R ₁ ) -CH ₂ (CH ₂ OH) ₄ -CH ₂ -OH and the preferred ester is a C ₂ -C ₂₀ fatty acid methyl ester. Most preferred is the product of the reaction of N-methylglutamine with C ₁₂ -C ₂₀ fatty acid methyl ester.

Methods for making polyhydroxy fatty acid amides are described in WO 92 6073, published April 16, 1992. This application describes the preparation of polyhydroxy fatty acid amides in the presence of solvents. In a highly preferred example of the invention, N-methylglutamine is reacted with C ₁₂ -C ₂₀ methyl ester. It also discloses that the granular detergent manufacturer finds it convenient to carry out the amidation reaction in the presence of solvents which include alkoxylated, especially ethoxylated (EO 3-8) C12-04 alcohols (page 15, lines 22 to 27). This directly provides the nonionic surfactant systems that are preferred in the present invention, such as those containing N-methylglutamide and 02-04 alcohols with an average of three ethoxy groups per molecule.

Nonionic surfactant systems and granular detergents produced by this process have been described in WO 92 6160, publ. April 16, 1992. This application describes (Example 15) granular detergent compositions prepared by gentle dispersion mixing in an Eirich RV 02 blender containing N-methylglutamide (10%), a non-ionic surfactant (10%).

Both of these patents disclose nonionic surfactant systems together with corresponding manufacturing processes for their synthesis, which have been shown to be suitable for use in the present invention.

The polyhydroxy fatty amino acid amide of the invention is from 0 to 40% by weight of the detergent, more preferably from 1 to 30% by weight, most preferably c

Cholinesters of itomen in the compositions of this component or composition, d 1 to 20% by weight.

Preferred cholinester derivatives are those of formula I:

o ch ₃ ¹¹ < ¹ R'C o ch, ch2n ⁺ ch3x1

CH, wherein R is C ₅ -C ₃₀ optionally branched alkyl, or which forms a compound at least dispersed selected from the group consisting of halides, preferably methylsulfate, chloride, bromide or iodide

As well as those wherein the ester bond in said ester, amide or inverted amide bond.

Particularly preferred examples of this type kationl agents include quaternary ammonium halides (R = C ₁₇ alkyl) quaternary palmitoylcholinester amo quaternary ammonium halides choline ester quaternary ammonium halides such as choline ester quaternary ammonium halides, choline esters (R = C ₁₇ -C _l5 alkyl and C _I3 -C ₁₉ alkyl, respectively.).

Other preferred cationic composite species of formulas II and III are as follows:

oo ch ₃

II II I

R ¹⁰ O (CH ₂ ) CO CH, CH ₂ N 'CH ₃ X'

I ch ₅

II is alkenyl, and X is an anion, preferably in water, preferably ulfate, sulfate and nitrate, and is replaced by an inverted, surfactant stearic acid line ester of halides (R '= C ₁₅ alkyl), myristic (R' = C ₁₃₎ alkyl), lauric (R ^{1 =} alkyl C _U) of the same acid of coconut and tallow choline ents are given RNA _{CH3 CH3} oo

I II II I x ch ₃ n ch ₂ - ch ₂ OC (CHJ-C-0 ch ₂ CH ₂ Ν ch ₃ x ⁺

II ch ₃ ch ₃

III wherein p is 0-20.

Preferred choline derivatives of the cationic compounds mentioned above are prepared by direct esterification of the desired fatty acid of the desired chain length with dimethylaminoethanol in the presence of an acid catalyst. The reaction product is quaternized with methyl halide to form the desired cationic material.

Choline-derived cationic materials are also prepared by direct esterification of a long chain fatty acid of the desired length with 2-haloethanol in the presence of an acid catalyst. The reaction product is quaternized.

The desired cationic substance is formed with trimethylamine.

Other suitable cholinesters used herein are derivatives of formulas IV, V, VI, VII, VIII, IX, X, and XI:

O CH ₃

II I

R ¹⁰ (CH, CH ² O) y (CH 2) CO CH 2 CH 2 N ⁺ CH ₃ X ₃

IV o ch ₃

II I

R ¹⁰ O (CH, CH, O) CO CH 2 CH 2 N ⁺ CH 3 X '

I ch ₃ v

ch ₃ o ch ₃

I II I

R 'O (CHCH ₂ O) _y CO CH ₂ CH ₂ N ⁺ CH ₃ X' ch ₃

VI ch ₃ o ch ₃

R ¹⁰ O (CHCH ₂ O) _y (CH ₂ ) CO CH ₂ CH ₂ N * CH ₃ CH ₃

VII ch ₃

AND

H, XR ^: O (CH ₂ CH ₂ O) _y C (CH ₂ ) CO CH ₂ CH ₂ N * Cl

CH

VIII

OH HO

CH,

R ^l 0 (CH ₂ CH ₂ O) CC = CC 0 CH ₂ CH ₂ N + CH ₃ X

AND

CH,

IX

O CH,

R ¹⁰ (CH ₂ CH ₂ CH, CH ₂ O) _y C CH ₂ N 'CH ₃ X'

I ch ₃

X o

II

R ¹ 0 (CH ₂ CH, CH, CH, O) (CH₃) CO CH ₂ CH

CH ₃

I | N ⁺ CH ₃ XI

CH,

XI wherein t is 0 or 1, y is 1-20, R and X are defined Cholinesters are present in an amount of 0-5 more preferably 1-30% by weight, even more preferably 1-2 (y above.

0% by weight of compositions,% by weight.

ai

Bleach activators - bleach activators are selected by their mixtures:

consists of the following components or

The alkanoyloxybenzenesulfonates - suitable alkanoyloxybenzenesulfonate bleach activators used in the present invention are compounds of formula XII:

wherein R, -C (O) - contains 8-12, preferably 8-11 carbon atoms and M is a suitable cation such as an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred.

Highly preferred hydrophobic alkanoyloxybenzenesulfonates are selected from the group consisting of nonanoyloxybenzenesulfonate, 3,5,5-trimethylhexanoyloxybenzenesulfonate, 2-ethylhexanoyloxybenzenesulfonate, octanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, and mixtures thereof.

Amide-derived bleach activators - The amide-derived bleach activators used in this invention are amide-substituted compounds of formulas XIII and XIV:

0 0 0

II II II II

R ¹ CNR ² CL R'N CR ² CL

I I

R ⁵ R ⁵

XIII XIV or mixtures thereof, wherein R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 1-14 carbon atoms, R ⁵ is H or alkyl, aryl or an alkaryl group having

1-10 carbon atoms and L is always a suitable leaving group. A leaving group is any group that is replaced in the bleach activator as a result of the nucleophilic action of the perhydroxide anion on the bleach activator. This perhydrolytic reaction leads to the formation of a peroxycarboxylic acid. Generally, to be a suitable leaving group, the group must use electron attraction. A stable entity may also be formed such that the rate of the reaction is negligible. This facilitates the nucleophilic action of the perhydroxide anion.

The L group must be sufficiently reactive for the reaction to take place within a certain time range (eg, the wash cycle). However, if L is too reactive, it will be difficult to stabilize this activator to use characteristics generally parallel to the pKa of the con group, although the exceptions of this conventional group having such behavior are those that have a pKa in the range of 4-13, preferably 6 The most preferred bleach activators are those listed above. selected from the group consisting of general pattern residues in a bleaching composition. These clogged acids make him claim. Commonly withdrawn from its conjugate acid 8-11.

of the general formula wherein L is XV, XVI and XVII:

—O '- ^c

XV

Rs

XVI

R ³ Y where R ³ is as defined above and Y is -SO ₃ 'M ⁺ or M is an alkali metal, ammonium or substituted is most preferably sodium and potassium.

Preferred examples of bleach activators include the above (δ-octanamidocaproyl) oxybenzenesulfonate, (6-non phonate, (δ-decanamidocaproyl) oxybenzenesulfonate, and U.S. Patent 4,634,551, incorporated herein by reference.

Benzoxazine-type activators - described 4,966,723, issued Oct. 30, 1990. Most preferred is a compound of Formula XVIII:

XVII to ₂ 'M', wherein the ammonium cation, said formulas include a [namidocaproyl) oxybenzene mixtures as described in

Hodgem et al in U.S. Pat. Patent of activator of benzoxazine type

Acyl lactam activators, in particular acyl caprolactams and acylvalerolactams of formulas XIX and XX:

O

II

C = CH = CHR 6 = C = N; CH;

^X CH — CH /

O

II

About C- <

II I R 6 —C-N

CH ·

CH

XIX

I.—CH.

-CH.

XX wherein R ⁶ is alkyl, aryl, alkoxyaryl or alkaryl having 1-12 carbon atoms or substituted phenyl having 6-18 carbon atoms. See co-pending US Patent Applications 08/064, and 08 / 082,270, which describe substituted benzoyl lactams. Most preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, decanoylvalererolactam, undanoylvalererolactam, undanoylvalerolactam, undanoylvalerolactam, undanoylvalerolactam, undanoylvalerolactam, undanoylvalerolactam, undanoylvalerolactam, undanoylvalerolactam, undanoylvalerolactam, See also US Patent 4,545,784, Sanderson, Oct. 8, 1985, incorporated herein by reference, which discloses acyl caprolactams including benzoyl caprolactam absorbed into sodium perborate.

