ES2708301T3 - Use of block or comb copolymers as antiredeposition agents for dirt and soil release agents in laundry processes - Google Patents

Abstract

Use of one or more block or comb copolymers as soil anti-redeposition agents and soil release agents in aqueous laundry washing processes in which block or comb copolymers have been prepared in a first step a) by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic or methacrylic acid; and in a second step b) has been modified in a transesterification reaction of polymer analogues with a primary or secondary alcohol to form a block or comb copolymer; wherein the block or comb copolymer has been prepared in step a) from n-butyl acrylate; and wherein the primary or secondary alcohol of step b) is an ethoxylate of formula (A) RA- [O-CH2-CH2-] n-OH (A) in which RA is a saturated or unsaturated alkyl, straight or branched chain, with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is from 1 to 150; containing a primary or secondary alcohol at least one tertiary amino group; such as N, N, N'-trimethylaminoethyl-15-ethanolamine; N-hydroxyethylmorpholine; or a primary alcohol whose chain is interrupted by at least one ester group such as polycaprolactone α-cetyloxy, - ω-hydroxy with a molecular weight of 750 to 2500 g / mol.

Description

DESCRIPTION

Use of block or comb copolymers as antiredeposition agents for dirt and soil release agents in laundry processes

The present invention relates to the use of block or comb copolymers that have been prepared by controlled free radical polymerization as anti-re-deposition agents for dirt and soil release agents in laundry processes. Other aspects of the invention are a method for preventing the redeposition of dirt and for an easier release of textile dirt in laundry processes and detergent formulations containing said block or comb copolymers.

In the usual domestic washing methods, the dirt, once freed from the textiles soiled in the washing water, can be re-deposited on the textiles, especially when using suboptimal detergent formulations and / or at lower washing temperatures. In this case, a graying of the clothing becomes evident after multiple washing cycles. An additional problem is that some types of dirt and stains are difficult to remove from textiles when using suboptimal detergent formulations and / or lower wash temperatures, since these soils and stains are strongly bonded to the surface of the fibers or are strongly absorbed inside the fibers.

It is known to use various agents as anti-re-deposition agents for dirt and soil release agents in washing processes. Examples thereof are carboxymethylcellulose or anionic derivatives of polymers of terephthalic acid and polyethylene glycol (see, for example, E. Smulders in "Laundry Detergents" Wiley-VCH Verlag GmbH, 2002, page 88). Anti-fouling agents can work through various mechanisms. With respect to soil release agents, it is often assumed that they deposit and accumulate on the surface of the fibers during laundry, thereby modifying the surface properties of the fibers. The dirt and stains that are subsequently deposited on this surface of modified fibers are released more easily in a subsequent washing cycle.

The international patent application WO 2010/003783 A1 discloses copolymers comprising the glycerol (meta) acrylate monomers and alkyl ether (poly) alkylene acrylate, the copolymer having a number average molecular weight of between 2000 and 100000 Daltons, and the use thereof to provide improved dirt release or improved anti-redeposition to a laundry detergent composition.

The object of the present invention is to provide an improved method, suitable for the domestic sector, by means of which the redeposition of the dirt can be prevented and the dirt and stains of the textile fibers can be more easily released in laundry processes. A further object is to provide washing formulations suitable for that method.

It has now been surprisingly discovered that the mentioned objects can be achieved to a large extent by the use of block or comb copolymers which have been prepared by controlled free radical polymerization and which have subsequently been subjected to a transesterification of polymer analogues. .

One aspect of the invention is the use of one or more block or comb copolymers as soil anti-redeposition agents and soil release agents in aqueous laundry washing processes in which block or comb copolymers have been prepared in a first step a) by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic or methacrylic acid; and in a second step b) has been modified in a transesterification reaction of analogues of polymers with a primary or secondary alcohol to form a block or comb copolymer; wherein the block or comb copolymer has been prepared in step a) from n-butyl acrylate; and wherein the primary or secondary alcohol of step b) is an ethoxylate of formula (A) RA- [O-CH2-CH2-] n-OH (A) in which R ^a is a saturated or unsaturated alkyl, straight or branched chain, with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is from 1 to 150; containing a primary or secondary alcohol at least one tertiary amino group; such as N, N, N'-trimethyl-aminoethylethanolamine;N-hydroxyethylmorpholine; or a primary alcohol whose chain is interrupted by at least one ester group such as polycaprolactone a-cetyloxy, -w-hydroxy with a molecular weight of 750 to 2500 g / mol. It has been found that controlled free radical polymerisation (CFRP) is a tool for use as antiredeposition agents for dirt or soil release agents during a washing process. The combination of the CFRP with the subsequent subsequent modification of the stabilizing block allows to increase the possible groups that can be used in the aforementioned detergent applications. With a CFRP process a large number of different polymeric materials become available. Block or comb copolymers prepared in such a reaction in two steps are described, for example, in WO 2006/0074969.

Free radical controlled polymerization using stable alkoxyamines or nitroxyl radicals is a well-known technique and has been extensively described in the last twenty years.

For example, US 4581429 discloses a free radical polymerization process that controls the growth of polymer chains to produce homopolymers and oligomeric or short chain copolymers. The process employs an initiator that has as formula (in part) R'R "NO-X, in which X is a free radical species capable of polymerizing unsaturated monomers and the radical R'R" NO ^ terminates the growth of the oligomer / polymer. US 5322912 discloses a polymerization process using a free radical initiator, a polymerizable monomeric compound and a stable free radical agent with the basic structure R'R "NO ^ for the synthesis of homopolymers and block copolymers which are finished. by the nitroxyl radical.

More recently, nitroxyl radial and additional nitroxyl ethers have been described. WO 98/13392, for example, discloses open chain alkoxyamine compounds, which have a symmetric substitution pattern and which are derived from NO gas or nitroso compounds.

WO 96/24620 describes a polymerization process in which very specific stable free radical agents are used such as, for example,

WO 98/30601 discloses specific nitroxyls based on imidazolidinones.

WO 98/44008 discloses specific nitroxyls based on morpholinones, piperazinones and piperazindiones.

These nitroxyl and nitroxyl ethers of the prior art are all suitable for the present invention. The nitroxyl ethers and nitroxyl radicals suitable for the invention are known mainly from US 4581429 or EP-A-621 878. Particularly useful are the open chain compounds described in WO 98/13392, WO 99/03894 and WO 00/07981, the piperidine derivatives described in WO 99/67298, GB 2335190 and GB 2361235 or the heterodclic compounds described in GB 2342649 and WO 96/24620. Recently, other nitroxyl radicals and nitroxyl ethers have been described in WO 02/48205, WO 02/48109 and WO 02/100831.

Also suitable are the compounds described by Hawker et al., Chem. Commun., 2001, 823-824.

Some compounds are available in the market or can be prepared according to the documents mentioned above.

For example, the structural element of the alkoxyamine,

is a structural element of formula (I) and the structural element of the stable nitroxyl radical,

is a structural element of formula (II)

in which

G1, G2, G3, G4 are independently C1-C6 alkyl, or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12 cycloalkyl group;

G5, G6 are independently H, C1-C18 alkyl, phenyl, naphthyl or a COO-C1-C18 alkyl group;

X is selected from the group consisting of -CH2-phenyl, -CH3CH-phenyl, (CH3) 2C-phenyl, (C5-Ca cycloalkyl) 2CCN, (CH3) 2CCN,

-CH2CH = CH2, CH3CH-CH = CH2 (C1-C4 alkyl) CR20-C (O) -phenyl, (C1-C4 alkyl) -CR20-C (O) - (C1-C4 alkoxy), (C1-6 alkyl) C4) -CR20-C (O) - (C1-C4 alkyl), (C1-C4 alkyl) -CR20-C (O) -N-di (C1-C4 alkyl), (C1-C4 alkyl) -CR20- C (O) -NH (C 1 -C 4 alkyl), (C 1 -C 4 alkyl) -CR 20 -C (O) -NH 2, wherein R 20 is hydrogen or (C 1 -C 4 alkyl) and

* denotes a Valencia.

