HU217365B - Composition inhibiting dye transfer in textiles during the washing and detergent containing it - Google Patents

Abstract

The present invention relates to inhibiting dye transfer compositions comprising polyamine N-oxide containing polymers and terephthalate-based polymers.

Description

FIELD OF THE INVENTION The present invention relates to a composition for inhibiting dye transfer during washing of textiles.

One of the most common and unpleasant problems with modem fabric washing operations is that some colored fabrics tend to release dye into the wash solution. The other fabrics washed with these materials are then colored by the dye.

One way to solve this problem is to complex or absorb fading inks washed from the dyed fabric before they have the ability to bind to other pieces in the wash. Polymers used to prevent dye transfer in detergent compositions are disclosed, for example, in EP-A-0102923, DE-A-2814329, FR-A-2 144721 and EP-265257.

In addition to dye setting, it is important to prevent the tendency of some colored fabrics to release ink into the wash solution. It has now been found that terephthalate-based soil release polymers increase the overall dye transfer inhibiting performance when added to the disclosed polyamine N-oxide dye transfer inhibiting compositions.

This recognition makes it possible to formulate detergent compositions which are very effective in preventing discoloration and in preventing the transfer of soluble or suspended inks.

BACKGROUND OF THE INVENTION Terphthalate-based soiling release polymers are also disclosed, e.g.

The present invention relates to dye transfer inhibiting compositions comprising

A) polyamine N-oxide polymers,

B) terephthalate-based polymers.

The compositions according to the invention contain as basic elements polyamine N-oxide polymers (A) and a terephthalate-based polymer (B).

A) Polyamine-N-oxide polymers:

The polyamine N-oxide polymers contain units of the general formula I which

P is a polymerizable moiety to which the N-O moiety is attached, or wherein the N-O moiety is part of the polymerizable moiety, or a combination of the two;

A is = NC (O) -, -C (O) O, = C = O, -O-, -S-, -N =;

x is 0 or 1;

R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the formulas a and b:

wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic, or combinations thereof, x and / or y, and / or z is 0 or 1, and wherein the nitrogen of the NO group may be attached thereto, or wherein NO nitrogen in these groups is part of these groups.

The N-O moiety may be part of the polymerizable moiety (P) or be linked to the polymer backbone or a combination of the two.

Suitable polyamine N-oxides wherein the N-O group is part of a polymerizable moiety wherein the R group is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.

A group of said polyamine N-oxides comprises a group of polyamine N-oxides wherein the nitrogen of the N-O group is part of the R group. Preferred polyamine N-oxides wherein R is a heterocyclic group such as pyridinyl, pyrrolyl, imidazolyl, pyrrolidinyl, piperidinyl and derivatives thereof. Another group 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 polyamine N-oxides are those polyamine oxides wherein the N-O group is attached to the polymerizable moiety. A preferred group of these polyamine N-oxides is the polyamine N-oxide of formula I wherein R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O functional group is part of that R group.

Examples of these groups are polyamine N-oxides wherein R is a heterocyclic group such as pyridinyl, pyrrolyl, imidazolyl and derivatives thereof.

Another preferred group of these polyamine N-oxides are the polyamine N-oxides of formula I wherein R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O functional group is attached to said R group.

Examples of these groups are polyamine noxides wherein the R groups may be an aromatic group such as phenyl.

Any polymer backbone may be used as long as the resulting amine oxide polymer is water soluble and has dye transfer inhibiting properties. Suitable polymer backbones include, for example, polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates, and mixtures thereof.

Typically, the amine N-oxide polymers of the invention have an amine / amine N-oxide molar ratio of from 10: 1 to 1: 1 million. However, the amount of amino oxide groups present in the polyamine oxide polymer may be varied by appropriate copolymerization or by appropriate degree of N-oxidation. The ratio of amine to amine N-oxide is from 3: 1 to 1: 1000000. The polymers of the present invention are in fact random or block copolymers, with one monomer type being an amine Noxide and the other monomer type being an N-oxide.

The amine oxide unit of the polyamine N-oxides has a PKa <10, preferably PKa <7, more preferably PKa <6.

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Polyamine oxides can be obtained at almost every stage of polymerization. The degree of polymerization is not critical provided that the material has the desired water solubility and dye-suspending power.

The average molecular weight is typically between 500 and 1000000; more preferably between 1000 and 500000; most preferably within the range of 5,000 to 100,000.

The polyamine N-oxides of the present invention are typically present in an amount of 0.01 to 10% by weight, more preferably 0.05 to 1% by weight, most preferably 0.05 to 0.5% by weight in the dye transfer inhibiting composition.

B) Polymer based on terephthalate, release release

It has been surprisingly found that the addition of terphthalate-based, soil release polymers improves the overall dye transfer performance of detergent formulations containing polyamine N-oxide polymers.

It is believed that polyamine N-oxide polymers improve the capacity for adsorption of terephthalate-based soil release polymers onto fabrics. As a result, the soil release polymer is more adsorbed to the surface of the fabric dipped in the wash solution. It is also believed that the backbone structure is important for adsorbing the polymers to the surface of the fabrics, while the end groups provide a soil release property. The adsorbed polyester then forms a film on the fabrics that prevents dye leakage from the fabric. The combination of the terephthalate-based polymers and the polyamine-N-oxide containing the polymers enables us to provide dye transfer inhibiting compositions which are very effective in preventing color leakage and in eliminating the transfer of soluble or suspended dyes.

The compositions according to the invention contain from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, of a terphthalate-based soil release polymer in the total dye transfer inhibiting composition. These soiling release polymers are described in detail in the prior art, for example, in U.S. Patent Nos. 4,116,885, 4,132,680, EP 185427, EP 199403, EP 241985 and EP 241 984.