Quaternary substituted bleach activators (QSBA) - QSBA are compounds of formula XXI:

E- [Z] n -C (O) -L

XXI wherein group E is referred to as head, group Z is referred to as a linker (n is 0 or 1, i.e., the group is present or not, although its presence is generally preferred) and L is referred to as a leaving group. These compounds generally contain at least one quaternary substituted nitrogen group that is contained in E, Z, or L. More preferably, a single quaternary nitrogen is present that is located in group E or Z. In general, L is a leaving group wherein pK a of its respective carbon of the acid (HL) lies in a general range of 5-10, more preferably 10-20, depending on the hydrophilicity of the QSBA. The pKa of leaving groups is further defined in U.S. Pat. No. 4,283,301.

Preferred QSBAs here are, on the one hand, water-soluble, but on the other hand, to a certain extent, tend to divide into micelles of surfactants, particularly. for micelles of nonionic surfactants.

The leaving groups and the tendency to dissolve the quaternary groups that are present in the QSBA are further described in U.S. Pat. No. 4,539,130, Sep. 3, 1985, incorporated herein by reference. This patent also describes QSBAs in which the quartz: group is present in the leaving group L.

Z is poly (methylene) and E is a quaternary group, the QSBA class suitable for quaternary ammonium esters group Z attached to E through the group via the ammonium carbonate linking atom. The atom is also known and in March 1992 and U.S. Pat. 4,904,406,

British Pat. 1,382,594, issued Feb. 5, 1975 after use in accordance with the present invention. In these or the olygo (methylene) group, i.e. the linker is alifa U.S. Pat. No. 4,818,426, issued Apr. 4, 1989, includes the use of the present invention. These carbonate compounds with reference to the above formula is a carbon atom, but it is attached to carbonyl oxygen. These compounds are thus quaternary homologous compounds lacking the linking oxygen useful herein. See. e.g. 5,093,022, issued Mar. 3, 27, 1990.

Furthermore, QSBAs are described in EP 552,812 A1 publ EP 540,090 A2 published May 5, 1993. All herein incorporated by reference.

Particularly preferred QSBAs have a caprolactam leaving group.

Preferred examples of QSBAs applicable in the following:

July 28, 1993, and the above-mentioned documents are the valerolactam of this invention are synthesized

CO-H

HnCl

 steed

N (CH ₂ ) n

The synthesis is described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION

Preparation of N-4- (triethylamoniomethyl) benzoylcaprolactam chloride

4-Chloromethylbenzoic acid chloride - One-necked round-bottomed flask was equipped with a dropping funnel, gas inlet, magnetic stirrer and charged with 4-chloromethylbenzoic acid (0.5mol), toluene (1, Omol acid / 3 50ml) and cooking stones under argon atmosphere. . Thionyl chloride (1.0 mol) was added dropwise via addition funnel. The dropping funnel was replaced with a reflux condenser and the reaction was heated to reflux for 4 hours under argon. The reaction was cooled to room temperature. The solvent was evaporated.

4-chloromethylbenzoylcaprolactam - round-bottomed three-necked flask equipped with a mechanical stirrer, reflux condenser, dropping funnel and gas inlet and filled with caprolactam (0.5mol), triethylamine (0.75mol) and 75% of the required toluene (l, 1mol caprolactam) , 51) under argon. The solution was heated to reflux. 4-Chloromethylbenzoic acid chloride (0.5mol) suspended in the remaining toluene is added in a slow stream. The reaction was stirred at reflux for 6 hours under argon, cooled slightly and filtered. The solid, triethylamine hydrochloride, was discarded and the filtrate was cooled to precipitate the product. The product is vacuum filtered, washed and dried.

N- [4- (triethylamoniomethyl) benzoylcaprolactam chloride - round-bottomed, one-necked flask was equipped with a magnetic stirrer, dropping funnel and gas inlet and charged with 4-chloromethylbenzoylcaprolactam (0.5mol) and acetonitrile (1mol caprolactam / 1.51). Triethylamine (1.0 mol) was added dropwise. The dropping funnel was replaced with a reflux condenser, and the reaction was heated to reflux for 4 hours under argon. The reaction was cooled to room temperature and the solvent was evaporated. Excess acetone was added to the flask with a magnetic stirrer to separate the products. The mixture is briefly heated to boiling and then cooled to room temperature. The product was vacuum filtered, washed and dried.

The above syntheses can be carried out except that valerolactam is substituted for caprolactam. The syntheses can also be performed by replacing trimethylamine with

Correspondingly, the cationic bleaching examples given for purposes of this invention should be regarded as limiting, even as a substitute for the group E or Z being part of: i the group L is hydrolytically: upine Z, in the latter case any of the structures:

triethylamine. In each example it is secured by an activator.

Although the foregoing QSBAs preferred preferred illustrations of the invention, their specific enumeration would include other QSBAs known in the art. Examples include modifications of said structures wherein the heterocycle or modifications in which they resist resistant covalent bond to both E and sl L are considered limited. outgoing group in who

E (Z) _n C (O) L or E (Z) _and C (O) L upins to form a peracid and after perhydrolysis further withdraws from E (Z) _n C (O) sk, which has one of the structures:

E (Z) _n COOH or E (Z) _n COOH L (O L 6 groups not attached to e are attached via an oxybenzene sulfonate atom). Examples of the aforementioned patents. in an amount of from 1% to 20% by weight, most preferably from 3 to 20%

In other examples known to QSBA, the leaving group E (Z) _n C (O) through a neutral nitrogen and oxygen atom, as in the conventional leaving group OBS (such variants have been documented in the literature including <Bleach activators are preferably incorporated herein) more preferably from 2 to 10% by weight of 5% by weight of the composition.

according to the invention are selected from N-vinylpyrrolidone and ylimidazoles, polyaspartates, 10,000, terpolymers having a molecular weight of 6Q% - a release agent in the ropoxy terminated oligomeric

Polymers - polymers for use according to the present group: polyamine N-oxide polymers, copolymers of N-vinylimidazole, polyvinyloxazolidones, polyvine polyglutamates or mixtures thereof having molecular β maleic / acyclic acids and vinyl alcohol, m? The selected agents are sulfonated polyethoxy / β esters and mixtures thereof. Said polymers are used in the range of 0.01-20% of the composition.

The sulfonated polyethoxy / propoxy terminated oligomeric esters of the present invention are described in U.S. Pat. Applications Nos. 08/088707 and 08/088705.

The esters of the present invention are simply characterized as oligomers that comprise a substantially linear ester backbone and terminating units that are derived from sulfonated monohydroxypolyethoxy / propoxy monomers, particularly 2- (2-hydroxyethoxy) ethanesulfonate. Appropriate selection of the structural units containing the ester backbone and the use of a sufficient amount of sulfonated terminating units result in desirable soil removal properties of these materials. Integration of the stabilizers into the oligomer reduces the crystallization of the oligomer during production, and upon insertion into the wash liquor the dissolution / dispersion and the removal of esters from the soil are increased.

The oligomeric ester used herein preferably comprises:

(i) 1-2 moles of sulfonated polyethoxy / propoxy terminated units of formula (XXII):

(MO ₃ S) CH ₂ ) _m (CH ₂ ) (CH ₂ CH ₂ O) (RO) _n

XXII wherein M is a cation-forming salt selected from the group consisting of sodium and tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or a mixture thereof, n is 0-2, (ii) 0.5 - 66mol units selected from the group consisting of of: a) oxyethyleneoxy units, b) mixtures of oxyethyleneoxy and oxy-1,2-propyleneoxy units, wherein said oxyethyleneoxy units are present in an oxyethyleneoxy to oxy-1,2-propylenoxy ratio in a molar ratio of 0.5: 1 to 10: 1 , c) mixtures of a) or b) with poly (oxyethylene) oxy units, wherein said poly (oxyethylene) oxy units have a degree of polymerization of 2-4. Assuming that said poly (oxyethylene) oxy units have a degree of polymerization of 2, the molar ratio of poly (oxyethylene) oxy units to total group ii) units is 0: 1 to 0.33: 1, and when said poly (oxyethylene) oxy units have a degree of polymerization of 3rd mill; the ratio of poly (oxyethylene) oxy units to total group ii) units is 0: 1 to 0.22: 1, and when said poly (oxyethylene) oxy units have a degree of polymerization of 4, the molar ratio of poly (oxyethylene) oxy units to total group (ii) units are 0: 1 to 0.14: 1; (iii) 1.5 - 40mol terephthaloyl units; and iv) 0 - 26mol 5-sulfoisophthaloyl units of formula - (O) C (C ₆ H ₃ ) (SO ₃ M) C (O) - wherein M is a salt forming cation.

Oligomeric esters - it is understood that the soil release agents herein are not of the type of resin, high molecular weight, macromolecular or fiber forming polyesters, but instead are of low molecular weight and contain components more descriptively described as oligomers than polymers. The individual ester molecules of the present invention, including terminating units, have a molecular weight of 500-8000. Relevant for purposes of comparison with glycol terephthalate fibrous polyesters (typical average 15,000 or more molecular weight) is a molecular weight range of 500-5000 within which molecules of preferred esters of the present invention which contain the necessary units and 5-sulfoisophthalate. Accordingly, the soil release enhancers used in the cleaning composition of the present invention are referred to as oligomeric esters rather than polyesters in the commonly used sense of the term used to refer to high polymers such as fibrous polyesters.

The molecular geometry esters used herein are all substantially linear in the sense that they are not significantly branched or crosslinked by including units having more than two ester bonding centers in their structure. (For comparison: a typical example of ester branching or crosslinking of the type excreted in the defined esters of this invention, see Sinker et al, US Patent 4,554,328, issued November 19, 1985.) Furthermore, no cyclic esters are essential for the soil release agent of of the present invention, but may be present in the detergent compositions of the present invention in small amounts as a result of side reactions during ester synthesis. Preferably, the cyclic esters do not exceed 2% by weight of the composition, most preferably, will be completely excluded from the composition.