In a very specific embodiment of the alkoxyamine used for controlled free radical polymerization is a compound of formula NOR01.

Preferably, the alkoxyamine compound is used in an amount of 0.01 mol% to 30 mol%, more preferably in an amount of 0.1 mol% to 20 mol% and most preferred in an amount of 0.1 mol% to 10 mol% based on the monomer.

Since CFRP is a "living" polymerization, it can be started and stopped practically at will. Also, the polymeric product retains the alkoxyamine functional group which allows a continuation of the polymerization in a living material. Thus, once the first monomer has been consumed in the initial polymerization step, a second monomer can be added later to form a second block on the growing polymer chain in a second polymerization step. Therefore, it is possible to carry out additional polymerizations with the same or another monomer or monomers in order to prepare multiblock copolymers.

Also, since this is a radical polymerization, the blocks can be prepared essentially in any order. It is not necessarily limited to the preparation of block copolymers in which the sequential polymerization steps must flow from the less stabilized polymer intermediate to the more stabilized polymer intermediate, as in the case of ionic polymerization. Thus, it is possible to prepare a multi-block copolymer in which a polyacrylonitrile block or a poly (meth) acrylate block is prepared first and then a block of styrene is attached thereto.

In addition, a linking group is not required to join the different blocks of the present block copolymer. You can simply add successive monomers to form successive blocks. It is possible that the blocks are separated by a tapered zone, in which the monomers of the previous and continuous blocks are present in different proportions.

A plurality of specifically designed polymers and copolymers such as the star and graft (co) polymers described, inter alia, by CJ Hawker in Angew. Chemie, 1995, 107, pages 1623-1627, the dendrons described by K. Matyaszewski et al. in Macromolecules 1996, Vol. 29, No. 12, pages 4167-4171, the graft (co) polymers described by CJ Hawker et al. in Macromol. Chem. Phys. 198, 155-166 (1997), the random polymers described by CJ Hawker in Macromolecules 1996, 29, 2686-2688, or the diblock and triblock copolymers described by NA Listigovers in Macromolecules 1996, 29, 8992-8993.

For example, the block or comb copolymer has a polydispersity, PD, from 1.0 to 2.5, preferably from 1.1 to 2.0.

In a preferred embodiment, the block or comb copolymer has amphiphilic properties.

Preferably, the block or comb copolymer has been prepared in step a) from n-butyl acrylate and, optionally, from one or more monomers without an ester linkage.

For example, the monomer without an ester linkage is selected from the group consisting of 4-vinyl pyridine, 2-vinylpyridine, vinyl imidazole, vinyl pyrrolidone, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methylstyrene, p-methyl. -styrene or p-tert-butyl-styrene, acrylonitrile. Ammonic monomers can also be used in their ionized or quaternized forms, or they can be modified later in a consecutive stage.

When the controlled free radical polymerization is carried out with a nitroxyl radical, a source of initiating radicals is additionally necessary. This source of initiator radicals is preferably an azo compound, a peroxide, a perester or a hydroperoxide.

Preferred preferred radical sources are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-) methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxivaleronitrile, dimethyl-2, 2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (N, N '-dimethylenisobutyramidine), free base or hydrochloride, 2,2'-azobis (2-amidinopropane), free base or hydrochloride, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl) ] propionamide} or 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] -propionamide; acetylcyclohexane sulfonyl peroxide, diisopropyl peroxydicarbonate, tamilo perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amyl perpivalate, bis (2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per-2-ethylhexanoate, bis- (4-chlorobenzoyl) peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis (t-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-butyl peroxyisopropylcarbonate, perisononazole t-butyl, 2,5-dibenzoate of 2,5-dimethylhexane, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2- bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butyl peroxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, a, a'-bis (t-butylperoxyisopropyl) -benzene, 3,5-bis (t-butylperoxy) 3,5-dimethyl-1,2-dioxolane, di-t-butyl peroxide, 2,5-diperoxide dimethylhexino-2,5-di-t-butyl, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxaciclononane, p-menthane hydroperoxide, pinane hydroperoxide, mono-a-hydroperoxide diisopropylbenzene, cumene hydroperoxide or t-butyl hydroperoxide.

The source of radicals is preferably present in an amount of 0.01 mol% to 30 mol%, more preferably in an amount of 0.1 mol% to 20 mol% and most preferred in an amount of 0.5 mole% to 10 mole% based on the monomer.

The molar ratio of the radical source to the nitroxyl radical can be from 1:10 to 10: 1, preferably from 1: 5 to 5: 1 and, more preferably, from 1: 2 to 2: 1.

The reaction conditions for stage a) of the CFRP are amply described in the documents listed above. In general, the polymerization temperature is between 60 and 180 ° C at normal pressure and the reaction time can vary from 30 minutes to 20 hours.

Normally the process of washing watery clothes is a domestic laundry washing process.

For example, the textile is made of polyester, polyacrylic, cotton, wool, polyamide or mixtures thereof, preferably cotton.

Another aspect of the invention is a method for preventing redeposition of dirt on textiles and for the removal of textile dirt in aqueous laundry processes, said method comprising applying a block or comb copolymer that has been prepared as defined above a) by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic or methacrylic acid;

and in a second step b) has been modified in a transesterification reaction of analogues of polymers with a primary or secondary alcohol to form a block or comb copolymer;

wherein the block or comb copolymer has been prepared in step a) from n-butyl acrylate;

and wherein the primary or secondary alcohol of stage b) is

an ethoxylate of formula (A) RA- [O-CH2-CH2-] n-OH (A) in which R ^a is a saturated or unsaturated alkyl, straight or branched chain, with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is from 1 to 150;

containing a primary or secondary alcohol at least one tertiary amino group; such as N, N, N'-trimethylaminoethylethanolamine;

N-hydroxyethylmorpholine; or

a primary alcohol whose chain is interrupted by at least one ester group such as polycaprolactone a-cetyloxy, -w-hydroxy with a molecular weight of 750 to 2500 g / mol.

When the block or comb copolymer is used as part of a detergent, it may be present in an amount of from 0.05 to 20% by weight based on the weight of the total detergent composition.

Also aspects of the invention are laundry detergent compositions comprising:

I) from 1 to 50% by weight, based on the total weight of the composition, A) of at least one surfactant;

II) from 0 to 70% by weight, based on the total weight of the composition, B) of at least one adjuvant detergency substance;

III) from 0 to 30% by weight based on the total weight of the composition, C) of at least one peroxide and / or a peroxide-forming substance;

IV) from 0.05 to 10% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 4% by weight, based on the total weight of the composition, D) of at least one block or comb copolymer as defined above;

V) from 0 to 60% by weight, based on the total weight of the composition, E) of at least one additional additive; VI) from 0 to 90% by weight, based on the total weight of the composition, F) of water.