Polymers of formula II are suitable for use in the present invention. In Formula AII, the oligomer or the polymeric backbone of the compounds is formed by the group ~ [(AR ¹ -AR ² ) U (AR ³ -AR ² ) V] -AR ⁴ -A.

Related A groups are essentially -C (O) O or -OC (O) - groups, i.e. the compounds of the invention are polyesters. As used herein, the term "A groups are essentially -OC (O) or -C (O) O-" refers to compounds wherein A is completely -OC (O) - or -C (O) They are O- or partially substituted with related groups such as -NHCO- or -C (O) NH- (amide) and -OC (O) NH- or -NHC (O) O- (urethane). Partial substitution with these other related groups should be such that they do not adversely affect the release properties. Preferably, the linked A groups are completely (i.e. 100%) -OC (O) - or -C (O) O-, i.e. each A is either -OC (O) - or -C (O) O - group.

R ¹ groups are essentially 1,4-phenylene groups. As used herein, the term "R ¹ groups is essentially 1,4-phenylene groups" refers to compounds wherein the R ¹ groups are wholly 1,4-phenylene or partially substituted with other arylene or alkarylene, alkylene, alkenylene or mixtures thereof. The arylene and alkarylene groups with which the 1,4-phenylene moiety may be partially substituted include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene. , 4,4'-biphenylene groups and mixtures thereof. Partially substituted alkylene or cycloalkylene groups include ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, octamethylene, 1,4-cyclohexylene groups and mixtures thereof.

The degree of partial substitution with groups other than the 1,4-phenylene moiety of the R ¹ groups should be such that they do not adversely affect the ability of the compound to dissolve. Generally, the degree of tolerable partial substitution will depend on the backbone length of the compound, i.e., for longer backbones, the partial substitution of 1,4-phenylene groups may be higher. Generally, compounds wherein R ^{1 contains from} 50 to 100% of 1,4-phenylene groups (from 0 to 50% of non-1,4-phenylene groups) exhibit satisfactory soil release activity. For example, polyesters prepared according to the invention with a molar ratio of (1,3-phenylene) -isophthalic acid to (1,4-phenylene) -terephthalic acid in a ratio of 40:60 have satisfactory soil release activity. But since most of the polyesters used in fiber manufacturing contain ethylene terephthalate units, it is usually desirable to have the

To minimize the degree of partial substitution with non-phenylene groups. Preferably, the R ¹ group consists entirely (i.e. 100%) of the 1,4-phenylene groups, i.e. each R ¹ group

1.4- Phenylene.

R ² groups are essentially ethylene groups or substituted ethylene groups containing C 1-4 alkyl or alkoxy substituents. As used herein, "R ² groups are essentially ethylene or substituted C 1 -C 4 alkyl or alkoxy substituents" as used herein to mean compounds of the present invention wherein R ^{2 is} wholly ethylene or substituted ethylene, or partially replaced by compatible groups. Examples of these other groups are linear C 3 -C 6 alkylene groups such as 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexamethylene, 1,2-cycloalkylene, e.g. cyclohexylene, 1,4-cycloalkylene groups such as 1,4-cyclohexylene and 1,4-dimethylene cyclohexylene groups, alkylated polyoxy-1,2-hydroxyalkylenes e.g.

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-CH ₂ -CHCH ₂ -O (CH ₂ CH ₂ O) _p -X and oxyalkylene groups such as -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ - or -CH ₂ CH ₂ OCH ₂ CH ₂ groups.

For R ² groups, the degree of partial substitution with these other groups should be such that it does not adversely affect the release properties of the compound in any significant way. In general, the degree of tolerable partial substitution will depend on the backbone length of the compound, i.e. longer backbones may have higher partial substitution. Generally, compounds wherein R ^{2 contains from} 20 to 100 mol% of ethylene or substituted ethylene (from 0 to 80% of other compatible groups) will have satisfactory soil release activity. For example, polyesters prepared according to the invention having a 75:25 molar ratio of diethylene glycol (-CH ₂ CH ₂ OCH ₂ CH ₂ -) / ethylene glycol have satisfactory soil release activity. However, such partial substitution should be minimized for best soil release activity. [During the preparation of the polyesters according to the invention, small amounts of these oxyalkylene groups (as dialkylene glycols) are typically formed by side reactions from glycols and are then incorporated into the polyester.] R ² groups preferably contain from 80 to 100% ethylene or substituted ethylene groups; from 20% other compatible groups.

The R ² moieties, suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2butilén-, mixtures of 1,2-hexylene, 3-methoxy-1,2-propylene and thereof. The higher percentage uptake of ethylene groups is intended to improve the anti-soiling activity of the compounds. Surprisingly, the inclusion of a higher percentage of 1,2-propylene groups is directed to improving the water solubility of the compounds.

The R ³ moieties, suitable substituted C2-18 hydrocarbon groups include C2-12 alkylene, alkenylene, arylene, and the like. The substituted alkylene or alkenylene groups may be linear, branched, or cyclic. The R ³ groups may also be the same (e.g., all substituted arylene) or a mixture (e.g., a mixture of substituted arylene and substituted alkylene). Preferred R ³ groups are substituted 1,3-phenylene groups.

The substituted R ³ groups preferably contain a -SO ³ M, -C00M, -O - [(R ⁵ O ³ m) (CH (Y) CH 2 O) _n -] - X or -A - [(R ² -AR ⁴ -A)] w - [(R ⁵ O) m (CH (Y) CH ₂ O) _n -] - X. M may be hydrogen or any compatible water-soluble cation. Suitable water soluble cations include the water soluble alkali metals such as potassium (K +) and especially sodium (Na +), as well as ammonium _(NH4 ®). Substituted ammonium cations of formula (c) wherein R 1 and R ₂ are each C 1 -C 20 hydrocarbon groups (e.g. alkyl, hydroxyalkyl), or together form a C 4 -C 6 ring or heterocyclic ring (e.g. piperidine, morpholine) are also suitable. ); R ₃ is C 1 -C 20 hydrocarbon; R4 is hydrogen (ammonium) or C1-C20 (quaternary ammonium). Representative substituted ammonium cationic groups in which they are hydrogen (ammonium) or C 1-4 alkyl, especially methyl (quaternary ammonium); R 1 is C 10 -C 18 alkyl, especially C 12 -C 14 alkyl; and R ₂ and R ₃ are each C 1 -C 4 alkyl, especially methyl.