In contrast, the term substantially linear as applied herein to esters, however, includes materials that contain side chains that do not react in ester formation or transesterification reactions. Thus, oxy-1,2-propyleneoxy units are an unsymmetrically substituted type, their methyl group does not form what is generally considered a branching in polymer technology (see Odian, Principles of Polymerization, Willey, NY, 1982, pp. 18-19). the description is incorporated herein by reference, with which the present definitions are consistent) and do not react in the formation of esters. Optional units in the esters of the soil release composition used herein may have side chains, provided they meet the same non-reactivity criteria.

Molecular structures - The following structures are illustrative structures of the ester molecules falling within the preferred examples shown, and demonstrate how the units are linked:

a) double-terminal ester molecule composed of the main units i), ii), iii)

b) simply terminated ester molecule composed of the main units i), ii), iii)

(c) a double-terminated ester molecule (referred to as a hybrid ester chain backbone) composed of the main units (i), (ii), (iii). Units (ii) are mixtures of oxyethyleneoxy and oxy-1,2-propyleneoxy units, and as follows: below in a 2: 1 ratio (on average, in the ester compositions as a whole, for comparison with the individual molecules as illustrated herein, the range of ratios is 1: 1 to 0: 1, and is most preferred when the compositions are based on units i), (ii), (iii),

(d) a double-terminal ester molecule composed of the main units (i), (ii), (iii), together with an optional unit (iv). On average in the ester compositions as a whole, for comparison with the individual molecules as illustrated below, the most preferred ratio of oxyethyleneoxy to oxy-1,2-propylenoxy unit is 0.5: 1 to 1: 0 when the compositions are based on units i), (ii), (iii), (iv),

Of the structures listed here, soil release polymer having the general formula XXIII is most preferred:

O II

CO-CK, CH ₂ OCH-, CH-, SO ₃ Na o II —ch ₂ choc R

XXIII wherein R is H or CH 3 in a ratio of 1.8: 1.

With respect to the structures of the ester molecules mentioned herein, it should be noted that they include not only the arrangement of units at the molecular level, but also the total ester mixtures that arise from the reaction schemes and which have the desired range of compositions and properties. Accordingly, when the amount of monomer units or the ratio of units is given, the number indicates the average amount of monomer units present in the oligomers of the composition.

The ester backbone - as shown in the structures listed below, in the soil release esters of the present invention, the backbone consists of oxyethyleneoxy and terephthalyl units interconnected. Optionally, the backbone is composed of 5-sulfoisophthaloyl units, terephthaloyl units, oxyethylenoys or a mixture of oxyethyleneoxy, oxypropyleneoxy and poly (oxyethyleneoxy) units interconnected with the aryldicarbonyl and oxyalkylenoxy units.

Similarly, the esters of the soil release composition of the present invention is a phrase that includes the unusual double and single terminated compounds described in the present invention, mixtures thereof, and mixtures of said terminated materials that inevitably contain some unfinished components. However, the amount of unfinished components will be zero or minimal in all the most preferred compositions. Thus, when simply referring to an ester, this is by definition generally related to a mixture of the resulting sulfonate terminated and non-terminated ester molecules formed from any single preparation.

Any ester molecules that are used in the compositions of the present invention that are not fully, i.e., double terminated, end groups must terminate with units that are suitable for attaching sulfonated polyethoxypropoxy terminating units. These ends will typically be hydroxyl groups or other groups that may be termed reactants forming a unit that is suitable for attaching another group. For example, in structure (b) above, the chain end position to which the -H hydroxyl group is attached. In other structures that can be constructed, units such as - (O) CC ₆ H ₄ C (O) -OCH ₃ can be found in the end positions. The most preferred ester molecules in the present invention are, however, as noted above, those having two sulfonate terminal units and no backbone unit at the terminal position.

Symmetry - In esters where oxy-1,2-propyleneoxy units are also present, the methyl groups of oxy-1,2-propyleneoxy units may alternate with one of the adjacent hydrogen atoms -CH ₂ - to reduce / ¾ ...... ....

ester chain symmetry. Thus, an oxy-1,2-propyleneoxy unit can be described with either -OCH ₂ CH (CH ₃ ) - orientation or with -OCH (CH ₃ ) CH ₂ O- opposite. In addition, the carbon atoms in the oxy-1,2-propylene units to which the methyl units are attached are asymmetric, i.e. chiral, having four non-equivalent chemical entities attached.

Unlike oxy-1,2-propyleneoxy units, oxyethyleneoxy units cannot be used herein as the sole source of oxy-1,2-alkyleneoxy units without the addition of stabilizers because they do not have the necessary asymmetric character. It is the presence of asymmetric units and / or stabilizers that inhibit the crystallization of oligomers during manufacture and later when added to the wash solution. The use of oxyethyleneoxy units or a high ratio of oxyethyleneoxy to oxypropyleneoxy units must be complemented by the use of stabilizers to delay crystal formation. Therefore, such compositions of the present invention comprise the sulfonate type hydrotropes, linear or branched alkylbenzene sulfonates, paraffin sulfonates and mixtures thereof integrated into the oligomeric compositions.

Preferably, the esters may include various optional units which increase hydrophilicity and are non-polyester type bases. The pattern of such incorporation is generally random. The preferred optional units are anionic hydrophilic substances such as 5-sulfoisophthaloyl or the like. Such units, when incorporated into the ester backbone, are generally divided into two or more hydrophobic groups separated by one or more hydrophilic groups.

It should be noted that uncharged aryldicarbonyl units need not be exclusively terephthaloyl units, provided that the structure of the polyester product is not severely disturbed. Therefore, for example, minor amounts of isomeric unbranched dicarbonyl units such as isophthaloyl and the like are suitable for inclusion in esters.

Poly (oxyethylene) oxy units - optional poly (oxyethylene) oxy units containing esters of the soil release agent used herein have a degree of polymerization of 2-40 and make up 0-25 mole percent of the total oxyalkyleneoxy units present. Preferably, poly (oxyethylene) oxy units are present when the base unit contains 8 or more terephthaloyl groups, however, at least some poly (oxyethylene) oxy units should be present in the esters per 1.5 terephthaloyl units. Poly (oxyethylene) oxy units, especially in esters with 8 or more terephthaloyl units, aid in the rate of dissolution of the soil release composition into the wash solution.

The amount of poly (oxyethylene) oxy units present in the backbone is related to its degree of polymerization. For example, oxyethyleneoxyethyleneoxy units (made up of diethylene glycol) having a degree of polymerization of 2 consist of 0-25 mole percent of the total oxyalkyleneoxy units in the backbone. (Oxyethylene) ₃ units (formed from triethylene glycol) having a degree of polymerization of 3 consist of 0-18 mole percent of the total oxyalkyleneoxy units in the backbone. (Oxyethylene) ₃ units (made up of tetraethylene glycol) having a degree of polymerization of 4 consist of 0-12 mole percent of the total oxyalkyleneoxy units present in the backbone.

Terminated Units - Terminated units used in esters of the soil release agent used herein are sulfonated polyethoxy / propoxy groups. These terminated units provide anionically charged sites when the esters are dispersed in an aqueous medium such as a wash solution. The end groups serve as aids in aqueous transport and provide hydrophilic sites on the ester molecules.

It is not intended to exclude the acid form, but most generally, esters are used herein as sodium salts, other alkali metal salts, such as nitrogen-containing cations (especially tetraalkylammonium) salts, or as dissociated ions in aqueous media. Examples of terminated groups include sodium isethionate, sodium 2- (2-hydroxyethoxy) ethanesulfonate, sodium 2- [2- (2-hydroxyethoxy) ethoxy] ethanesulfonate, sodium 5-hydroxy-4-methyl-3-oxapentane sulfonate, alpha-3-sulfopropyl -omegahydroxypoly (oxy-1,2-ethanediyl) sodium (with an average degree of ethoxylation of 1-2),

Sodium 5-hydroxy-3-oxo-hexanesulfonate and mixtures thereof.

On a marine basis, the soil release composition herein preferably comprises one to two moles of sulfonate-terminated units per mole of ester. Most preferably, the esters are double-capped, i.e., there are two moles of terminated units per mole of esters. In view of the composition of the composition, it is clear that the contribution of the terminated unit fraction to the molecular weight of the esters will decrease as the molecular weight of the ester backbone increases.

Optional Stabilizer-Reducing Stabilizers - The stabilizers used in the detergent composition of the present invention are water-soluble or water-dispersible. Stabilizing agents useful in the present invention include sulfonate type hydrotropes, optionally branched alkylbenzene sulfonates, paraffin sulfonates and other thermally stable 4-20 carbon alkyl sulfonate variations. Preferred stabilizers include sodium dodecylbenzenesulfonate, sodium cemensulfonate, sodium toluenesulfonate, sodium xylene sulfonate, and mixtures thereof. When higher amounts of stabilizers are used, hydrotrope mixtures and / or other stabilizers are preferred over pure components to ensure full integration into the oligomer and reduce the possibility of crystallization of the stabilizer.

Generally, the amount of such stabilizers is kept as low as possible, provided that the primary benefit, i.e. the reduction in the amount of crystallization that occurs in the soil release composition during manufacture, storage and after addition to the wash solution, is maintained. The composition contains 0.5-20% stabilizer. Most preferably, the ester of the soil release composition comprises an amount sufficient to reduce crystallization of the oligomer during manufacture, and upon addition to the wash solution, i.e. at least 3% by weight.