The composition according to the invention can be, for example, a high-performance detergent containing a solid peroxide, a detergent powder for delicate textiles, a detergent powder for washing colored laundry, or a liquid detergent based on structured water. (that is, cloudy) or unstructured (that is, transparent). Surfactants of component A)

The detergent formulation will normally include at least one surfactant which may be anionic, cationic, nonionic or amphoteric.

The anionic surfactant can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof. Preference is given to alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to a salt of an asulfonic fatty acid or an ester thereof.

Preferred sulfonates are, for example, alkylbenzene sulfonates having from 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical, and salts of fatty acids derived from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety. The average number of moles of ethylene oxide units added to the alkyl ether sulphates is from 1 to 20, preferably from 1 to 10. The cation in the anionic surfactants is preferably an alkali metal cation, especially sodium or potassium, more especially sodium. Preferred carboxylates are the alkali metal sarcosinates of formula R19-CON (R20 ') CH2COOM1 wherein R19' is C9-C17 alkyl or C9-C17 alkenyl, R20 'is C1-C4 alkyl and M1 is an alkali metal, especially sodium .

The nonionic surfactant may be, for example, an ethoxylate of a primary or secondary alcohol, especially an aliphatic C 8 -C 20 alcohol ethoxylated with an average of 1 to 20 moles of ethylene oxide per alcohol group. Preference is given to the primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of 1 to 10 moles of ethylene oxide per alcohol group. Also, non-ethoxylated nonionic surfactants can be used, for example, alkyl polyglucosides, glycerol monoethers and polyhydroxyamides (glucamide).

In addition to the anionic and / or nonionic surfactants, the composition may contain cationic surfactants. Possible cationic surfactants include all common cationic surfactant compounds, especially surfactants that have a softening effect on textiles.

Non-limiting examples of cationic surfactants are given in the following formulas:

in which

each radical Ra is, independently of the others, alkyl, alkenyl or hydroxyC1-6alkyl; each radical Rp is, independently of the others, alkyl or alkenyl Cs-28;

Ry is Ra or (CH2) n-T-Rp;

R ^b is Ra or Rp or (CH2) nT-Rp; T = -CH2-, -O-CO- or -CO-O- and

n is between 0 and 5.

Preferred cationic surfactants present in the composition according to the invention include hydroxyalkyl trialkylammonium compounds, especially alkyl (Ci2-i8) - (hydroxyethyl) dimethylammonium compounds and, especially preferred, the corresponding chloride salts.

The compositions of the present invention may contain between 0.5% by weight and 15% by weight of the cationic surfactant, based on the total weight of the composition.

The total amount of surfactants is preferably from 1 to 50% by weight, especially from 1 to 40% by weight and, more especially, from 1 to 30% by weight.

Adjuvant detergency substance B)

Suitable builder substances B) are, for example, alkali metal phosphates, especially acid tripolyphosphates, carbonates and carbonates, in particular their sodium salts, silicates, aluminosilicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylene polyols. (alkylene phosphonates) and mixtures of such compounds.

Silicates which are especially suitable are the sodium salts of crystalline layered silicates of the formula NaHSitO2t + 1.pH2O or Na2SitO2t + 1.pH2O where t is a number from 1.9 to 4 and p is a number from 0 to 20.

Among aluminosilicates, preference is given to those available in the market with the names of zeolite A, B, X and HS, and also to mixtures comprising two or more such components. Particular preference is given to zeolite A. Among polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates and acrylates, and also to copolymers thereof with maleic amphiphilic acid. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate either in racemic form or enatiomerically pure form (S, S).

The phosphonates or aminoalkylene poly (alkylene phosphonates) which are especially suitable are the alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrile-tris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid, and salts of the same. Also preferred are polyphosphonates having the following formula

in which

R18 is CH2PO3H2 or a soluble salt thereof and

d is an integer with value 0, 1,2 or 3.

Especially preferred are polyphosphonates in which b is a whole number with value 1.

Component peroxide C)

As the peroxide component C), any compound which is capable of hydrogen peroxide in aqueous solutions is taken into account, for example, the organic and inorganic peroxides known in the literature and available on the market which whiten textile materials at conventional washing temperatures, for example, at a temperature of 10 to 95 ° C. Preferably, however, inorganic peroxides are used, for example, persulfates, perborates, percarbonates and / or persilicates.

All these peroxide compounds can be used alone or together with a peroxyacid bleach precursor and / or a bleach catalyst. Peroxyacid precursors are often referred to as bleach activators. Suitable bleach activators include bleach activators that carry O- and / or N-acyl groups and / or substituted or unsubstituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED); the acylated glycolurils, especially tetraacetyl glycolurea (TAGU), N, N-diacetyl-N, N-dimethylurea (DDU); sodium 4-benzoyloxy-benzenesulfonate (SBOBS); sodium 1-methyl-2-benzoyloxy-benzene-4-sulfonate; sodium 4-methyl-3-benzoyloxybenzoate; the trimethylammonium toluoxy-benzenesulfonate; acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); compounds of formula (6):

wherein R22 is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R21 is a linear or branched (C7-C15) alkyl, especially activators known under the names SNOBS, SLOBS and DOBA; the nitrile compounds that form perimino acids with peroxides are also taken into account as bleach activators. These bleach activators can be used in an amount of up to 12% by weight, preferably from 2 to 10% by weight, based on the total weight of the composition.

It is also possible to use additional bleach catalysts, which are commonly known, for example transition metal complexes such as those disclosed in EP 1194514, EP 1383857 or WO04 / 007657.

Additional bleach catalysts are disclosed in the following documents: US 2001044401, EP 0458397, WO 9606154, EP 1038946, EP 0900264, EP 0909809, EP 1001009, WO 9965905, WO 0248301, WO 0060045, WO 02077145, WO 0185717, WO 0164826, EP 0923635, DE 19639603, DE102007017654, DE102007017657, DE102007017656, US 20030060388, EP 0918840B1, EP 1174491A2, EP 0805794B1, WO 9707192A1, US 6235695B1, EP 0912690B1, EP 832969B1, US 6479450B1, WO 9933947A1, WO 0032731A1, WO 03054128A1, DE102004003710, EP 1083730, EP 1148117, EP 1445305, US 6476996, EP 0877078, EP 0869171, EP 0783035, EP 0761809 and EP 1520910.

The compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes of bis-triazinylamino-stilbenedisulfonic acid, bis-triazolyl-ethylbenzenesulphonic acid, bis-styryl-biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a bis-benzimidazolyl derivative or a coumarin derivative or a pyrazoline derivative.

The compositions may further comprise one or more additional additives. Such additives are, for example, soil suspending agents, for example, sodium carboxymethylcellulose; pH regulators, for example, alkali metal or alkaline earth metal silicates; foam regulators; for example, soaps; salts for adjusting the properties of granulation and spray drying, for example, sodium sulfate; perfumes; and also, if appropriate, antistatic and softening agents such as, for example, smectite; bleaching agents; pigments; and / or shading agents. These constituents must be especially stable with respect to any bleaching agent employed.

If such auxiliary compounds are used, they are added in a total amount of 0.1-20% by weight, preferably 0.5-10% by weight, especially 0.5-5% by weight, based on in the total weight of the detergent formulation.

In addition, the detergent optionally may also comprise enzymes. Enzymes can be added in order to remove stains. Enzymes normally improve action on spots caused by proteins or starches such as, for example, blood, milk, grass or fruit juice. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes that react with cellulose and its derivatives and hydrolyze them to form glucose, cellobiose and cello-oligosaccharides. Cellulases eliminate dirt and, in addition, have the effect of enhancing the soft touch of the tissue.