The R ³ groups containing the substituents of formula _A - [- (R 2 -A-R 4 -A) -] _w - [(R ₅ O) _m (CH ₂ OCH ₂ O) _n -] - X provide a branched backbone to the compounds. R ³ groups having the formula -A - [(R ² -AR ⁴ -A) -] _W -R ² -A- provide cross-linked backbone compounds. Indeed, the syntheses used to prepare the branched backbone compounds typically yield at least some crosslinked backbone compounds.

The groups - [(R ⁵ O) - (CH (Y) CH 2) n] - and - [- (CH (Y) CH 2) n (OR ⁵ ) m -] - - (R ⁵ O) - and - (CH (Y) CH2 O) - groups is preferably öszszekeverhetjük or - ^(R5 O) - and - (CH (Y) CH2 O) - group -moieties. Preferably, the blocks of the - (R ⁵ O) - groups are located adjacent to the backbone of the compound. When R ⁵ is -R ² -AR ⁶ -, m is 1; preferably the -R ² -AR ⁶ - group is also located adjacent to the backbone of the compound. For R ⁵ , the preferred C ₃ -C 4 alkylene is C ₃ H ₆ (propylene); when R ⁵ is C 3 -C 4 alkylene, preferably m is a number from 0 to 5, and most preferably 0. R ⁶ is preferably methylene or

1,4-phenylene. The - (CH (Y) CH ₂ O) - group preferably contains at least 75% by weight of the group [(R ⁵ O) _m (CH (Y) CH ₂ O) -], and most preferably 100% by weight. (m is 0).

The Y substituents on each - [(R ⁵ O) _m (CH (Y) CH ₂ O) _n -] - group are -CH ₂ (OCH ₂ CH ₂ ) _p OX ether groups, or more typically mixtures of this ether group and hydrogen; p is in the range from 0 to 100, but typically 0. When the Y substituents are a mixture, the - (CH (Y) CH ₂ O) n - group may be represented by the following general formula: d, wherein Π] is at least 1, and n is the sum of n [+ n ₂ . Typically n! average value is between 1 and 10. Mixed with (CH ₂ CH ₂ O) _n2 groups, but typically and - - e and groups of blocks to form - (CH ₂ CH ₂ O) _n2. X may be hydrogen, C 1 -C 4 alkyl or -C (O) R ⁷ wherein R ⁷ is C 1 -C 4 alkyl. Preferably X is methyl or ethyl, and most preferably methyl. Each n value is at least 6, but preferably at least 10. Each n value is usually in the range of 12 to 113. Typically, each n value is in the range of 12 to 43.

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The backbone groups - (- A-R'-AR ² -) - and - (- AR ³ -AR ² -) can be mixed with either - (- A-R'-AR ² -) - and - (- A-R ³ -). AR ² -) groups can be formed into blocks. It has been found that the value of u + v must be at least 3 in order for the compounds of the invention to have significant contaminant release activity, the maximum value of u + v is usually determined by the method of preparation of the compound, but may be up to 25 The compounds of the invention are oligomers or low molecular weight polymers. By way of comparison, fiber-forming polymers typically have much higher molecular weights, e.g., 50 to 250 units of ethylene terephthalate. Typically, the sum of u + v for the compounds of the invention will range from about 3 to about 10.

Generally, the higher the u + v value, the less soluble the compound is, especially when the R ³ groups do not have -COOM or -SO ³ M substituents. As the n values increase, the u + v values increase, so that the compound will be deposited more on the fabric during washing. When R ^{3 is} -A - [- (R ² -AR ⁴ -A) -] w - [(R ⁵ O) _m (CH (Y) CH ₂ O) _n -] - X (branched-chain compounds) or

-A - [(R ² -AR ⁴ -A) -] _W -R ² -A- (cross-linked compounds), typically having a w value of at least 1 and determined by the process by which the compound is prepared. For these branched and cross-linked backbones, u + v + w is between 3 and 25.

The polymers of this group of preferred compounds IV block polyesters of the formula wherein each R ¹ group is 1,4phenylene; the R ² moieties are essentially ethylene moieties, 1,2-propylene moieties or mixtures thereof; all R ³ groups are potassium or preferably sodium-5-sulfo-1,3-phenylene or substituted 1,3-phenylene having 5 at position 5; R ⁴ is R ¹ or R ^3, or a mixture thereof; each X is ethyl or preferably methyl; each ni is from 1 to 5; each n, + n ₂ values are from 12 to 43; when w is 0, u + v is between 3 and 10; if w is at least 1 then u + v + w is between 3 and 10.

Particularly preferred block polyesters are those in which v is 0, i.e., linear block polyesters. For these most preferred linear block polyesters, the u will typically be between about 3 and about 8. Of these linear block polyesters, they are most soluble in water, where u is from about 3 to about 5.

Other polymers suitable for use in the present invention are polymers of formula V. In this formula,

- [(A-R'-AR ² ) u (A-R'-AR ³ ) v -] - A-R'-A- form the oligomeric or polymer backbone of the compounds. At the ends of the oligomer / polymer backbone, X - [(OCH ₂ CH (Y) _n (OR ⁴ ) m -) - and - [(R ⁴ O) m (CH (Y) CH ₂ O) _n -] - X groups of formula II are attached.