The stabilizers are added to the soil release composition in several different ways. Preferably, the stabilizers are added to the oligomeric reagents in the early stages prior to full oligomerization. The stabilizers thus integrate evenly into the oligomer. Another method requires first melting the preformed oligomer and then uniformly mixing the stabilizer into the molten oligomer. The use of alkylbenzene sulfonates as surfactants in detergent compositions does not provide stabilization and the effect of reducing crystallization during dissolution of the soil release composition in the wash solution, such as when adding a stabilizer as described above.

Dye transfer inhibiting polymer

The selected polymeric dye retarding agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinyl imidazole, polyvinyl oxazolidones and polyvinyl imidazoles, and mixtures thereof. These polymers are used in amounts of 0.001-10%, preferably 0.01-2%.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use include units of the following formula (XXIV):

P

AND

AND

R

XXIV wherein P is a polymerizable unit to which the R-N-O group is attached or in which the R-N-O group forms part of the polymerizable unit or a combination of both.

0 0

II II II

A is NC, CO, C, -O-, -S-, -N-, x is 0 or 1

R is aliphatic, ethoxylate aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group is attached, or wherein the nitrogen of the N-O group is part of these groups.

The N-0 group is represented by the following formulas XXV and XXVI:

(R 1) x -N- (R 2) y I (R 3) 2

XXV = N- (R1) x

XXVI wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or / and y or / az is 0 or 1, and wherein the nitrogen of the N-O group is attached or wherein the nitrogen of the N-O group they form part of these groups.

The N-O group is part of a polymerizable unit (P) or is attached to a polymer backbone or a combination of both. Suitable polyamine N-oxides wherein the N-O group forms part of a polymerizable unit that contains polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

One class of said polyamine N-oxides comprises a group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of said polyamine N-oxides comprises a group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.

Other suitable N-oxides are polyamine oxides in which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides are the polyamine N-oxides of formula (XXIV) wherein R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the N-O functional group is part of said R group.

Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof.

Another preferred group of polyamine N-oxides are the polyamine oxides of formula (XXIV) wherein R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the N-O functional group is attached to said R groups.

Examples of these classes are polyamine oxides wherein the R groups are aromatic such as phenyl.

Any polymer backbone may be so long that the amide oxide polymer is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are vinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention have a typical amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by a suitable degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is 2: 3 to 1: 1 000 000. More preferably from 1: 4 to 1: 1 000 000, most preferably from 1: 7 to 1: 1 000 000. The polymers of the present invention include, irregular or block copolymers wherein one monomeric type is an amine N-oxide and the other monomeric type is either an amine N-oxide or not. The amine N-oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, most preferably pKa < 6. Polyamine oxides can be obtained at almost any degree of polymerization. The degree of polymerization is not critical provided the material has the desired water solubility and color retention power.

Typically, the average molecular weight is in the range of from 500 to 1,000,000, preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) N-vinylpyrrolidone and N-vinylmidazole copolymers

The polymers of N-aminimidazole of N-pyrrolidone used in the present invention have an average molecular weight of 5,000 to 1,000,000, more preferably 20,000-200,000.

Highly preferred polymers for use in the detergent compositions of the present invention comprise a polymer selected from N-vinylimidazole of N-vinylpyrrolidone copolymers, wherein said polymer has an average molecular weight of 5,000-50,000, more preferably 8,000-30,000, most preferably 10,000-20,000.

The average molecular weight range was determined by light scattering as described by Barth H.G. and Mays J.W. Chemical Analysis vol. 115, Modem Methods of Polymer Characterization. Most preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

N-vinylmidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight provide excellent dye transfer inhibiting properties, although they do not adversely affect the cleaning performance of the detergent compositions in which they are contained.

N-vinylmidazole The N-vinylpyrrolidone copolymers of the present invention have a molar ratio of N-vinylmidazole to N-vinylpyrrolidone of 1: 0.2, more preferably 0.8: 0.3, most preferably 0.6: 0.4.

c) Polyvinyloxazolidone

The detergent compositions of the present invention may also utilize polyvinylpyrrolidone (PVP with an average molecular weight from the detergent compositions of the present invention also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. 200,000, most preferably from 5,000 to 15,000.

d) Polyvinylimidazole

The detergent compositions of the present invention also use polyvinylimidazole as a dye transfer inhibiting agent. Said polyvinylimidazoles have an average molar mass of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.

Peroxidase enzymes

Peroxidase enzymes are used in combination with oxygen sources such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are preferably used for the bleach solution, i.e., they prevent the transfer of dyes or dye removed from the fabrics during the wash operation to other fabrics in the wash solution, they are also used as bleaching agents. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chlorine and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO91 / 05839.

When peroxidase is used, the amount should be such as to provide an activity in the range of 0.10 to 1.00 PoDU / ml wash solution.

The peroxidase is typically added as a component of the laundry detergent composition, and is added in an amount of from 0.01 to 100mg of enzyme per liter of washing liquid, preferably in an amount of

0.04-0.1mg of enzyme per liter.

Amylase enzymes

The composition of the present invention also comprises amylase enzymes.

Suitable amylases include, for example, amylases obtained from a special strain of B. lichenifor, described in more detail in GB-1,296,839 (Novo). Preferred commercially available amylases include, for example, Rapidasa, sold by International Bio-Synthetics Inc and Termamyl, sold by Novo Nordisk A / S.

Other suitable amylases are fungal components such as Fungamyl®, commercially available from Novo Nordisk A / S.

Amylases are used in an amount of from 0.05 to 1.5% by weight of the detergent composition. When a bacterial amylase such as Termamyl® is used, the amount of amylase is such as to provide activity in the range of 1-500 KNU / 100g detergent composition (Kilo Novo Units).

When a fungal amylase such as Fungamyl® is used, the amount is such as to provide an activity in the range of 1-5,000 FAU / 100g detergent composition (Fungal Apha Amylase Unit).

ΒβΟΟΟβ »9β & 9 ·? <* Η ·· * · Χ · ´ **

EDDS chelating agent

This chelating agent is ethylenediamine disuccinate (EDDS), especially the [S, S] isomer as disclosed in U.S. Pat. No. 4,704,233, November 3, 1987 to Hartman and Perkins.

EDDSs are typically used in an amount of from 0.1 to 10% by weight of the compositions, preferably from 0.12 to 5%.

Perfume encapsulants

The particulate perfume encapsulants are present in the compositions in an amount of from 0.001 to 10%, preferably from 0.1 to 3%.

Perfume encapsulants contain perfumes dispersed in certain carriers.

In the context of the present application, the term perfume means any aromatic material or anti-odor material. In general, such materials are characterized by a vapor pressure greater than atmospheric pressure at ambient temperatures. The perfume or deodorant materials used herein are most often liquid at ambient temperatures, but can also be solid as the various tamponade perfumes known in the art. A wide variety of chemicals for perfumery are known which include materials such as aldehydes, ketones, esters, etc. More commonly, naturally occurring plant and animal oils and effusions containing complex mixtures of different chemical components are known for use as perfumes, and such materials can be used herein. use. The perfumes used herein may be of relatively simple composition or may contain very complex, complex mixtures of natural and synthetic chemical components, all selected to provide any desired odor.

Perfumes that are normally solid are also used in the present invention. These are mixed with a liquefying agent such as a solvent prior to incorporation into the particles or simply melted and incorporated unless sublimated or decomposed upon heating.

The invention also includes the use of odor control materials. These materials, although referred to as perfumes below, may not have a recognizable odor but hide or reduce any unpleasant odors. Examples of suitable smelly stun guns are disclosed in U.S. Pat. No. 3,102,101, issued Aug. 27, 1963 to Hawley et al.

There is a wide variety of capsules that allow the release of the perfume effect at different times in the cleaning or conditioning process. Less protection ensures results in a greater perfume effect in the product or wash / conditioning process. Greater protection results in greater perfume effect during the drying process or even after the surface has been treated.

Examples of such housings with different encapsulated materials are housings made by microencapsulation. Here, the perfume comprises a shell core that is completely covered with a material that may be polymeric. U.S. Pat. No. 4,145,184, Brain et al., Issued Mar. 20, 1979; No. 4,234,627, Schilling, issued

November 18, 1980, describes the use of a rigid packaging material that substantially prevents diffusion from perfume. The perfume is delivered to the fabric in the microcapsules and is subsequently released by cleavage of the microcapsule as it happens during substance handling.

Another method involves providing protection of the perfume during the wash cycle and releasing the perfume under increased dryer heat conditions. U.S. Pat. No. 4,096,072, Brock et al., Issued June 20, 1978, discloses a method for delivering conditioning agents to textiles during a washing and drying cycle with particles comprising hydrogenated castor oil and a fatty quaternary ammonium salt. Perfume can be incorporated into these particles.

U.S. Pat. U.S. Patent 4,152,272 to Young discloses incorporating perfumes into wax particles to protect perfume during storage in dry compositions and to increase particulate deposition on fabrics during rinsing by concomitant use of a cationic surfactant. The perfume thus permeates through the wax matrix of the particles on the fabrics under increased dryer heat conditions.

Greater protection may be provided by selecting the encapsulating material to be used to form the capsules, the perfume to encapsulation ratio, or the agglomeration of the particles.

The choice of encapsulating material used in the perfume particles of the present invention depends on the amount of particular perfume used. Some perfumes will require more protection than others, and the encapsulation material used herein will be selected accordingly.

In general, the encapsulating materials of the perfume particles are a water-insoluble or water-soluble encapsulating material.