Examples of common enzymes include, but are not limited to, the following: proteases such as those described in US 6242405, column 14, lines 21 to 32; lipases such as those described in US 6242405, column 14, lines 33 to 46; amylases such as those described in US 6 242405, column 14, lines 47 to 56; and cellulases such as those described in US 6242405, column 14, lines 57 to 64;

detergent proteases commercially available, such as Alcalase®, Esperase®, Everlase®, Savinase®, Kannase® and Durazym®, marketed for example, by NOVOZYMES A / S;

commercially available detergent amylases, such as Termamyl®, Duramyl®, Stainzyme®, Natalase®, Ban® and Fungamyl®, marketed for example, by NOVOZYMES A / S;

cellulase detergents available on the market, such as Celluzyme®, Carezyme® and Endolase®, marketed for example, by NOVOZYMES A / S;

commercially available detergent lipases, such as Lipolase®, Lipolase Ultra® and Lipoprime®, marketed, for example, by NOVOZYMES A / S;

suitable manasas such as Mannanaway®, marketed by NOVOZYMES A / S.

The enzymes, when used, may be present in a total amount of from 0.01 to 5% by weight, especially from 0.05 to 5% by weight and, more especially, from 0.1 to 1% by weight. 4% by weight, based on the total weight of the detergent formulation.

Other preferred additives for the compositions according to the invention are dye fixing agents and / or polymers which, during the washing of the textiles, prevent stains caused by the dyes in the washing water that have been detached from the textiles in the fabrics. washing conditions. Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60000, more especially from 10000 to 50000. If such polymers are used, they are usually employed in a total amount of from 0.01 to 5% by weight, especially from 0.05 to 5% by weight and, more especially, from 0.1 to 2% by weight, based on the total weight of the detergent formulation. Preferred polymers are those mentioned in WO-A-02/02865 (see especially page 1, last paragraph, and page 2, first paragraph) and those mentioned in WO-A-04/05688.

The compositions of the present invention may also optionally contain one or more heavy metal chelating agents, such as hydroxyethyldiphosphonate (HEDP). More generally, chelating agents suitable for use herein may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Other chelating agents suitable for use herein are the DEQUEST commercial series, and the chelators of Nalco, Inc.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglicines, alkali metal salts, ammonium and substituted ammonium thereof, and mixtures thereof.

The amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates).

Other biodegradable scavengers are, for example, amino acid acetates, such as Trilon M (BASF) and Dissolvine GL (AKZO), as well as asparagus acid derivatives, such as Baypure CX.

Preferably, the amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS").

If used, these selective transition metal chelating or sequestering agents will generally comprise from about 0.001% by weight to about 10% by weight, more preferably from about 0.05% by weight to about 1% by weight of the detergent compositions for laundry of the present document.

Preferred compositions herein may additionally comprise a dispersant polymer. When present, a dispersing polymer is normally at levels in the range of from 0 wt% to about 25 wt%, preferably from about 0.5 wt% to about 20 wt%, more preferably from about 1% by weight to about 8% by weight of the detergent composition.

Suitable polymers are preferably at least partially neutralized or salts of alkali metals, ammonium or substituted ammonium (for example, mono-, di-, or triethanolammonium) of polycarboxylic acids. Most preferred are the alkali metal salts, especially the sodium salts. Although the molecular weight of the polymer can vary over a wide range, it is preferably from about 1000 to about 500000, more preferably from about 1000 to about 250000.

Unsaturated monomeric acids which can be polymerized to form suitable dispersing polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, acomatic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments which do not contain carboxylate radicals, such as methyl vinyl ether, styrene, ethylene, etc., is suitable provided that such segments do not constitute more than about 50% by weight of the dispersing polymer.

Acrylamide and acrylate copolymers having a molecular weight of from about 3000 to about 100000, preferably from about 4000 to about 20,000, and an acrylamide content of less than about 50% by weight, preferably less than about 20% can also be used. by weight of the dispersant polymer. Most preferably, such a dispersant polymer has a molecular weight of about 4000 to about 20,000, and an acrylamide content of about 0% by weight to about 15% by weight, based on the total weight of the polymer.

Particularly preferred dispersing polymers are the modified low molecular weight polyacrylate copolymers. Such copolymers contain as monomer units: a) from about 90% by weight to about 10% by weight, preferably from about 80% by weight to about 20% by weight of acrylic acid or salts thereof and b) from about 10% by weight to about 90% by weight, preferably from about 20% by weight to about 80 % by weight of a substituted acrylic monomer or a salt thereof and have the general formula: - [(C (Ra ') C (Rb') (C (O) ORc ')] in which the valences apparently not filled they are in fact occupied by hydrogen, and at least one of the substituents Ra ', Rb', or Rc ', preferably Ra' or Rb ', is an alkyl or hydroxyalkyl group with 1 to 4 carbon atoms; Ra' or Rb It can be a hydrogen and Rc 'can be a hydrogen or a salt of an alkali metal The most preferred is a substituted acrylic monomer in which Ra' is methyl, Rb 'is hydrogen, and Rc' is sodium.

A suitable low molecular weight polyacrylate dispersing polymer preferably has a molecular weight less than about 15,000, preferably about 500 to about 10,000, most preferably about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein it has a molecular weight of about 3500 and is the fully neutralized form of the polymer comprising about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid.

Other dispersant polymers useful herein include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000.

Other additional dispersant polymers useful herein include cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate and hydroxypropyl cellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group.

Other suitable dispersing polymers are carboxylated polysaccharides, particularly starches, celluloses and alginates.

Still another group of acceptable dispersants are organic dispersant polymers, such as polyaspartate.

Organic solvents that can be used in laundry detergent formulations according to the invention, especially when the latter are in liquid or paste form, include alcohols having from 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols having from 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof, and ethers derivable from the classes of compounds mentioned. Such water-miscible solvents are present in the laundry washing formulations according to the invention preferably in amounts of not more than 20% by weight, especially in amounts of 1% by weight to 15% by weight.

Detergent laundry detergent formulations can be presented in a variety of physical forms such as, for example, powdered granules, pills, gel and liquid. Examples thereof include, among others, conventional high-performance laundry detergent powders, supercompact high-performance laundry detergent powders, conventional high-performance laundry detergents, high-strength pellets and gels. .

The laundry detergent formulation can also be in the form of an aqueous liquid containing from 5% by weight to 90% by weight, preferably from 10% by weight to 70% by weight of water, or form of a non-aqueous liquid containing not more than 5% by weight, preferably from 0% by weight to 1% by weight of water. Non-aqueous liquid laundry detergent formulations may comprise other solvents such as vehicles. Low molecular weight primary or secondary alcohols, for example, methanol, ethanol, propanol and isopropanol, are suitable for this purpose. The solubilizing surfactant used is preferably a monohydric alcohol, although polyols, such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (eg, 1,3-propanediol, ethylene glycol, glycerol, and the like) can also be used. , 2-propanediol). Such vehicles are generally used in a total amount of 5% by weight to 90% by weight, preferably from 10% by weight to 50% by weight, based on the total weight of the detergent formulation for laundry . Detergent laundry detergent formulations can also be used in the so-called "unit liquid dosage" form.

The definitions and preferences given above apply equally to all aspects of the invention. The following examples illustrate the invention.

Abbreviations and reagents:

GPC: gel permeation chromatography

Patron-PS: polystyrene standards for the GPC calibration, mbara = absolute pressure millibars SC = solid content, measurement by a Mettler Toledo halogen dryer (at 150 ° C, 0.5 g of sample). (The result is obtained as a% by weight).