Binder A groups are essentially -C (O) O- or -OC (O) - groups, i.e. the compounds of the invention are polyesters. As used herein, the term "A groups are essentially -C (O) O- or -OC (O) - groups" refers to compounds wherein A groups are entirely of -C (O) O- or -OC (O) - groups. or partially substituted with linker groups such as -NCH (O) - or -CONH- (amide) and -OC (O) NH or NHC (O) O- (urethane). The degree of partial substitution with these other bonding groups must be such that the release properties are not significantly adversely affected. Preferably, the binding groups A are fully (i.e. 100%) -OC (O) - or -C (O) O-, i.e. each A is either -OC (O) - or -C (O) O-. group.

R ¹ groups are essentially 1,4-phenylene groups. According to this application, “R ¹ groups are basically

1.4- expression moieties "refers to compounds where the ^R1 moieties consist entirely 1,4phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof. The arylene and alkarylene moieties which may be partially substituted for the 1,4-phenylene moiety include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene,

2,2-biphenylene, 4,4'-biphenylene groups and mixtures thereof. Partially substituted alkylene and cycloalkenylene groups include ethylene, 1,2-propylene, 1,4-butylene,

1.5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene and mixtures thereof.

These other arylene, alkarylene, alkylene and alkenylene groups may be unsubstituted or at least one -SO ₃ M, -COOM or

- A - R ⁷ - [- A - R ¹ - A - R ⁷ - O] w - X or at least one other R> group cross-linked -AR ⁷ - [- A-R'-AR ⁷ -] wA - may contain a group wherein R ⁷ is R ² or R ³ ; and w is 0 or at least 1. These substituted R ¹ groups are preferably only one -SO ₃ M, -COOM or

-AR ⁷ - [- AR'-AR ⁷ -O] _w -X. M can be hydrogen or any compatible water-soluble cation. Suitable water soluble cations include the water soluble alkali metals such as potassium (K +) and especially sodium (Na +), as well as ammonium _(NH4 ®) ions. Also suitable are substituted ammonium ac cations of general formula wherein R, and _R2 are all a C1 -C20 hydrocarbyl group (e.g. alkyl, hydroxyalkyl group) or with a C4-6 ring or heterocyclic ring (e.g., piperidine, morpholine ); R ₃ is C 1-20 hydrocarbon; and R ₄ is hydrogen (ammonium) or C 1-20 hydrocarbon (quaternary ammonium). Typical substituted ammonium cationic groups are those wherein R ₄ is hydrogen (ammonium) or C 1 -C 4 alkyl,

In particular methyl (quaternary ammonium); R

C 10 -C 18 alkyl, especially C 12 -C 14 alkyl; and R ₂ and R ₃ are each C 1 -C 4 alkyl, especially methyl.

The AR ⁷ - R ¹ groups containing - [A-R'-AR ⁷ -O] _w X substituents provide branched backbone compounds. The

R ¹ groups bearing the formula -AR ⁷ - [- AR> -AR ⁷ -] _w -A- provide crosslinked backbone compounds. Indeed, the syntheses used to prepare the branched backbone compounds typically yield at least some crosslinked backbone compounds.

The degree of partial substitution with groups other than the 1,4-phenylene moiety of the R ¹ groups should be such that they do not adversely affect the ability of the compound to dissolve. Generally, the degree of tolerable partial substitution will depend on the backbone length of the compound, i.e. longer backbones may have higher partial substitution on 1,4-phenylene groups. Generally, compounds wherein R ^{1 contains from} 50% to 100% of 1,4-phenylene groups (O to 50% other than the 1,4-phenylene group) exhibit satisfactory soil release activity. However, since most polyesters used in fiber making contain ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution by groups other than the 1,4-phenylene moiety for best soil release activity. Preferably the R ¹ group is completely (i.e. 100%)

It is composed of 1,4-phenylene groups, i.e. each R ¹ group is 1,4-phenylene.

The R ² groups are essentially substituted C 1 -C 4 alkyl or alkoxy substituents. As used herein, the term "R ² groups are substituted ethylene groups having substantially C 1-4 alkyl or alkoxy substituents" refers to compounds of the present invention wherein R ² groups are fully substituted ethylene groups or are partially substituted with other compatible groups. Examples of these other groups include linear C2-C6 alkylene groups such as ethylene, 1,3-propylene, 1,4-butylene,

1,5-pentylene or 1,6-hexamethylene, 1,2-cycloalkylene groups such as 1,2-cyclohexylene, 1,4-cycloalkylene groups such as 1,4-cyclohexylene and 1,4-dimethylene cyclohexylene, alkylated polyoxy, -1,2-hydroxyalkylene groups, for example

-CH ₂ -CHI

CH ₂ -O (CH ₂ CH ₂ O) _p -X and oxyalkylene groups such as -CH ₂ CH ₂ OCH ₂ CH ₂ -.

For R ² groups, the degree of partial substitution with these other groups should be such that it does not directly affect the release properties of the compound in any significant way. Generally, the degree of tolerable partial substitution will depend on the dissolution and solubility properties required, the backbone length of the compound (i.e., longer backbones may have higher partial substitution) and the type of moiety involved (e.g., higher partial substitution with ethylene groups generally reduces solubility). Generally, compounds wherein R ^{2 contains from} 20 to 100% substituted ethylene (from 0 to 80% other compatible groups) will exhibit satisfactory soil release activity. However, for the best soil release activity and solubility properties, it is generally necessary to minimize such partial substitution. [During the preparation of the polyesters according to the invention, small amounts of oxyalkylene groups (as dialkylene glycols) may be formed by side reactions from glycols and then incorporated into the polyester.] Preferably, R ² groups contain from 80 to 100% substituted ethylene groups and from 20 to group. For the R ² groups, the corresponding substituted ethylene groups are: 1,2-propylene,

1,2-butylene, 3-methoxy-1,2-propylene and mixtures thereof. Preferably the R ² groups are essentially 1,2-propylene.