Non-limiting examples of useful water-insoluble materials include polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyacrylates, vinyl polymers and polyurethanes, and mixtures thereof.

Non-limiting examples of suitable water-soluble packaging materials include such materials as methylcellulose, maltodextrin and gelatin. Such containers contain 1-25% by weight of the particles.

Particularly suitable water-soluble encapsulating materials are shells which contain a matrix of polysaccharides and polyhydroxy compounds as described in GB 1,464,616.

Other suitable water-soluble or water-dispersible encapsulating materials include dextrins derived from non-gelatinized substituted dicarboxylic acid starch esters as described in U.S. Pat. Patent 3,455,838. These dextrin acid esters are preferably prepared from such starches as corn wax, sorghum wax, sago palms, tapioca and potatoes. Suitable examples of such encapsulating materials are N-Lok®, manufactured by National Starch, Narlex® (ST and ST2), Capsul E®. These encapsulating materials comprise pregelatinized corn wax starch and, optionally, glucose. The starch is modified by the addition of monofunctional substituted groups such as octenylsuccinic anhydride.

Water-soluble encapsulating materials are particularly suitable when the perfume is to be incorporated into a dry granular or powdered product. Such water-soluble containers thus protect the perfume during storage of the product from other conventional laundry detergent compounds such as bleach, enzymes, and clay.

For increased protection of perfume particles in the liquid product, it is preferable to encapsulate the perfume with a pH sensitive material, i.e. a material that remains as a coating on the particle in one pH environment but which is removed from the particle in a different pH environment. For example, such a material is used to encapsulate perfume in a liquid softening composition and having a pH of 3. When such composition is added to the wash water wherein the pH is greater than 6, the packaging material is removed. This allows for further protection of perfume in liquid formulations over a long shelf life, i.e., the perfume does not dissipate readily from the particle in the liquid medium. Thus, diffusion of perfume from the separated particle occurs after the particles are contacted with a different pH environment.

The perfume may also be encapsulated with a material that makes the particles more substantive to the surface being treated, for example, with the fabric in the laundry process. Such materials help deliver particles to the fabric and maximize the release of perfume directly onto the fabric. In general, these materials are water-insoluble cationic materials. Examples of materials used include any cationic (including imidazolium cation) compounds disclosed in US Patent 3,686,025, Morton, issued Aug. 22, 1972, incorporated herein by reference. Such materials are known in the art and include, for example, a quaternary ammonium salt having at least one, preferably two C ₁₀ -C ₂₀ fatty alkyl substituents, alkyl imidazolium salts, wherein the at least one alkyl group comprises a C ₃ -C ₂₅ chain, a C ₁₂ -C _{25 20} alkylpyridinium salts and the like.

Alternative materials used for encapsulating materials to be more substantive substantive are described in U.S. Pat. No. 4,234,627, Schilling, issued

On November 18, 1980, incorporated herein by reference.

Encapsulated perfume particles are prepared by mixing the perfume with the encapsulation matrix by spray drying an emulsion comprising the encapsulating material and the perfume. In addition, the particle size of the product from the drying shower tower can be adjusted. These treatments include specific manufacturing steps, such as agglomeration steps (e.g., fluidized bed) behind the particle size tower and / or manufacturing steps in which the surface properties of the encapsulants, such as hydrophobic silica dusting, are modified to reduce the hygroscopicity of the encapsulants.

A particularly preferred encapsulation process is an emulsification process followed by spray drying and finally quartz dusting. Emulsions are formed by:

a) disperses the starch matrix in water at room temperature in a ratio of 1: 2. It is preferred that the starch matrix be pregelatinized so that the emulsion is formed at this temperature. This minimizes the loss of perfume. The starch viscosity must be low in order to achieve a high starch concentration in water and a high perfume filling.

b) adding the perfume oil to the above mixture in a ratio of 0.8-1.5: 1: 2, and then emulsifying the mixture using a high speed mixer. Rotation must result in oil droplets of less than 1 micron and the emulsion must be stable in this form for at least 20 minutes (the starch function is to stabilize the emulsion if it is mechanically manufactured).

c) spray-drying the mixture in a circulating tower containing a centrifugal dike atomizer. The intake air temperature is low - 150 ° C - 200 ° C. This type of spray drying ensures minimal loss of perfume and high drying rate. The granules are 50-150 microns in size.

d) the resulting dry encapsulants contain up to 5% unencapsulated oil on the surface of the granules. To improve flowability, hydrophobic silicon is added to the encapsulation up to 2% by means of a belt mixer.

Other suitable perfume encapsulants include perfumes dispersed in certain carriers. Examples of such carriers are clay or zeolite materials as described in EP 535 942. Preferred carriers include zeolites as described in US Serial No. 08/071 124. Said zeolites have a nominal pore size of at least 6 Angstoms, whereby the perfume is absorbed into the zeolite pores of particles. The particles are then matrixed or coated with a mixture of a water-resistant polyol or diol and a solid polyol containing more than 3 hydroxyl groups.

It may be desirable to add additional perfume to the composition as it is without shell protection. Such perfume filling results in an aesthetically pleasing fragrance to the composition. Opening the package containing the composition and adding the product to the water will immediately release the desired odor.

The perfume is added by conventional means, for example by mixing as it is to a liquid composition or by spraying on dry compositions.

The laundry detergent compositions of the present invention can be incorporated into a wide variety of compositions that deliver perfume to the fabric, including detergent and rinse compositions.

Packaging system

A packaging system comprising the detergent compositions of the present invention is characterized in that it comprises at least one unit having a moisture vapor transmission rate of less than 20g / m ² / day, preferably 1g / m ² / day to 15g / m ² / day.

Moisture evaporation transfer rate is measured by a known method as described in ASTM Standard E-96-53T, by a test for measuring the water vapor transmission of layered materials, and TAPPI Standard T464 m-45, Water vapor permeability in laminates at high temperature, and humidity.

The method used in the context of the present invention is referred to as a procon test using a Permatran-W TWIN device.

Here's how:

Equipment

- aluminum test cups with lid (4 and 6 in diameter)

- template 1 (for slicing samples)

- template 2 (for wax application)

- electric cooker

- laboratory oven with temperature control (accuracy +/- 1 ° C)

- laboratory cabinet with humidity control (accuracy +/- 2%)

- microcrystalline wax (Mobel Oil Wax 2305 or equivalent)

calcium chloride, anhydrous, granulated,

- petrolatum

- an electric container with a thermostat for melting the wax

- cutting mat

- scissors or circular cutting knife

- laboratory scales (eg Mettler K-7, type Mikrowa FW-31-6 etc.) with an accuracy of +/- 0.05g.

Material preparation

The test sample is cut from the material to be tested. Another test sample of a uniform protective layer of material of known moisture vapor transmission rate is used as a control (eg, a linear layered bitumen or a wax layered plate).

Test procedure

1) The wax is heated to 90-110 ° C in an electric container. Heat the test crucibles in a laboratory oven or hot plate for 30 minutes at 90 ° C. One test crucible is removed from the oven after this time and the crucible is filled up to 2/3 of the height of the dish with calcium chloride, the petrolatum is carefully added along the slanted edge of the template 2. The bottom of the template 2 is wiped dry where it comes into contact with the test sample. . Place the sample in a crucible. The template 2 is placed over the sample and centered with respect to the crucible. The molten wax is poured into a circular space formed by the slanted edge of the template 2 and the rim of the crucible. When the wax solidifies, the template 2 is removed using a slight twisting motion. Weigh the composite crucible to the nearest 0,05 g before placing it in a test atmosphere. Crucibles are stored at 35 ° C / 80% eRH (Relative Humidity Equilibrium).

2) After two days in the humidity cabinet, weigh the crucibles every 24 hours until a constant weight gain is achieved in three consecutive measurements (maximum deviation 0.25g). The crucibles are weighed immediately after being removed from the humidity cabinet and covered with an aluminum lid as they are moved from the cabinet to the scale.

All weighings were recorded and the daily weight gain for each dish was calculated. Water vapor transmission rate is recorded in g / m ^2/24 hours and calculated as follows:

a) effective flat sample: 66.6cm ² (bowl 4 diameter)

X ^ ~ 600 g / m ^2/24 hours y

b) effective sample area: 133cm ² (bowl 6 in diameter)

800 x ^ - jg / m ^2/24 hours yy where x = total weight gain in grams y = time in hours (both calculated on the basis of 3 consecutive measurements with a daily constant weight gain)

A packaging system of at least one unit is a recipient of the detergent compositions of the present invention according to the present invention, such a unit being typically a consumer unit such as a bottle / can or bag / sachet or carton or cylinder containing the composition of the present invention designed to be used / stored Consumer households.

If such a unit already reaches the water vapor transmission rate characteristic of the present invention, it can be used alone and therefore form a packaging system according to the present invention.

However, it is possible that the water vapor transmission rate characteristic of the present invention is achieved by means of an outer packaging unit protecting the consumer unit, eg for shipping purposes. In such a case, the alice system comprises a consumer unit and one or more outer units, said outer units being made of plastic and / or paper layers or cardboard. These materials are described in more detail below.

The packaging system also consists of many consumer units that are connected for shipping purposes, eg in packs. In such a case, the outer unit will usually be a plastic container combined with a wide tray holding said consumer units together.

Depending on the embodiment of this system, the amount of detergent compositions contained in the packaging systems ranges from 250 g (individual small consumer units) to 20 kg (package consumer units).

The consumer units of these packaging systems are preferably bags or sacks, and such units are typically used in the form of refilled bags.