THF: tetrahydrofuran

EtOH: ethanol

MeOH: methanol

TFAA: trifluoroacetic antidrid

PTSA: para-toluenesulfonic acid monohydrate

MPA: 1-methoxy-2-propyl acetate

n-BA: n-butyl acrylate

PD: polydispersity (the polydispersity of a sample is defined as the weight-average molecular weight Mw divided by Mn and gives an indication of how narrow a distribution is)

4VP: 4-vinylpyridine, obtainable from Schenectady International. Cetflic alcohol (1-hexadecanol 98% pure, available from Cognis)

LIAL® 125 A: straight-chain and mono-branched C12-15 alkanol mixture from Sasol Olefins and Surfactants GmbH.

LuN400: Lupragen® N 400: N, N ', N "-trimethylaminoethylethanolamine, obtainable from BASF

PCL1075: polycaprolactone alpha-cetyloxy-, omega-hydroxy- with Mn of 1075 g / mol.

LuON70: Lutensol® ON 70 (polyethylene glycol mono-isodecyl ether with Mn of 466 g / mol, obtainable from BASF)

MPEG500 (polyethylene glycol monomethyl ether with Mn 500 g / mol, available from Clariant) Solketal: racemic mixture of glycerol protected with the isopropylidene group, (+/-) - 2,2-dimethyl-4-hydroxymethyl-1,3 -oxiolane

HEMO: N-hydroxyethylmorpholine

LitOBu: Lithium tert-butoxylate obtainable from Aldrich Inc

DOWEX 50WX8 is an acid ion exchange resin obtainable in the company DOW. To activate Dowex resin, it was immersed overnight in a 2% solution of HCl, then it was filtered, washed with water and dried in an oven. 80 ° C.

NOR 01: polymerization regulator, which is prepared according to GB 2335190.

Idealized general structure of comb copolymers based on free radical polymerization

Transesterification occurs randomly. This is not properly reflected in many of the formulas, according to which it seems that there is a block of butyl esters and a block of other esters (R1 to R6). The above general formula means that the esters are present randomly and the indices show the approximate molar amounts of the respective esters. It should be noted, however, that the abbreviated names, for example poly (n-BA-co-MPEG500A) of Example A1, do not mention the end groups of both ends of the polymer, ie, the 1-phenyl-ethyl group and the fragment of NOR as shown in the above general formula. The designation "-co-" in the abbreviated names indicates that the monomers that formally constitute the polymer, in this example the n-BA and the MPEG500-acrylate, are present in a random manner.

The designation "-b-", as shown in Example B3, poly (n-BA-b-4VP), means that the polymer consists of two defined blocks, the first of monomer units n-BA and the second 4-vinylpyridine monomer unit block.

Behavior of the LCST solution

If the obtained polymers are water-soluble, they can show a behavior of the LCST-type solution (LCST = lower critical solution temperature ), ie, the solubility of the polymer decreases as the temperature increases. For example, a 1% by weight solution of the final polymer in demineralized water is a clear solution at room temperature, but becomes cloudy at elevated temperatures, for example above 50 ° C (= LCST). Analogously, this observation can be made in a salt solution (for example, 1% NaCl in water) and normally for the obtained polymers, the LCST in salt solution could be lower than in demineralized water. The polymers with an LCST lower than TA are obtained in the form of an emulsion in water, polymers with an LCST greater than 85 ° C remain a transparent solution throughout the measurement and do not show an LCST in the range of interest (from TA to 90 ° C) for washing applications. An indication of> 85 ° C means that an LCST is not observed up to the maximum measurement temperature of 85 ° C, which means that the solution remains transparent up to 85 ° C.

A) Preparation of polymers and copolymers

Example B1: Synthesis of a linear poly (n-BA) polymer.

Into a 1000 ml 3-neck round bottom flask equipped with a magnetic stir bar, a condenser, a thermometer and an addition funnel are added 150.10 g of n-butyl acrylate (n-BA, 128, 2 g / mol), 8.55 g of NOR 01 (317.5 g / mol) and 122.13 g of MPA, degassed three times with N2 / ford and polymerized at 135 ° C in an N2 atmosphere until a conversion of approximately 8% in moles is achieved. Slowly add 338.89 g of n-BA to the reaction with an addition funnel and polymerize at 135 ° C in an N 2 atmosphere until a conversion of approximately 48 mol% is reached (by SC measurement). The residual monomers and solvents are separated by distillation at 80 ° C and 1.2 kPaA (12 mbar).

A total of 291.29 g of a yellowish clear liquid polymer is obtained. GPC (THF, Patron-PS, Mn = 7800 g / mol, PD = 1.27). According to the 1H-NMR analysis, the degree of polymerization is 78.

Example A1: Poly (n-BA-co-MPEG500A)

Transesterification using MPEG500

Into a 100 ml flask equipped with an overhead stirrer and a distillation column with cooling of dry ice and acetone, 37.0 g of poly (n-BA) are added according to example B1 and 17.89 g of MPEG500 (Mn = 500 g / mol, 10 mol% based on the original amount of n-butyl esters) and dried by degassing at 60 ° C for 60 min at 6 kPaA (60 mbara). The transparent reaction mass in the flask is heated to 135 ° C. Two portions of 93 mg of LiOtBu are added for 4.5 h at 130-135 ° C. The n-butanol formed (approx.

2.50 g) is separated by distillation under reduced pressure (10 kPaA (100 mbar)).

50.10 g of poly (n-BA-co-MPEG500A), A1, are obtained in the form of a brown viscous liquid. Mn = 12900 g / mol, PD = 1.4. The analyzes by GPC and 1H-NMR indicate an almost quantitative conversion of the polyglycol. SC = 98.0%.

Polymer A1 was emulsified at room temperature as a 1% solution in water. The same behavior was observed in a NaCl solution, with the difference that at 50 ° C the polymer precipitated.

Examples A2 to A6

In a manner analogous to that described for polymer A1, polymers A2 to A6 are prepared with the molar ratios indicated in Table 1.

The resulting polymers also form clear 5% by weight solutions in the following organic solvents: butyl acetate, MPA, methoxypropanol, butyl glycol and xylene.

Example A7: Poly (n-BA-co-MPEG500A-co-LuON70A)

Co-transesterification using MPEG500 and Lutensol® ON 70 (ethoxylated iso-C10 alcohol)

Into a 100 ml flask equipped with an overhead stirrer and a distillation column with cooling of dry ice and acetone, 25.0 g of poly (n-BA) are added according to example B1 and 24.17 g. of MPEG500 (Mn = 500 g / mol, 20 mol% based on the original amount of n-butyl esters) and 11.26 g of Lutensol® ON 70 (Mn about 466 g / mol, 10 mol% based in the original amount of n-butyl esters), and dried by degassing at 60 ° C for 60 min at 6 kPaA (60 mbar). The transparent reaction mass in the flask is heated to 135 ° C. Four portions of 108 mg of LiOtBu are added for 6 h at 130-135 ° C. The n-butanol formed (approximately 5.3 g) is removed by distillation under reduced pressure (5 kPaA (50 mbar)).

52.46 g of poly (n-BA-co-MPEG500A-co-LuON70A), A7, are obtained in the form of a brownish viscous liquid. Mn = 14330 g / mol, PD = 1.6. The analyzes by GPC and 1H-NMR indicate an almost quantitative conversion of the glycol ethers. SC = 98.0%.