R ³ groups are essentially - (CH 2 CH 2 O) q -CH 2 CH 2 - polyoxyethylene groups. As used herein, the term "R ² groups are essentially - (CH ₂ CH ₂ O) _q -CH ₂ CH ₂ - polyoxyethylene)" refers to compounds of the invention wherein R ³ groups are wholly of this poly ( oxyethylene) or other compatible groups. Examples of these other groups are C3-C6-oxyalkylene groups, such as oxypropylene and oxybutylene groups, and alkylated polyoxy-1,2-hydroxyalkyleneoxy groups, e.g.

-OCH ₂ CHCH ₂ O (CH ₂ CH ₂ O) _p -X.

These other groups may be present to such an extent that the contaminant release properties of the compounds are not adversely affected to any significant degree. In the compounds of the invention, about 50 to about 100% of each R ³ group is typically polyoxyethylene. Preferably, the polyoxyethylene groups represent 90-100% of each R ³ group. [During the preparation of polyesters according to the invention, very small amounts of oxyalkylene groups can be attached to the polyoxyethylene group in side reactions and thus incorporated into the R ³ groups.]

For the polyoxyethylene groups, q is at least 9 and preferably at least 12. q is usually from about 12 to about 90.

The groups - [(R ⁴ O) m (CH (Y) CH 2 O) n -] - and - [(OCH (Y) CH 2) n (OR ⁴ ) m -] - are - (R ⁴ O) - and - ( CH (Y) CH 2 O) - groups may be mixed together, or preferably, - (R ⁴ O) - and - (CH (Y) CH 2 O) - groups may be formed into blocks. The blocks of the (R ⁴ O) groups are preferably located adjacent to the backbone of the compound. When R ⁴ is -R ² -AR ⁵ -, m is 1;

The group -R ² -AR ⁵ - is also preferably adjacent to the backbone of the compound. For R ⁴ , the preferred C 3 -C 4 alkylene is C 3 H ⁶ (propylene); when R ^{4 is C} 3 -C ⁴ alkylene, m is preferably 0 to 10, and most preferably 0. R ^{5 is} preferably methylene or 1,4-phenylene. Preferably, the - (CH (Y) CH 2 O) - group is at least 75% by weight of the - [- (R ⁴ O) _m (CH (Y) CH ₂ O) _n -] - group and most preferably 100% by weight (m is 0).

The Y substituents on each [(R ₅ O) _m (CH (Y) CH ₂ O) _n ] group are hydrogen, -CH ₂ (OCH ₂ CH ₂ ) _p OX ether groups, or a mixture of this ether group and hydrogen; p may range from 0 to 100, but typically 0. Each Y substituent is typically hydrogen. When Y is a mixture of ether and hydrogen, the group - (CH (Y) CH ₂ O) _n - may be represented by d, where Π] is at least 1 and n is the sum of n + n ₂ . n _t typically has an average value between 1 and 10. The e and - (CH ₂ CH ₂ O) 2 - groups can be mixed, but typically the e and - (CH ₂ CH ₂ O) 2 - groups form blocks.

X can be hydrogen, C 1-4 alkyl or -C (O) R ⁷ wherein R ⁷ is C 1-4 alkyl. Preferably X is methyl or ethyl, and most preferably is methyl. Each n has a value of at least 6, but preferably at least 10. Each n value is typically in the range of 12 to 113.

The - (- A-R 'AR ² -) - and - (- A-R' ³ AR -) backbone groups are - (- A-R 'AR ² -) - and - (- AR' -AR ³ -) - may form blocks, but they are typically randomly mixed. For these backbone groups, the average value of u can range from 2 to 50; and the average value of v is from 1 to 20; and the mean values of u + v can range from 3 to 70, the mean values of u, v and u + v being generally determined by the method of preparing the compound. In general, the higher the mean value of v, the lower the mean value of u + v, and the more soluble the compound is. Typically, the average value of u is between 20 and 20; the mean value of v is between 1 and 10; and u + v average between 6 and 30. Usually the ratio of u to v is at least 1 and typically between 1 and.

Very useful for use in the present invention are polymers of formula VII wherein X is any suitable leaving group, with each X group being hydrogen and alkyl or acyl groups having 1 to 4 carbon atoms, preferably 1-2 carbon atoms, most preferably alkyl groups. we select it. The value of n is selected for water solubility and its range is generally on average between 10 and 50, preferably between 10 and 25, and the selection of u is critical for the preparation of a liquid with a relatively high ionic strength. Very few amounts of material, preferably less than 10 mol%, more preferably less than 5 mol%, most preferably less than 1 mol%, are greater than 5. Further, at least 20 mol%, preferably at least 40 mol%, of the substance is in which u is between 3 and 5.

R ¹ groups are essentially 1,4-phenylene groups. As used herein, the term "R ¹ groups are essentially 1,4-phenylene groups" refers to compounds wherein the R 'groups are wholly 1,4-phenylene groups or partially substituted with other arylene or alkarylene groups, alkylene groups, alkenylene groups, or mixtures thereof. The arylene and alkarylene groups with which the 1,4-phenylene moiety may be partially substituted include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene. , 4,4'-biphenylene groups and mixtures thereof. Partially substituted alkylene or cycloalkylene groups include ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, octamethylene, 1,4-cyclohexylene groups and mixtures thereof.