Re-filled bags are easily compressible shipping containers that have been designed to reduce the amount of plastic packaging materials disposed of in the environment.

Re-filled bags are used by emptying the contents into a stable package such as a plastic, metal or cardboard box which is used by the consumer to store detergent products.

In such an embodiment, the refilled bag is not resealed, but bags / sacks that can be resealed are also included in the present invention.

The sacks / bags herein are padded bags or reinforced bags, and any, but particularly reinforced bags, have reduced or no dead space, can be made of preformed and / or pre-filled material and are sealed in various ways, eg, heat, adhesive / adhesive , adhesive tapes.

Sacks / bags are made of films, either monolayer, including compressed or layered materials. Such films are typically paper or plastic, or a combination of the two, preferred bag materials are plastic and / or paper laminates. Plastic materials are typical polyolefins, and both plastic and paper are as yet unused or recycled material. Films are printed in different ways, typically gravure, fiexography, offset.

Also included are films having moisture properties which are obtained by resins either compressed or with differently laminated layers, or by coating, eg lacquers.

Consumable units may also consist of a cardboard box, packages or cylinders on which either fluted or laminated materials or a combination of both are used. The materials are either unused or recycled or plastic bottles and containers.

Said cardboard boxes / packages / cylinders are, if necessary for obtaining a suitable water vapor transfer rate, covered on the outside or inside with a layer of material, usually a metal or plastic layer, which provides the water vapor transfer rate unit of the present invention.

Cardboard boxes / packages / cylinders are printed as described above and / or coated with materials such as lacquers to provide protective properties.

Optional additives

The compositions of the present invention, in addition to one or more of the selected ingredients listed above, may also contain other ingredients as described below.

In one example of the present invention, when the bleach activators described above are used, granular laundry detergent compositions may also contain a (non-enzymatic) bleaching agent, however, bleach-free granular detergent compositions are also suitable, particularly for treating a particular agent requiring special care. Therefore, such bleach-free detergent compositions are also included in the present invention.

In such bleach-free embodiments, the selected moisture sensitive materials of the present invention are preferably selected from the group of choline polyaspartate esters, polyglutamates, maleic / acyclic acid / vinyl alcohol terpolymers, sulfonated polyethoxy / propoxy terminated ester oligomers, peroxidase enzymes, and mixtures thereof.

Bleaching agent

The bleaching agent, if used, is either an inorganic persulfate such as perborate, persulfate, percarbonate or a preformed organic peracid or perimidic acid such as N, N-phthaloylaminoperoxycaproic acid, 2-carboxy-phthaloylaminoperoxycaproic acid,

Ν, Ν-phthaloylaminoperoxyvaleric acid, peroxyadipic acid nonylamide, 1,12-diperoxydodecanoic acid, peroxybenzoic acid and peroxybenzoic acid substituted on the ring, monoperoxyphthalic acid (magnesium salt, hexahydrate), diperoxy- / razzs-13-docosenoic acid.

The bleach-containing laundry detergent herein typically comprises 1-40%, preferably

3-30%, most preferably 5-25% by weight of the bleaching agent.

The perborate bleach is usually in the form of its sodium salt and is present as a monohydrate to a tetrahydrate.

The percarbonate bleach is usually in the form of a sodium salt having an average size of 250-900 microns, preferably 500-700 microns. Sodium percarbonate is a mixed compound which corresponds to formula 2Na ₂ CO ₃ »3H ₂ 0 _second In order to increase the stability of the percarbonate, the bleach can be coated with, for example, a further mixed alkali metal sulfate and carbonate salt. Such coverage together with the deposition process was previously described in GB-1,466,799, provided by Interox on March 9, 1977. The weight ratio of the mixed salt of the wrapping material to the percarbonate is 1: 2,000 to 1: 4, more preferably 1:99 to 1: 9 and most preferred 1:49 áž 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the formula Na ₂ SO ₄ .n.Na ₂ CO ₃ wherein n is 0.1-3, preferably n is 0.3-1.0, and most preferably n is 0, 2-0,5.

Other suitable coating materials are sodium silicate in a SiO ₂ : Na ₂ O ratio of 1.6: 1 to 2.8: 1, and magnesium silicate.

Commercially available percarbonate bleached carbonates / sulfates may contain low levels of heavy metal masking agents such as EDTA, 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) or aminophosphate, which is added during the manufacturing process.

Preferred heavy metal masking agents for incorporation as described above include organic phosphonates and aminoalkylene polyes (alkylene phosphonates) such as the alkali metal salts of ethane-1-hydroxy diphosphonates, nitrile trimethylene phosphonates, ethylenediaminetetramethylene phosphonates, and diethylenetriaminepentamethylene phosphonates.

Surfactants

Preferred laundry detergent compositions herein comprise surfactants selected from the following ingredients:

Alkyl sulfate surfactants

The alkyl sulfate surfactants of the present invention are water-soluble salts or acids of formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbon, preferably an alkyl or hydroxyalkyl whose alkyl component consists of C ₁₀ -C ₂₀ alkyl, more preferably C ₁₂ - C ₁₈ alkyl or hydroxyalkyl, and M is H or a cation, eg an alkali metal cation (eg sodium, potassium, lithium), or an ammonium cation or a substituted ammonium cation (eg methyl, dimethyl, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for low wash temperatures (e.g., below 50 ° C) and C ₁₆ -C ₁₈ alkyl chains are preferred for higher wash temperatures (e.g., above 50 ° C).

Alkylalkoxylated sulfate surfactant

Alkyl alkoxylated sulfate surfactants of the present invention are water soluble salts or acids of the formula RO (A) _m SO ₃ M wherein R is a C ₁₀ -C nesubstiuovaná ₂₄ alkyl or hydroxyalkyl group whose alkyl moiety consists of C _I0 -C ₂₄ alkyl, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, even more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than 0, typically 0.5-6, more preferably 0.5-5, M is H or a cation which is, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.) ammonium or a substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are included in the present document. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethyl-ammonium dimetylpiperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are C ₂ C _g alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ E (l, 0) M), C ₁₂ -C _L8 alkyl polyethoxylate (2.25) sulfate, C _I2 -C _I8 E (2.25) M ), C ₁₂ -C ₁₈ alkylpolyethoxylated (3,0) sulfate, C ₁₂ -C ₁₈ E (3,0), and C ₁₂ -C ₁₈ alkylpolyethoxylated (4,0) sulfate, C ₁₂ -C ₁₈ E (4, O) M) sulfate, wherein M is commonly selected from sodium and potassium.

Other anionic surfactants

Other anionic surfactants useful for cleaning purposes are also included in the laundry detergent compositions of the present invention. These include salts (including, for example, sodium, potassium, ammonium cation, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C ₉ -C ₂₀ linear alkylbenzene sulfonates, C ₈ -C ₂₂ primary or secondary alkanesulfonates, C ₈ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g. as described in British patent specification No. 1,082,179, C ₈ -C ₂₄ alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) acyl glycerol sulfonates, fatty sulfates, glycerol, oil residues, alkyl phenol ethylene oxide sulfates, parafínosulfonáty, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ,, - C _I8 monoesters) diesters of sulfosuccinate (ZVI. saturated and unsaturated C _{14 and} -C diesters), acyl sarcosinates, sulfátyalkylpolysacharidú such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those the formula RO (CH ₂ CH ₂ O) _c CH ₂ COO-M ⁺ wherein R is a C ₈ -C ₂₂ alkyl, k is an integer from 0 to 10, M is a cation which forms a water soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in Surface Active Agents and Detergents ¹ '(Vol. I and II by Schwartz, Perry and Berch). A wide variety of these surfactants is also generally summarized in US Patent 3,929,678, issued December 30, 1975 to Laughlin, et al., Col. 23, line 58 through Col. 29, line 23 (herein incorporated by reference).

Preferred surfactants for use in the compositions of the present invention are alkyl sulfates, alkylalkoxylated sulfates, and mixtures thereof.

When included herein, laundry detergent compositions typically comprise from 1 to 40%, preferably from 3 to 20% by weight of anionic surfactants.

Nonionic surfactants

The present laundry detergent detergent compositions preferably also contain nonionic surfactants.

Although any nonionic surfactant can normally be used according to the present invention, two classes of nonionic surfactants have been found which are particularly useful. They are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and nonionic surfactants based on amidation products of fatty acid esters and N-alkyl polyhydroxyamine. Amidation products of esters and amines are generally understood to mean polyhydroxy fatty acid amides. Particularly useful according to the present invention are compositions comprising two or more nonionic surfactants, characterized in that at least one nonionic surfactant is selected from the group of alkoxylated alcohols and from the group of polyhydroxy fatty acid amides.

Suitable nonionic surfactants include compounds formed by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature. The length of the polyoxyalkylene group that condenses with any individual hydrophobic group can be readily adjusted to provide a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements.

Particularly preferred for use in the present invention are nonionic surfactants such as polyethylene oxide condensates with alkylphenols, e.g., C ₆ -C ₁₀ alkylphenol condensation products, in a straight chain or branched chain configuration with 4-25 moles of ethylene oxide per mole of alkylphenol.

Preferred nonionic surfactants are the water-soluble condensation products of C ₈ -C ₂₂ aliphatic alcohols, in a straight chain or branched chain configuration, with an average of 25 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having C ₉ -C ₁₅ alkyl with 2-10 moles of ethylene oxide per mole of alcohol and the condensation products of propylene glycol with ethylene oxide. Most preferred are the condensation products of alcohols having C ₁₂ -C ₁₅ alkyl with an average of 3 moles of ethylene oxide per mole of alcohol.