Polymer A7 is a clear solution at room temperature in the form of a 1% by weight solution in water. In a 1% solution of NaCl, a LTCS at 85 ° C is observed.

Examples A8 to A11

In a manner analogous to that described for polymer A7, polymers A8 to A11 containing Lutensol® ON 70 were prepared with the molar ratios indicated in Table 2.

Example B2: Synthesis of PCL1075 monool.

In a 500 ml flask equipped with an overhead stirrer, 49.73 g of cetyl alcohol (MW = 242.5 g / mol, 1 molar equivalent) and 171.3 g of epsilon-caprolactone (MW = 114) are placed. , 7.3 molar equivalents) and heated up to 170 ° C in an atmosphere of dry nitrogen. Two drops (about 100 mg) of dibutyltin dilaurate catalyst are added at 170 ° C and the content is subsequently stirred for 8 hours until a SC> 98% by weight is reached. The resulting colorless polyester is cooled to 80 ° C and poured into a glass bottle, where it solidifies to 219 g of a white waxy solid.

The 1H-NMR shows a total conversion of the polycaprolactone monool, and the OH number is determined at 52.02 mg KOH / g, a SC of 98.57% and a Gardner color <1.

Example A12: Poly (n-BA-co-MPEG500A-co-PCL1075A)

Co-transesterification using MPEG500 and PCL1075

Into a 100 ml flask equipped with an overhead stirrer and a distillation column with cooling of dry ice and acetone, 20.0 g of poly (n-BA) are added according to example B1 and 19.34 g of MPEG500 (Mn = 500 g / mol, 20 mol% based on the original amount of n-butyl esters) and 20.11 g of PCL1075 (example B2) (Mn about 1075 g / mol, 10 mol%) based on the original amount of n-butyl esters) and dried by degassing at 60 ° C for 60 min at 6 kPaA (60 mbar). The transparent reaction mass in the flask is heated to 135 ° C. Four 100 mg portions of LiOtBu are added for 6 h at 130-135 ° C. The n-butanol formed (approximately 4.3 g) is removed by distillation under reduced pressure (5 kPaA (50 mbar)).

52.31 g of poly (n-BA-co-MPEG500A-co-PCL1075A), A12, are obtained in the form of a brownish viscous liquid. Mn = 22560 g / mol, Pd = 1.69. The analyzes by GPC and 1H-NMR indicate a conversion> 95% of MPEG500 and polyesterol. SC = 98.3%

Polymer A12 forms an emulsion in both water and a 1% solution of NaCl, and in the latter it precipitates at 60 ° C.

Example A13: Poly (n-BA-co-MPEG500A-co-PCL1075A)

Consecutive transesterification using MPEG500 and PCL1075

Into a 100 ml flask equipped with an overhead stirrer and a distillation column with cooling of dry ice and acetone, 20.0 g of poly (n-BA) are added according to example B1 and 19.34 g of MPEG500 (Mn = 500 g / mol, 20 mol% based on the original amount of n-butyl esters) and dried by degassing at 60 ° C for 60 min at 6 kPaA (60 mbara). The transparent reaction mass in the flask is heated to 135 ° C. Three portions of 93 mg LiOtBu are added over 5.5 h at 130-135 ° C. After finishing the conversion (no formation of n-butanol), 20.11 g of PCL1075 (example B2) are added (Mn about 1075 g / mol, 10 mol% based on the original amount of n-butyl esters) ) to the reaction mass and the transesterification continued at 135 ° C for another 4 hours with the addition of three 93 mg portions of LiOtBu. The total amount of n-butanol formed (approximately 4.3 g) is separated by distillation under reduced pressure (5 kPaA (50 mbar)). 51.39 g of poly (n-BA-co-MPEG500A-co-PCL1075A), A13, are obtained in the form of a brown viscous liquid. Mn = 22690 g / mol, PD = 1.78. The analyzes by GPC and 1H-NMR indicate a conversion> 95% of MPEG500 and polyesterol. SC = 98.4%.

Polymer A13 forms a translucent emulsion in water at RT, which becomes turbid at 65 ° C, whereas in an 1% solution of NaCl at RT an emulsion is formed and the polymer precipitates at 60 ° C.

Examples A14 to A15

In a manner analogous to that described for polymer A13, polymers A14 to A15 and A25 containing PCL1075 are prepared with the molar ratios indicated in Table 3.

T l: r r n n n l n n n n l l

Example A18: Poly-BA-co-MPEG500A-co-HEMOA

Co-transesterification using MPEG500 and HEMO

Into a 100 ml flask equipped with an overhead stirrer and a distillation column with cooling of dry ice and acetone, 27.0 g of poly (n-BA) are added according to example B1, 26.11 g of MPEG500 (Mn = 500 g / mol, 20 mol% based on the original amount of n-butyl esters) and 3.42 g of HEMO (MW = 131 g / mol, 10 mol% based on the original amount of n-butyl esters) and dried by degassing at 80 ° C for 60 min at 8 kPaA (80 mbar). The transparent reaction mass in the flask is heated to 135 ° C. Four portions of 98 mg LiOtBu are added for 6 h at 130-135 ° C. The n-butanol formed (approx.

5.8 g) is separated by distillation under reduced pressure (4.5 kPaA (45 mbar)).

49.0 g of poly (n-BA-co-MPEG500A-co-HEMOA), A18, are obtained in the form of a brownish viscous liquid. Mn = 11430 g / mol, PD = 1.76. The analyzes by GPC and 1H-NMR indicate a conversion> 95% of the MPEG500. SC = 98.2%.

Polymer A18 does not show an LCST below 85 ° C in pure water, but does show an LCST of 60 ° C in 1% NaCl. Examples A19 to A24

In a manner analogous to that described for polymer A18, polymers A19 to A24 containing HEMO are prepared with the molar ratios indicated in Table 4.

T l 4: r r i n lim n n in n n n n l l l HEM

Example A26: Poly (n-BA-co-SolketalA)

Transesterification using Solketal ((+/-) - 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane.) In a 100 ml flask equipped with an overhead stirrer and a distillation column with dry ice cooling and acetone, add 40.0 g of poly (n-BA) according to example B1 and 25.56 g of Solketal (Mn = 132 g / mol, 50 mol% based on the original amount of esters of n- butyl) and dried by degassing at 80 ° C for 60 min at 8 kPaA (80 mbar) The transparent reaction mass in the flask is heated to 135 ° C. Five portions of 100 mg LiOtBu are added for 13 hrs. -135 ° C. The n-butanol formed (ca.14.3 g) is separated by distillation under reduced pressure (6 kPaA (60 mbara)).

43.1 g of poly (n-BA-co-SolketalA), A26, are obtained in the form of a brown viscous liquid. Mn = 10470 g / mol, PD = 1.57. The SC is determined at 96.9%. The analyzes by GPC and 1H-NMR indicate a total conversion of the Solketal without deprotection of the diol.

Polymer A26 does not show solubility in pure water or in a 1% NaCl solution.

Examples A27 to A31

In a manner analogous to that described for the polymer A26, the polymers A27 to A31 containing HEMO are prepared with the molar ratios indicated in Table 5.