The degree of partial substitution of the groups R 'with groups other than 1,4-phenylene should be such that it does not adversely affect the release properties of the compound. Generally, the degree of tolerable partial substitution will depend on the backbone length of the compound, i.e., for longer backbones, the partial substitution of 1,4-phenylene groups may be higher. Generally, compounds having R 'containing 50-100% 1,4-phenylene groups (O-50% groups other than 1,4-phenylene groups) will exhibit satisfactory soil release activity. For example, polyesters prepared according to the present invention with a molar ratio of (1,3-phenylene) -isophthalic acid to (1,4-phenylene) -terephthalic acid in a ratio of 40:60 have satisfactory soil release activity. However, since most of the polyesters used in fiber making contain ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution with groups other than 1,4-phenylene for best soil release activity. Preferably, the R 'groups are completely (i.e. 100%) composed of 1,4-phenylene groups, i.e. each R' group is 1,4-phenylene.

Suitable ethylene or substituted ethylene groups for R ² are ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene, and mixtures thereof. Preferably, the R ² groups are essentially ethylene or preferably 1,2-propylene or mixtures thereof. Although the incorporation of higher percentages of ethylene groups shows an improving tendency for the compounds to decontaminate, the water solubility limits the percentage that can be added. When the compounds contain a higher percentage of 1,2-propylene, their water solubility shows a surprisingly improving tendency, and consequently their ability to form an isotropic aqueous detergent composition is improved without significantly impairing the soil release activity.

The use of 1,2-propylene groups, or a similar branched equivalent, in the present invention is extremely important for incorporating a maximum percentage of the soil release ingredient in high performance liquid detergent compositions. Preferably, 75-100%, more preferably about 90-100% of the R ² groups is 1,2-propylene.

HU 217 365 Β

In general, the soil release components that are soluble in cold (15 ° C) ethanol may also be used in the compositions of the invention.

n has an average value of at least 10 but a range of n values are present. Each n value is usually in the range of about 10 to about 50. Preferably, each of the n values is in the range of 10 to 25.

A preferred process for preparing a soil release component comprises the step of extracting a representative polymer with substantially anhydrous ethanol at low temperatures, e.g., 10-15 ° C, preferably below 13 ° C, containing a substantial amount of a material, in which the u value is equal to or greater than 6. The ethanol-soluble fraction is essentially free of longer polymers and is much easier to incorporate into isotropic high performance fluids, especially those containing higher builder quantities. Although polymers with a u value of less than 3 are essentially non-valuable in terms of their release effects, they are easier to incorporate in liquids than larger u values.

Direct synthesis is preferred for the preparation of the soil release component.

Most preferred polymers for use in the agent according to the invention, the polymers of formula VII, wherein X is methyl, n is 16, ^R1 is 1,4-phenylene, ^R2 is

Is 1,2-propylene and u is essentially a number from 3 to 5.

The present compositions are readily used as additives in conventional laundry detergent formulations. The present invention also relates to dye transfer inhibiting compositions which contain detergent ingredients and thus serve as detergent compositions.

A wide range of surfactants can be used in detergent compositions. A representative list of anionic, nonionic, ampholytic and zwitterionic groups and the types of these surfactants are disclosed in U.S. Patent No. 3,664,961.

Particularly useful according to the invention are mixtures of anionic surfactants, preferably mixtures of sulfonate and sulfate surfactants in a weight ratio of 5: 1 to 1: 2, preferably 3: 1 to 2: 1, more preferably 3: 1 to 1: 1. Preferred sulfonates in the alkyl group are 9 to 15, preferably

C 11 -C 13 alkylbenzene sulfonates and the sulfonated methyl fatty acid esters in which the fatty acid

It is derived from a C12-C18 fat source, preferably a C16-C18 fat source. In each case, the cation is an alkali metal, preferably sodium. Preferred sulfate surfactants in the alkyl group are C 12 -C 18 alkyl sulfates, optionally in the alkyl group 10 to 20, preferably 10 to 16 carbon atoms and

With an average degree of ethoxylation of 1-6 in admixture with ethoxysulfates. Examples of preferred alkyl sulfates of the invention are tallow alkyl sulfate, coconut alkyl sulfate and

C 14 -C 15 alkyl sulfates. In each case, the cation is again an alkali metal cation, preferably sodium.

A group of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic group having an average hydrophilic lipophilic range of 8 to 17, preferably 9.5 to 13.5, more preferably 10 to 12.5. have an equilibrium (HLB). The hydrophobic (lipophilic) moiety may be aliphatic and aromatic, and the length of the polyoxyethylene moiety condensed with any individual hydrophobic moiety may be rapidly adjusted to provide a water-soluble compound having the desired degree of equilibrium between the hydrophilic and hydrophobic moieties.

Particularly preferred nonionic surfactants of this type are the C 9 -C 15 primary alcohol ethoxylates containing from 3 to 8 moles of ethylene oxide per mole of alcohol, especially the C 14 -C 15 primary alcohols containing 6 to 8 moles of ethylene oxide and C12 -C14 primary alcohols containing -5 mol / mol of ethylene oxide alcohol.

Another class of nonionic surfactants comprises alkyl polyglycoside compounds of formula VIII wherein Z is a glucose moiety; R is a saturated hydrophobic alkyl group containing from 12 to 18 carbon atoms; t is a number from 0 to 10, and n is 2 or 3; x is between 1.3 and 4 for compounds containing less than 10% unreacted fatty alcohol and less than 50% lower alkyl polyglucoside. Compounds of this type and their use in detergents are disclosed in EP-B 0070077, 0 075 996 and 0094118.