Also useful as the nonionic surfactant in the surfactant system of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, LIenado, issued January 21, 1986, having a hydrophobic group _{with a} C, -C ₃₀ alkyl, preferably C ₁₆ -C _I0 alkyl polysaccharide, and , e.g., a polyglycoside hydrophilic group having 1.3-10, preferably 1.3-3, most preferably 1.3-2.7 carbohydrate units. Any reducing carbohydrates having 5 or 6 carbon atoms may be used, eg, glucose, galactose, and galactosyl groups may replace glucosyl groups (optionally, the hydrophobic group is attached at 2-, 3-, 4-, etc. positions to form glucose or galactoses (substances referred to as glucoside or galactoside). Sugar linkages are, for example, between one position of subsequent saccharide units and 2-, 3-, 4-, and / or 6- positions of previous saccharide units.

Preferred alkyl polyglucosides are those of formula XXVII

R ² O (C _n H 2 _n O) _t (glucosyl) _x

XXVII wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof wherein the alkyl groups have 10-18 carbon atoms, more preferably 12-14 carbon atoms, n is 2 or 3, preferably 2, t is 0- 10, preferably 1.3-3, most preferably 1.3-2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form a glucoside (attachment at position 1-). Other glycosyl units may be attached by position 1- to the preceding glycosyl units at positions 2-, 3-, 4-, and / or 6-, preferably the position 2-,

Other surfactants

The laundry detergent compositions of the present invention also include the cationic surfactants, ampholytic, zwitterionic and semipolar surfactants (other than those described above) and other nonionic surfactant agents including the semi-polar nonionic amine oxides described below.

The cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having a single long hydrocarbon chain. Examples of such cationic surfactants include ammonium surfactants such as alkyldi or trimethylammonium compounds, and such surfactants are those of formula XXVIII:

[R ² (OR ³ ) y] [R ⁴ (OR ³ ) y] ₂ R ⁵ N + XXXVIII wherein R is an alkyl or alkylbenzyl group having 8-18 carbon atoms in the alkyl chain, wherein each R ³ is selected from the group consisting of with -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 -, and mixtures thereof, each R ⁴ is selected from the group consisting of C 1 -C ₄ alkyl, C 1 -C ₄ hydroxyalkyl benzyl rings formed by the attachment of two R ⁴ groups, -CH 2 COH-CHOHCOR ^& CHOHCH 2 OH wherein R ⁶ is any hexose or hexose polymer having a molecular weight of less than 1000 and hydrogen when y is not 0, R ³ is the same as R ⁴ or it is an alkyl chain wherein the total number of carbon atoms R ² plus R ⁵ is not greater than 18, each y is from 0 to 10 and the sum of the y values is 0-15, X is any compatible anion.

Other cationic surfactants used herein are also described in U.S. Pat. No. 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.

When included herein, the laundry detergent compositions of the invention typically comprise 0-25%, preferably 3-15% by weight of such a cationic surfactant.

Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical is straight or branched. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8-18 carbon atoms, and at least one contains an anionic water-soluble group, e.g., carboxyl, sulfonate, sulfate. See. U.S. Pat. Patent No. No. 3,929,678, Laughlin et al., Issued Dec. 30, 1975, column 19, line 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.

When included, the laundry detergent compositions of the present invention typically comprise 0-15%, preferably 1-10% by weight of such an ampholytic surfactant.

Zwitterionic surfactants are also suitable for use in laundry detergent compositions. Such surfactants are generally described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. Patent No. No. 3,929,678, Laughlin et al., Issued Dec. 30, 1975, column 19, line 38, column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.

When included, the laundry detergent compositions of the present invention typically comprise 0-15%, preferably 1-10% by weight of such a zwitterionic surfactant.

Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one C ₁₀ -C _Ig alkyl group and two groups selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1-3 carbon atoms, water-soluble phosphine oxides an alkyl group having one C ₁₀ -C _Ig and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1-3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants of formula XXIX:

O t

R ³ (OR ⁴ ) x N (R ⁵ ) 2

XXIX

Filler

Preferred detergent compositions comprise a builder, preferably non-phosphate detergent builders, although phosphate-containing ingredients are not excluded from the scope of the present invention. These include, but are not limited to, carbonates, bicarbonates, silicates, aluminosilicates, alkali metal carboxylates, and mixtures thereof. The filler system is present in an amount of from 1 to 80% by weight of the composition, typically preferably 20-60% by weight in the granular laundry detergent compositions of the present invention and 1-30% in the liquid laundry compositions of the present invention.

Suitable silicates are those having a SiO ₂ : Na ₂ O ratio in the range of 1.6-3.4, so-called amorphous silicates preferably have a SiO ₂ : Na ₂ O ratio of 2.0-2.8.

From the class of silicates, particularly preferred materials are crystalline layered sodium silicates of formula XXX:

NaMSi _x O ,, + lyHjO XXX wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For purposes of the present invention, x in the general formula above is 2, 3 or 4 and is preferably 2. More preferably, M is sodium and y is 0, and preferred examples of this formula include Na ₂ Si ₂ O ₅ . These materials are available from Hoechst AG FRG as NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is -Na ₂ Si ₂ O ₅ , NaSKS-6. Crystalline layered silicates are incorporated either as dry mixed solids or as solid components of agglomerates with other components.

A variety of aluminosilicate ion exchange materials can be used, preferred sodium aluminosilicate zeolites having a unit cell of Formula XXXI:

Na _z [(AlO ₂ ) _z . (SiO ₂ ) _y ] - _x H ₂ O

XXXI wherein z and y are at least 6, the molar ratio of z k is 1.0 to 0.4 and z is 10-264. The amorphous hydrated aluminosilicate materials used herein have the empirical general formula XXXII:

M _z (zA10 ₂ .ySi0 ₂ )

XXXII wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said materials having a magnesium exchange capacity of at least 50 milligrams of CaCO ₃ equivalent hardness per gram of anhydrous aluminosilicate. Preferred is hydrated sodium Zeolite A having a particle size of 1-10 microns.

The aluminosilicate ion exchanger fillers are in hydrated form and contain 10-28% by weight of water, if they are crystalline materials, and potentially higher amounts of water, if any; o amorphous materials. Highly preferred crystalline aluminosilicate ion exchange materials contain 18-22% water in the crystal matrix. Crystalline aluminosilicate ion exchange materials are further characterized by a particle size of 0.1-10 microns in diameter. Amorphous materials are often smaller, e.g., smaller (less than 0.01 microns. Preferred ion exchange materials have a particle size of 0.2-4 microns in diameter. The average particle size here represents the average particle size on average for the weight of the ion exchanger material as is determined by conventional analytical techniques such as scanning electron microscopy.

The aluminosilicate ion exchange materials used in the process of the present invention are commercially available. The aluminosilicates used in the present invention are crystalline or amorphous structures and are naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Pat. Patent No. No. 3,985,669, Krummel et al., Issued Oct. 12, 1976, incorporated herein by reference. Preferred synthetic crystalline ion exchange materials used herein are available under the designation Zeolite A, Zeolite X, P and MAP, the latter being described in EPA 384070. In a particularly preferred example, the crystalline aluminosilicate ion exchanger Zeolite A having the general formula XXXIII:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO 2) ₁₂ ] -xH ₂ O

XXXIII wherein x is 20-30, especially 27, and the particle size is less than 5 microns.

Suitable carboxylate builders that contain a single carboxyl group include lactic acid, glycolic acid, and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686 and 2,446,687 840,623. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 5,960,549. 1,379,241, the lactoxysuccinates described in the Netherlands Application

7205873, and oxypolycarboxylate materials such as the 2-oxa-1,3,3-propane tricarboxylates disclosed in British Patent No. 5,960,249; 1,387,447.

Polycarboxylates containing four carboxy groups include the oxydisuccinates disclosed in British patent no. 1,261,829 and 1,2,2-etantetracarboxylates,

1,1,3,3-propantetracarboxylates and 1,1,2,3-propantetracarboxylates. Polycarboxylates containing sulfo substituents include sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent Nos. 3,936,448 and sulfonate pyrrolized citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphonium substituents are disclosed in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentancis, cis, cis-tetracarboxylates, cyclopentadienyl pentacarboxylates,

2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5, 6-hexanehexacarboxylates and carboxymethyl derivatives of polyhydroxyl alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and phthalic acid derivatives disclosed in British Patent No. 5,960,049. 1,425,343.

Other optional ingredients

Other ingredients known for use in detergent compositions can also be used as optional ingredients in the various examples of the present invention, such as other bleach activators, other chelating agents, other enzymes, suds suppressors, fabric softening agents, especially clay softening agents, as well as dyes, fillers, optical brighteners, pH-regulating agents, non-alkaline fillers, enzyme-stable agents, hydrotropes, solvents, perfumes.

Other bleach activators

Other bleach activators include N-, N, N N tetraacetyl compounds of formula XXXV:

ch ₃ co

li cch ₃

cch ₃ o

XXXV where x is 0 or an integer between 1 and 6.

Examples include tetraacetylmethylenediamine (TAMD), where x = 1, tetraacetylethylenediamine (TAED), where x = 2, and tetraacetylhexylenediamine (TAHD), where x = 6. These and analogous compounds are disclosed in GB-A-907,356. The most preferred peroxyacid bleach activator additional bleach component is TAED.