T: r r n n n l n l n l l l l l l l l

Example A32: Deprotection of poly (n-BA-co-MPEG500A-co-SolektalA) to poly (n-BA-co-MPEG500A-co-glyceryl) with TFAA

In a 100 ml flask equipped with an overhead stirrer 5.5 g of polymer according to Example A30 are dissolved in 11.0 g of THF, 11.0 g of H2O and 5.0 g of MeOH. 1.1 g of trifluoroacetic anhydride (MW = 230) are added at room temperature, followed by heating to 80 ° C and stirring the contents for 18 h. The resulting brown solution is analyzed by NMR to ensure that all acetal groups have disappeared. The polymer solution is concentrated under reduced pressure (10 kPaA (100 mbar)) to a SC of 94.5% to give 4.5 g of a brown viscous liquid. Mn = 10770 g / mol, PD = 1.50. The 1H-NMR indicated total deprotection of the Solketal units.

Polymer A32 shows an LCST of 55 ° C in pure water and 50 ° C in a 1% solution of NaCl.

Example A35: Deprotection of poly (n-BA-co-MPEG500A-co-SolektalA) to poly (n-BA-co-MPEG500A-co-glyceryl) with Dowex

Into a 100 ml flask equipped with an overhead stirrer, 5.55 g of the polymer according to Example A29 are dissolved in 11.1 g of THF, 11.1 g of H2O and 5.0 g of EtOH. 1.1 g of DOWEX 50WX8 (acid resin) are added at room temperature, followed by heating to 80 ° C and stirring the contents for 18 h. To the resulting brown solution was added another portion of DOWEX 50WX8 (1.1 g), followed by 1.0 g of H2O. After a further 18 h of stirring at 80 ° C, the polymer solution is filtered and concentrated under reduced pressure (10 kPaA (100 mbar)) to a SC of 98.8% to give 4.3 g of a viscous liquid of brown color. Mn = 13200 g / mol, PD = 1.62. The 1H-NMR indicated total deprotection of the Solketal units. Polymer A35 is converted into an emulsion in both pure water and a 1% NaCl solution.

Example A37: Deprotection of poly (n-BA-co-MPEG500A-co-SolektalA) to poly (n-BA-co-MPEG500A-co-glyceryl) with a combination of TFAA and PTSA

In a 100 ml flask equipped with an overhead stirrer, 12.5 g of polymer according to Example A31 are dissolved in 6.5 g of THF, 0.65 g of H2O and 6.0 g of EtOH. At room temperature 0.185 g of trifluoroacetic anhydride (MW = 230) and 0.75 g of para-toluenesulfonic acid monohydrate (MW = 190) are added, followed by heating to 80 ° C and stirring the contents for 18 h. Add another portion of PTSA and TFAA (the same amounts) and 2.0 g of water, and stir for another 18 h at 80 ° C. Finally, the polymer solution is concentrated under reduced pressure (10 kPaA (100 mbar)) to a SC of 96.5% to give 10.9 g of a brown viscous liquid. Mn = 8670 g / mol, PD = 1.49. The 1H-NMR indicated total deprotection of the Solketal units. The resulting polymer shows an LCST of 55 ° C in pure water and 50 ° C in a 1% solution of NaCl.

Examples A33 to A38

In a manner analogous to that described for polymer A32, polymers A33 to A38 are prepared from the precursors of Table 6.

T l: r r n n l n l l l l l l l l l l l l l l l l l l l l l l l l l l

Example A34: Preparation of poly (n-BA-co-HEMO [H +] A-co-glyceryl)

Into a 100 ml flask equipped with an overhead stirrer, 5.55 g of polymer according to Example A28 are dissolved in 11.1 g of THF, 11.1 g of H2O and 5.0 g of EtOH. 1.1 g of TFAA (M ^w = 230) are added at room temperature, followed by heating to 80 ° C and stirring the contents for 18 h. The polymer solution is concentrated under reduced pressure (10 kPaA (100 mbar)) to a 95.5% SC to give 5.1 g of a brown viscous liquid. Mn = 5340 g / mol, PD = 2.16. The 1H-NMR indicates a total deprotection of the Solketal units, part of the HEMO groups (25%) are obtained in the form of trifluoroacetates.

Polymer A34 has an LCST greater than 85 ° C in both pure water and a 1% solution of NaCl, while the starting polymer A28 shows no solubility in either of the two media.

Example A39: Preparation of poly (n-BA-co-HEMOcuat [+] A-co-glyceryl)

In a 100 ml flask equipped with an overhead stirrer, 5.0 g of polymer according to Example A18 are dissolved in 10.0 g of H 2 O, and 1.42 g of ethyl bromide are added (MW = 109 , 50% in moles with respect to the HEMO units) at room temperature. The clear solution is stirred for 6 h at RT, and subsequently it is poured into a glass flask, without any further elaboration (yield of 15.97 g). The content of solids of 28.5%. Due to the insolubility of the quaternized polymer in THF, analysis by GPC can not be carried out.

Polymer A39 has an LCST greater than 85 ° C in both pure water and a 1% NaCl solution.

Example A40

In a manner analogous to that described for polymer A39, polymer A40 is prepared from Example A21 as indicated in Table 7.

^

Example A51: Poly (n-BA-co-MPEG500A-co-LuN400A)

Co-transesterification using MPEG500 and Lupragen® N 400

Into a 100 ml flask equipped with an overhead stirrer and a distillation column with cooling of dry ice and acetone, 27.0 g of poly (n-BA) are added according to example B1, 26.11 g of MPEG500 (Mn = 500 g / mol, 20 mol% based on the original amount of n-butyl esters) and 3.82 g of Lupragen® N 400 (Mn = 146 g / mol, 10 mol% based on the original amount of n-butyl esters) and dried by degassing at 70 ° C for 60 min at 10 kPaA (100 mbar). The transparent reaction mass in the flask is heated to 135 ° C. Four 100 mg portions of LiOtBu are added for 6 h at 130-135 ° C. The n-butanol formed (approx.

5.8 g) is separated by distillation under reduced pressure (8 kPaA (80 mbar)).

48.57 g of poly (n-BA-co-MPEG500A-co-LuN400A) are obtained in the form of a brown viscous liquid. Mn = 16760 g / mol, PD = 1.88. The analyzes by GPC and 1H- ^r M ⁿ indicate a conversion> 95% of the MPEG-OH and the aminoalcohol. SC = 97.8%.

Examples A52 to A54

In a manner analogous to that described for polymer A51, polymers A52 to A54 containing Lupragen N 400 are prepared with the molar ratios indicated in Table 8.

T l: r r n n n r n n n n l n

Example B3: Synthesis of a poly linear block copolymer (nBA-b-4VP)

In a 500 ml 3-neck round bottom flask equipped with a magnetic stir bar, a condenser and a thermometer, 214.18 g of poly (n-BA) are added according to example B1 with a degree of polymerization. of 74 units of nBA (per 1 H-NMR), 70,90 g of 4-vinylpyridine (4VP, MW = 105 g / mol) and 79,70 g of MPA, degassed three times with N 2 / ford and polymerized to 125 ° C in N2 atmosphere for 8 h. The residual monomers and solvents are separated by distillation at 80 ° C and 1.2 kPaA (12 mbara) until an SC of> 98% is reached and subsequently diluted to a SC of 80% with 60.0 g of MPA to give B3 (302.2 g) in the form of a yellowish orange viscous liquid. A small sample of the polymer without solvent is analyzed by GPC (THF, Patron-PS, Mn = 8600 g / mol, PD = 1.24). The length of the blocks is determined by 1H-NMR in 73 units of nBA and 15 units of 4VP.