Also suitable as nonionic surfactants are the polyhydroxy fatty acid amides of formula IX wherein R ¹ is hydrogen or R ¹ is C 1 -C 4 hydrocarbon, 2-hydroxyethyl,

2-hydroxypropyl, or a mixture thereof, R ² is a C 5 -C 31 hydrocarbon group, and Z is a polyhydroxy hydrocarbon group having at least 3 hydroxyl groups directly attached to the chain or an alkoxylated derivative thereof. Preferably, R 'is methyl, R ² is a straight alkyl or alkenyl chain of 11 to 15 carbon atoms, or an alkoxylated derivative thereof, such as coconut alkyl or mixtures thereof, and Z is a reducing sugar such as glucose, fructose, maltose, lactose, from a reductive amination reaction.

The compositions of the invention may further comprise a builder system. Any conventional builder system suitable for use in the present invention, including aluminum silicate materials, silicates, polycarboxylates and fatty acids, materials such as (ethylenediamine) tetraacetic acid, metal ion sequestering agents such as aminophosphonate tetramethylenediamine, and (diethylene triamine) pentamethylene phosphonic acid. Phos8 can be used in the invention

However, they are less advantageous for obvious environmental reasons.

A suitable builder may be an inorganic ion exchange material, generally an inorganic hydrated aluminum silicate material, more preferably a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.

Another suitable inorganic builder is layered silicate, for example SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na ₂ Si ₂ O ₅ ).

Polycarboxylate builders suitable for use in the present invention include succinic acid derivatives of the formula R-CH (COOH) CH ₂ (COOH) in the form of citric acid, preferably water-soluble salt, wherein R is C 10-20 alkyl, preferably C 12-16 alkyl or alkenyl. or wherein R may be substituted by hydroxy, sulfo, sulfoxyl or sulfone. Representative examples are lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanol ammonium salts.

Other suitable polycarboxylates are mixtures of oxodisuccinates and monobasic tartrate and dibasic tartrate, for example as disclosed in U.S. Patent 4,663,071.

Suitable fatty acid builders for use in the present invention, particularly in liquid form, are saturated or unsaturated fatty acids having from 10 to 18 carbon atoms and suitable soaps. Preferred saturated compounds in the alkyl chain have from 12 to 16 carbon atoms. The preferred unsaturated fatty acid is oleic acid.

Preferred builder systems for use in granular formulations comprise a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid.

When used in granular compositions for the purposes of the invention, the builder may also include other builder materials, inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as organic phosphonates, aminopolyalkylene phosphonates and polycarboxylates.

Other suitable water-soluble organic salts are homo- and copolymeric acids and their salts in which the polycarboxylic acid contains at least two carboxyl groups not more than two carbon atoms apart.

Polymers of this type are disclosed in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 2000-5000 and their copolymers with maleic anhydride, and such copolymers have a molecular weight of 20,000 to 70,000, preferably 40,000.

The composition generally contains from about 10 to about 80% by weight of washable builders, preferably from about 20 to about 70% by weight, and most typically from about 30 to about 60% by weight.

Other ingredients may also be included in detergent compositions, such as bleaching agents, anti-foaming agents, anti-foaming agents, enzymes and stabilizers or activators, anti-soot suspending agents, anti-soaking agents, optical brighteners, abrasives, bactericides, opacifiers, and anti-light agents.

Combinations with technologies that also offer the advantage of color protection are particularly advantageous. Examples of these technologies are polyvinylpyrrolidone polymers and other polymers which have dye transfer inhibiting properties. Another example of these technologies is the use of cellulase for color retention / regeneration.

The detergent compositions of the present invention may be in liquid, paste or granular forms. The granular compositions of the present invention may also be in a "compact form", i.e., of a relatively higher density than conventional granular detergents, i.e., between 550 and 950 g / l; in this case, the granular composition of the invention contains a smaller amount of "inorganic filler salt" than conventional granular detergents; typical filler salts of the alkaline earth metal salts are sulfates and chlorides, typically sodium sulfate; "compact" detergents typically do not contain more than 10% by weight of filler salt. The liquid compositions of the present invention may also be in "compact form" and in this case the liquid detergent compositions of the present invention will contain less water than conventional liquid detergents.

The process of the composition of the invention may conveniently be carried out during the washing process. The washing process is preferably carried out at 5 ° C to 75 ° C, typically at 20 ° C to 60 ° C, but the polymers are effective at 95 ° C. The pH of the treatment solution is preferably between 7 and 11, typically between 7.5 and 10.5.

The following examples are provided to illustrate the compositions of the present invention by way of examples, which are not necessarily limited to, or otherwise limited to, the scope of the invention, which is further defined by the claims.

Example 1

We produce the following composition according to the invention.

wiping liquid detergent composition (% by weight). C, _H, linear C ₁₃ alkyl benzene sulfonate 10 C ₁₂ -C ₁₃ alkyl sulfate 4 C | ₂ -C ₁₅ fatty alcohol ethoxylate (7 EO) 12 C ₂ -C ₁₄ fatty acids 10 Oil week 4 Citric acid 1 Sodium hydroxide 3.4 propanediol 1.5 ethanol 10 Poly (4-vinylpyridine) -N-oxide 0.3 Polymer based on terephthalate 0.4 Other ingredients 100

HU 217 365 Β

Example 2

A compact granular detergent composition according to the invention (wt.%) Is prepared as follows:

Linear C ₁ - C ₃ - ₃ alkylbenzene sulfonate 11.40

Tallow alkyl sulfate C 1 -C 8 alkyl sulfate C 3-C 7 ethoxylated alcohol 4.00

times ethoxylated tallow alcohol 1.80

Dispersant 0.07

Silicone liquid 0.80

Trisodium citrate 14.00

Citric acid 3.00

Zeolite 32.50

Maleic / Acrylic Acid Copolymer 5.00

DETMPA (diethylene triamine pentamethylene phosphonic acid) 1.00

Cellulase (active protein) 0.03

Alkalase / BAN 0.60

Lipase 0.36

Sodium silicate 2.00

Sodium sulfate 3.50

Glucose 10.00

Poly (4-vinylpyridine) -N-oxide (M = 50,000) 0.3

Polymer based on terephthalate 0.4

Other ingredients up to 100

3-4. examples

The present invention is further illustrated by the following examples. The following liquid detergent compositions are prepared by blending the listed ingredients in the ratios (% by weight) listed.