Another group of other suitable peroxyacid bleach compounds are substituted amide compounds of the following formulas XXXVI and XXXVII:

R>. C - NR ² - C - L or R 1 - N - CR ² - C - L

It I 11 II or ⁵ or ^s oo

XXXVI XXXVII wherein R 1 is an aryl or alkaryl group having 1-14 carbon atoms, R ² is alkylene, arylene and alkarylene group containing 1-14 carbon atoms, R ⁵ is H or an alkyl, aryl or alkaryl group containing 1-10 carbon atoms and L is necessarily any leaving group. R ¹ preferably contains 6-12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ has a straight chain or is a branched alkyl, substituted aryl or a branched alkyl, substituted aryl or both and is obtained either from synthetic sources or natural sources including, for example, tallow. Analogous structural variations are permissible for R ^2nd Substitution includes alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ do not contain a total of more than 18 carbon atoms. Compounds of substituted bleach activator amides of this type are described in EP-A-0170386.

Other chelating agents

The detergent compositions herein may contain chelating agents for iron and / or manganese other than EDDS. Such chelating agents are selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof as defined herein. Without wishing to be bound by theory, it is believed that the utility of these materials is due in part to their exceptional ability to remove ferric and manganese ions from washing solutions by forming soluble chelates;

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetraprionates, triethylenetetraamine hexaacetates, diethylenetriaminepentaacetates and ethanediglycines, ammonium salts thereof, ammonium salts thereof, ammonium salts thereof, ammonium salts thereof, ammonium salts thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least a low amount of total phosphorus content is allowed in detergent compositions and include ethylene diamine tetrakis (methylene phosphonates) such as OEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also used herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Other enzymes

Enzymatic materials other than peroxidases and amylases are incorporated herein into detergent compositions. Proteases, lipases, cellulases and mixtures thereof are suitable. A suitable Upase enzyme is manufactured and sold by Novo Industries A / S (Denmark) under the trade name Lipolase and listed together with other suitable lipases in EP-A-0258068 (Novo Nordisk).

Suitable cellulases are described, for example, in WO-91/17243 and WO 91/17244.

Suitable commercially available protease enzymes include those sold under the trade names Alcalase and Savinase from Novo Industries A / S (Denmark) and Maxatase from International BioSynthetics, Inc. (The Netherlands).

Other proteases include Protease A (see European Patent Application 130 756, issued January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130 756, Bott et al., issued January 9, 1985).

A preferred process for forming laundry detergent compositions.

In a preferred process for making the laundry detergent compositions of the present invention, particularly when high bulk density is desired, a portion of all surfactants contained in the resulting composition is incorporated as discrete particles, said particles being in the form of flakes, noodles, strips, beads, but they are preferably granular in shape. The most preferred method of operating the particles is to agglomerate powders (such as aluminosilicate, carbonate) with highly active paste surfactants and control the particle size of the resulting agglomerates within prescribed limits.

Such a process involves mixing a useful amount of powder with highly active paste surfactants in one or more agglomerates such as a bowl agglomerator, Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad , Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably, a high-speed mixer such as Lodige CB (trade name) is used.

A highly active surfactant in the form of a paste is used which contains 50-95% by weight, preferably 70-85% by weight of the surfactant. The surfactant system may include any of the group of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants or mixtures thereof. The paste is sprayed into the agglomerator at a temperature high enough to maintain a viscosity such that the substance can be pumped but low enough to prevent degradation of the anionic surfactants used. A typical paste temperature of 50-80 ° C is typical.

A particularly suitable process for forming surfactant particles from highly active paste surfactants is described in more detail in EP 510 746, issued October 28, 1992.

The free-flowing surfactant particles formed by the process described above are then mixed with the other detergent ingredients to form the resulting detergent composition.

This mixing can take place in any suitable apparatus. Liquid detergents such as nonionic surfactant and perfume are sprayed onto the surface of one or more of the constituent granules or into the resulting composition.

Example 3

Additional detergent compositions of the invention were prepared by:

Component Weight part Examples 1 2 3 4 5 6 7 8 Examples Linear alkylsulfonate 7 0 0 0 0 0 0 0 Tallow-derived alkyl sulfate 3 0 0 0 0 0 0 0 Alkylsulfate 0 9 6 9 12 12 9 6 Alkyl ethoxylate sulfate 0.2 2 1 2 2 3 3 3 Cholinesters derived from coconut oil 0 0 0 0 0 0 0 Alkyl ethoxylate (5 to 7 times ethoxylated) 4 5 10 6 4 7 8 Ί2 Alkyl-N-methylglucosamide 0 2 3 3 1 3.5 3.5 3.5 Peroxoboritan 22nd 0 0 0 0 0 0 0 Percarbonate 0 22nd 19 Dec 22nd 24 0 0 0 (6-Okanamido-capryloyl) oxy- benzenesulfonate 0 5 0 0 0 0 0 0 Benzoylkaproíaktam 0 0 2 5 0 0 0 0 N- [4- (trimethylammoniumethyibenzoyl) caprolactam chloride 0 0 0 0 4 0 0 0 Ν, Ν, Ν, tetra-tetraacetylethylene- amine 5 0 2 5 0 0 0 0 S, S-ethylenedisuccinic acid 0 0 0.5 0.5 0.5 0 0 0 Peroxidase 1 PODU 0 0.4 0 0.3 0.1 0.2 0 0.1 Termamyl 60 KNU 0.6 0.3 0 0.2 0.5 0.8 0.2 0.2 Fungamyl 1600 FAU 0 0.125 0.2 0.2 0 0 0.3 0.3 Lipolasa 165 KLU 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2

q-fe. • «μ **** · —52

Granular laundry detergent Examples 3 4 5 6 7 8 9 10 Cellulasa 1000 Vascular 0.1 0.2 0.3 0 0.3 0.2 0.2 0.2 Endoglucanase 5000 S-CEVU 0 0.1 0.1 O 0.1 0.1 0.1 0.1 Protease (Savinasa) 13 KNPU 0.4 0.5 0.7 ob 0.5 0.7 0.7 0.7 Aluminosilicate (zeolite A) 21 13 15 Dec 15 Dec 18 19 Dec 21 23 Layered silicate 0 12 11 11 9 9 11 7 Sodium citrate 6 5 4 4 3 11 9 8 Sodium carbonate 16 8 7 7 7 11 11 9 Sodium silicate 3 0 0 0 0 4 6 8 Sulfate 4 0.6 0.6 0.6 0.6 0 0 0 Soil Release Polymer * 0.3 0.3 0.2 0.2 0.2 0.2 0.2 0.2 Polyvinyl-N-oxide 0.3 0 0> 5 0.2 0.2 0.4 0.3 PVPVI 0 0.05 0 O 0.2 0.5 0.1 Maleic acid / acyclic vinyl alcohol terpolymer 0 0 3 4 0 3 0 0 Polyaspartate 0 0 0 0 0 4 2 Encapsulated fragrances 0 0 0.2 0 0 0 0 0.4 Secondary components Coll. to 100

‘As described above

Industrial applicability

When said compositions are stored at 35 ° C / 80% eRH (relative humidity equilibrium) environment in plastic or polyethylene layered refillable bags with a measured MVTR (water vapor transmission rate) of 5g / m ² / day, or plastic containers with a measured MVTR 0 , 5g / m ² / day, the composition shows excellent stability after four weeks of storage, the eRH measured at 35 ° C of the composition has a range from 10 to pack to 28 after 4 weeks of storage.

Claims (11)

PATENT CLAIMS A detergent composition comprising at least one wet-sensitive additive selected from the group consisting of: - non-ionic polyhydroxy fatty acid amide surfactants cholinesters of cationic surfactants - bleach activators selected from alkanoyloxybenzene sulfonates, amide-derived components, benzoxazine-type components, quaternary-substituted components and mixtures thereof polymers selected from polyamine N-oxides, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl oxazolidones and polyvinylimidazoles, polyaspartate, polyglutamate, vinyl alcohol / maleic acid / acrylic terpolymer, sulfonated polyethoxy / propoxy terminated ester oligomers, and mixtures thereof peroxidase enzymes amylase enzymes - the ethylenediamine disuccinic acid chelating agent - perfume encapsulants mixtures thereof with a packaging system comprising said composition, characterized in that the composition has an equilibrium relative humidity below 35% at 35 ° C, and that the packaging system comprises at least one unit having a water vapor transmission rate of less than 20g / m ² / day. The composition of claim 1, wherein said packaging system has a rate of 1g / m ² / day-20g / m ² / day. that the vapor transfer unit Composition according to claim 2, characterized in that the unit in the packaging system has a water vapor transmission rate of 1g / m ² / day-15g / m ² / day. A composition according to claims 2 and 3, characterized in that the at least one packaging system unit consists of a bag or sachet made of single-ply or laminated paper and / or plastic film. Composition according to claim 4, characterized in that the packaging system consists of such a bag or bag. 6. The composition of claim 4 or 5, wherein the bag or bag is refillable bag. A composition according to any one of claims 1 to 6 wherein the granular detergent composition is a detergent composition comprising a surfactant and a filler. 8. The composition of claim 8 wherein the composition has a bulk density of greater than 650 g / L. 9. The composition of claim 9 wherein at least one portion of the surfactant is added to the composition in the form of an agglomerate or extrudate. 10. A composition according to any one of claims 7 to 10 wherein the composition comprises a peroxygen or peroxyacid bleaching agent. 11. A composition according to any one of claims 7 to 10 wherein the composition is free of a bleaching agent and selected from: cholinester cationic surfactant polymers selected from: polyaspartate, polyglutamate, vinyl alcohol / maleic acid / acyclic acid terpolymer, sulfonated polyethoxy / propoxy terminated ester oligomers peroxidase enzymes - and mixtures thereof.