Example C1: poly ([n-BA-co-MPEG500A] -b-4VP)

Into a 350 ml flask equipped with a magnetic stir bar and a distillation column with cooling of dry ice and acetone, 150.0 g of poly (n-BA-b-4VP) are mixed in MPA, prepared in accordance with example B3 (80% solids) with 80.0 g MPEG 500. At 90 ° C, the solvent is removed by distillation under reduced pressure, and subsequently heated at 130 ° C to the ford (2 kPaA (20 mbar) ) for one hour to eliminate traces of moisture. Three portions of 800 mg LiOtBu are added for 6 h at 115-130 ° C. The n-butanol formed (ca. 11.8 g) is removed by distillation under reduced pressure (2 kPaA (20 mbar)). The final product (188.2 g, brown liquid) is diluted to 50% by weight with H2O. Analyzes by GPC and 1H-NMR indicate a complete conversion of MPEG500. GPC: Mn = 9120 g / mol, PD = 1.87.

Polymer C1 is a clear solution in water (10% by weight) at room temperature and showed an LCST above 65 ° C.

Examples C2 to C4

In a manner analogous to that described for the polymer C1, the block polymers C2 to C4 containing MPEG 500 were prepared with the molar ratios indicated in Table 9.

T l: r r i n ^ lim r l l n n n l l l MPE

B) Results of application

Testing of the dirt release effect of the copolymers in the comb according to the invention in detergents

Treat a cloth of 5 g of white polyester fabric (WfK 30A) in 100 ml of wash water. The wash water contains water with a hardness of 16 ° German, a conventional washing agent (detergent WOB reference liquid conventional AATCC 2003 n ° of order 08804) in a concentration of 4.7 g / l and, optionally, 0.094 g / l of one of the active polymers of the invention. The treatment is carried out in a steel beaker in a LINITEST device for 30 minutes at 40 ° C. After this, the textiles are rinsed under the water tap, centrifuged and dried for 30 min at 45 ° C. This procedure is repeated 2 times (therefore 3 cycles of prewash in total) with the same cloth but with new washing water.

Afterwards, the cloths are acclimated for 2 h at room temperature and then each one is stained with 50 pl of dirty motor oil that is applied with a pipette. The spots are allowed to dry overnight at room temperature. On the following day the brightness Y (CIE) of the spots is measured with a GRETAG SPM100 reference spectrometer. Subsequently, each soiled cloth is washed in a Linitest beaker in 100 ml of wash water under the same conditions and in the same wash water composition as those described above for the prewash cycle. Then the cloths are dried for 30 min at 45 ° C and allowed to acclimate for 2 hours at room temperature before measuring the brightness and spots.

The difference in brightness Y of dirty engine oil stains before and after washing is called DY and gives a measure of the washing performance of the washing water.

The DY values for several polymers of types A, B or C are shown in Table B1.

Table B1: Performance results in dirt release tests

A significant increase in the brightness improvement DY of dirty engine oil stains is observed for the copolymers of the invention.

Testing the antiredeposition effect of the copolymers of the invention in detergents

A washing water containing water with a hardness of 16 ° German, a conventional washing agent (Detergent WOB of reference liquid conventional AATCC 2003 n ° of order 08804) in a concentration of 4.7 g / l, hollm is prepared (Corax N765) in a concentration of 0.03 g / l and, optionally, 0.075 g / l of one of the active polymers of the invention. The washing liquors are stirred first with a magnetic stirrer for 10 min, then treated in an ultrasonic bath for 10 min and, finally, stirred again for 10 min with a magnetic stirrer. 100 g of the washing water are poured into a beaker of a Linitest apparatus with stirring and a 5 g cloth of white cotton fabric (WfK 13AK) is added. The beakers are closed and the white cotton is treated for 30 min at 40 ° C in the wash water. After this, the textiles are rinsed under the water tap, centrifuged and dried for 30 min at 45 ° C. This procedure is repeated 2 times (therefore 3 washing cycles in total) with the same cloth of cotton but with new washing water and new hollm. The Y brightness (CIE) of the pads is then measured with a DATA-Co LOR Spectra Flash SF500 reference spectrometer.

The brightness Y of the cotton pads after the three washing cycles is a measure of the antiredeposition performance of the washing water, which contains the copolymer of the invention. When the panos are washed in the same way but without adding the hollm, the panos have a luminosity Y of approximately 89.

The values of Y for several polymers of types A, B or C are shown in Table B2.

Table B2: Performance results in dirt release tests

A significant increase in the brightness Y of the cotton pads is observed after three washing cycles for the washing waters containing the copolymers of the invention. In many cases, even a significant improvement is observed with respect to sodium carboxymethyl cellulose, the current state of the art.

Claims (5)

1. Use of one or more block or comb co-polymers as anti-fouling agents and dirt release agents in aqueous laundry washing processes in which the block or comb copolymers have been prepared in a first stage a) by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic or methacrylic acid; and in a second step b) has been modified in a transesterification reaction of analogues of polymers with a primary or secondary alcohol to form a block or comb copolymer; wherein the block or comb copolymer has been prepared in step a) from n-butyl acrylate; and wherein the primary or secondary alcohol of stage b) is an ethoxylate of formula (A) RA- [O-CH2-CH2-] n-OH (A) in which Ra is a saturated or unsaturated alkyl, straight or branched chain, with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is from 1 to 150; containing a primary or secondary alcohol at least one tertiary amino group; such as N, N, N'-trimethylaminoethylethanolamine; N-hydroxyethylmorpholine; or a primary alcohol whose chain is interrupted by at least one ester group such as polycaprolactone a-cetyloxy, -w-hydroxy with a molecular weight of 750 to 2500 g / mol. 2. Use according to claim 1, wherein the block or comb copolymer has a PD polydispersity of 1.0 to 2.5. 3. Use according to claim 1 or 2, wherein the block or comb copolymer has amphiphilic properties. 4. A method for preventing redeposition of dirt on textiles and for the release of textile dirt in aqueous laundry processes, said method comprising applying a block or comb copolymer that has been prepared in a first stage to ) by controlled free radical polymerization of a C 1 -C 10 alkyl ester of acrylic or methacrylic acid; and in a second step b) has been modified in a transesterification reaction of analogues of polymers with a primary or secondary alcohol to form a block or comb copolymer; wherein the block or comb copolymer has been prepared in step a) from n-butyl acrylate; and wherein the primary or secondary alcohol of stage b) is an ethoxylate of formula (A) RA- [O-CH2-CH2-] n-OH (A) in which R ^a is a saturated or unsaturated alkyl, straight or branched chain, with 1-22 carbon atoms, or alkylaryl or dialkylaryl with up to 24 carbon atoms and n is from 1 to 150; containing a primary or secondary alcohol at least one tertiary amino group; such as N, N, N'-trimethylaminoethylethanolamine; N-hydroxyethylmorpholine; or a primary alcohol whose chain is interrupted by at least one ester group such as polycaprolactone a-cetyloxy, -w-hydroxy with a molecular weight of 750 to 2500 g / mol. 5. Detergent compositions for washing clothes that include: I) from 1 to 50% by weight, based on the total weight of the composition, A) of at least one surfactant; II) from 0 to 70% by weight, based on the total weight of the composition, B) of at least one adjuvant detergency substance; III) from 0 to 30% by weight based on the total weight of the composition, C) of at least one peroxide and / or a peroxide-forming substance; IV) from 0.05 to 10% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 4% by weight, based on the total weight of the composition, D) of at least one block or comb copolymer as defined above; V) from 0 to 60% by weight, based on the total weight of the composition, E) of at least one additional additive; VI) from 0 to 90% by weight, based on the total weight of the composition, F) of water.