These compositions contain a pH jump system consisting of polyhydroxy fatty acid amide surfactants and borate and / or propanediol. The compositions are formulated at a pH below 7, preferably at a pH of 6.5. When diluted, these formulations provide a wash pH of at least 7.4. This pH jump allows formulations with a lower pH η to be made which are unstable at certain pH. Examples of such compositions are polymeric compositions wherein the polymers have better stability at lower pH. Other advantages of a pH-jumping system include better bleaching dye removal during pretreatment and reduced production costs, since less neutralizing agents are required to achieve a higher pH.

Third 4th C12-C15 alkyl sulfate 21.0 - C12-C15 ethoxylated alkyl sulfate (EO = 3) 4.0 25.0 C12-C14 N-methyl- glucamide 9.0 9.0 C12-C14 fatty alcohols- ethoxylate (EO = 7) 6.0 6.0 C12-16 fatty acids 14.0 14.0 Citric acid, anhydrous 3.5 3.5 Diethylenetriamine pentamethylene acid 2.0 2.0

3.4.

Monoethanolamine 12.8 11.0 propanediol 13.1 10.0 ethanol 4.7 5.4 enzymes 2.0 2.0 Polymer based on terephthalate 0.5 0.5 Poly (4-vinylpyridine) -N-oxide 0.5 0.5 Boric acid 2.8 2.8 2-Butyl octanol 2.0 2.0 DC 3421 R (1) 0.3 0.4 FF 400 R (2) Water & other ingredients Up to 100% by weight

(1) DC 3421 is a commercially available silicone oil from Dow Coming.

(2) A silicone oil emulsifier available from Dow Coming.

Comparative study

A liquid detergent composition was prepared by mixing the following components:

Parts Quantity by weight C 1 -C ₁₃ linear alkylbenzene sulfonate 10 C ₁₂ -C ₁₃ alkyl sulfate 4 C ₂ -C ₁₅ fatty alcohol ethoxylate (EO = 3) 12 C _{] 2} -C _{1 4} fatty acids 10 oleic acid 4 Citric acid 1 Sodium hydroxide 3.4 propanediol 1.5 ethanol 10 Terphthalate based soil release polymer 0.5 Water and other additives To 100

Color transfer between fabrics was determined by Hunter color measurement. According to the method, the color of the fabric is evaluated as Ac, which represents the change in a and b values determined by reflection spectrometry. The Ac value can be calculated using the following equation: Ac = {(af - aj) ² + (bf - bj ² } ^{l / 2.} The subscripts i and f represent the Hunter value of the dye before and after washing.

The degree of color transfer of fabrics of different colors was determined after a 30 minute wash cycle. The washing machine was filled with 200 ml of detergent composition and washed with a 10 x 10 cm colored cloth and a piece of multifilament was placed to indicate color loss. The wash was performed at pH 7.8.

Preparation: as defined in the table above, without polyamine N-oxide,

Formulation B: 10 ppm of poly (4-vinylpyridine) -N-oxide (average molecular weight 50,000; 1: 4 molar amine / amine N-oxide) was added according to the table.

In the industry's judgment, Ac 2 is already noticeable by the consumer and less than that is excellent

EN 217 365 jelent denotes the ability to inhibit color transmission. If the Ac value is greater than 10, this is a complete inability.

The results are shown in the following table:

Color-woven fabric cloth color THE preparation Ac value B preparation Ac value First 55% cotton / 45% polyester green 4.2 1.7 Second Jeans blue 15.7 3.3 Third 60% polyester / 40% flax blue 4.3 1.9

The results of the table show that the color transfer inhibitory properties of composition B according to the invention are significantly higher than those of composition A. For example 2, for example, the improvement is 12 units better than formulation B. For samples 1 and 3, the Ac value fell below the visual conspicuity.

Claims (5)

PATENT CLAIMS CLAIMS 1. A dye transfer inhibitor composition comprising: A) 0.01 to 10% by weight of amine oxide units of formula I having a pKa value of less than 10, in the presence of conventional additives. P is a polymerizable moiety to which the N-O moiety is attached, or wherein the N-O moiety is part of the polymerizable moiety, or a combination of the two; A is = NC (O) -, -C (O) O, = C = O, -O-, -S-, -N =; x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group to which the nitrogen of the NO group is attached or in which the nitrogen of the NO group is part of these groups, the NO group being of formula (a) and (b) ¹ , R ² , R ³ are aliphatic, aromatic, heterocyclic or alicyclic, or combinations thereof, x and / or y, and / or z are 0 or 1, and the nitrogen atom of the NO group is attached thereto, or The nitrogen atom of the group A contains a water-soluble polyamine N-oxide polymer which is part of these groups and B) 0.01 to 10% by weight of a known terephthalate-based polymer. Second dye transfer inhibiting composition according to claim 1, characterized in that the polymer is a terephthalate-based polymer (VII) - wherein X is methyl, n is 16, ^R1 is 1,4-phenylene, ^R2 is 1,2 -propylene, and u is 3-5. The dye transfer inhibiting composition according to claim 1 or 2, characterized in that the polyamine noxide is polyvinylpyridine N-oxide. 4. A dye transfer inhibitor composition according to any one of claims 1 to 3, characterized in that it is a non-dusting, granular or liquid laundry detergent additive. A detergent composition comprising surfactants, builders, enzymes, and other conventional detergent ingredients, wherein the detergent composition of any one of claims 1-4. A dye transfer inhibiting composition according to claims 1 to 4.