WO2002006580A1

WO2002006580A1 - Fabric treatment composition, method of treating fabric and perfluoroalkyl amphiphilic compounds

Info

Publication number: WO2002006580A1
Application number: PCT/EP2001/006376
Authority: WO
Inventors: Jun Huang; De-Bao Su; Shang-Ren Wu
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2000-07-17
Filing date: 2001-06-05
Publication date: 2002-01-24
Also published as: GB2364702A; AU2001279644A1; GB0017520D0

Abstract

Compounds of general formula (I): Rf-A-C(O)-N(R)-CH2-(CHOH)4CH2OH, wherein: Rf is a group of formula (II): (CmX2m+1)-, where = an integer in the range 3-12, preferably 6-10 and X is a halogen atom, wherein at least 50 % of the halogen atom X are fluorine atoms and the reminder are chlorine or bromine atoms, A is a divalent linking group, and R is a hydrogen atom or a C1-C18 alkyl or alkenyl group, are used to give oil, soil and water repellency to fabric. They can be used in fabric treatment compositions. Compositions according to general formula (I) but in which R is a C1-C18 alkyl or alkenyl group are novel compounds.

Description

FABRIC TREATMENT COMPOSITION, METHOD OF TREATING FABRIC AND PERFLUOROALKYL AMPHIPHILIC COMPOUNDS

The present invention relates to a fabric treatment composition comprising a perfluoroal yl amphiphilic compound. The present invention also relates to a method of treating fabric using a perfluoroalkyl amphiphilic compound. The present invention further provides a novel class of perfluoroalkyl amphiphilic compounds. The present invention further provides a method of synthesising perfluoroalkyl amphiphilic compounds for use in fabric treatment.

The present invention is concerned with fabric treatment. The fabric treatment may be treatment before use, for example during the manufacture of fabric or garments, or it may take place after use of the fabric. Fabric treatment that takes place after use of the fabric, here termed fabric care, is used to reverse degradation of fabric that occurs as a result of use of the fabric, for example soiling and staining. Such treatments include laundering and the application of non-laundry fabric care products, such as spray-on products.

Considerable attention has been focused on components for inclusion in laundry and non-laundry compositions, which are specifically intended for fabric care. For example, colour care components such as photofading inhibitors and fluorescence inhibitors have been provided. Fabric softening components can be used. Soil release polymers are sometimes included in fabric care compositions which are deposited onto the fabric to allow soil and stains to be more easily removed during laundering.

EP-A-0240601 (Hoechst) discloses perfluoroalkyl polyglycerine compounds of general formula A:

R_f(Q)_k-A-0- (CH₂-CH(CH₂OH) -0)_pH

wherein R_f is a perfluoro alkyl moiety, Q is a divalent linking group, K is 0 or 1, A is an alkenylene or divalent aryl linking group and p is 1-15.

These compositions can be used to give oil and soil repellency to textiles, leather, wood or paper.

Compounds of formula A are amphiphilic - the polyglycerine chain has hydrophilic properties whereas the perfluoroalkyl moiety has hydrophobic properties.

Compounds of general formula A include an ether group between the polyglycerine chain and the rest of the molecule. Such ether bonds can be difficult to synthesise in practice.

EP-A-0255443 (ATTA) discloses surfactants, typically for use in pharmaceutical preparations, having a polyhydroxylated hydrophilic moiety, a highly fluorinated moiety and a functional junction group linking the moieties together. Included in the disclosure of EP-A- 0255443 are compounds of general formula B:

R_f- CH₂CH₂CON ( CH₃ ) CH₂ ( CHOH ) ₄CH₂OH , B

wherein R_f =CsFn , C F₁₅ or C₈F₁

However, there is no mention that these compounds may have any application in the treatment of fabrics.

EP-A-0255443 further discloses a process for preparation of the compounds thereof. The process involves reacting a polyol or aminopolyol in which the hydroxy groups, or part thereof, are protected, with a highly fluorinated derivative so as to link the polyol or aminopolyol moiety with the highly fluorinated moiety through a functional junction group. The highly fluorinated derivative may be an alcohol, an amine, an anhydride, a mixed anhydride or an acyl chloride. Compounds of general formula B are synthesised by reacting glucamide with an acid anhydride derivative of the highly fluorinated moiety.

The present invention sets out to provide fabric treatment compositions which use perfluoroalkyl amphiphilic compounds which are easy to synthesise and which give water, soil and oil repellency to fabric. The present invention further sets out to provide perfluoroalkyl amphiphilic compounds which are simple to synthesise.

Accordingly, in one aspect, the present invention provides fabric treatment compositions comprising a perfluoroalkyl amphiphilic compound of general formula (I) : Rf-A- C ( O) -N (R) - CH₂ ( CHOH) ₄CH₂OH ( I )

wherein :

Rf i s a group of the formula ( I I ) :

( C_mX2m+l ) - ( I I )

where m = an integer in the range 3-20, preferably 4-18, and X is a halogen atom, wherein at least 50% of the halogen atom X are fluorine atoms and the reminder are chlorine or bromine atoms,

A is a divalent linking group, and

R is a hydrogen atom or a Ci-C^ alkyl or alkenyl group .

The present inventors have discovered that perfluoroalkyl glucamides are relatively easy to synthesise because of the amide bond. However, the amide bond is found to be stable on storage. The compounds are found to give excellent soil and oil repellency to cotton and polyester fabrics, and water repellency to polyester fabrics .

In another aspect, the present invention provides the use of a perfluoroalkyl amphiphilic compound according to general formula (I) above in a method of polyester fabric treatment, to give oil, soil and water repellency to the polyester fabric.

In a further aspect, the present invention provides the use of a perfluoroalkyl amphiphilic compound according to general formula (1) above in a method of cotton fabric treatment, to give oil and soil repellency to the cotton fabric .

In another aspect, the present invention provides a method of treating a fabric comprising applying a fabric treatment composition comprising the perfluoralkyl amphiphilic compound of general formula (I) above to the fabric.

In another aspect, the present invention provides a perfluoroalkyl amphiphilic compound of general formula (III) :

R_f-A-C(O) -N(R) -CH₂- (CHOH)₄-CH₂OH (III)

wherein R_f and A have the meanings given in relation to general formula (I) above and R is a C_!-C₁₈ alkyl or alkenyl group .

In another aspect of the present invention, there is provided a method of synthesising the perfluoroalkyl compound of general formula I comprising the step of reacting with N-alkyl glucamine a compound of general formula (IV) ;

R_f-A-C(0)ORι (IV)

wherein R_f, A have the meanings given in relation to general formula I above and Ri is an alkyl group. Detailed Description of the Invention

Preferred aspects of the present invention will be described below.

Perfluoroalkyl Amphiphilic Compounds

Any suitable perfluoroalkyl amphiphilic compound falling within general formula I above may be used. However, the following features are particularly preferred.

Preferably, the perfluoroalkyl group R_f is a highly fluorinated moiety wherein at least 50% of the atoms bonded to the carbon skeleton are fluorine atoms, the other atoms bonded to the carbon skeleton being hydrogen, chlorine or bromine atoms. Preferably, there are at least four fluorine atoms.

The perfluoroalkyl group R_f is preferably of general formula C_qF_2q-_H or C_qF_qCl-, wherein q is an integer in the range 3-12. It is preferred that q is in the range 4-12, more preferably 6-12, most preferably 8-10.

The divalent linking group A is preferably selected from Ci-Cis alkylene, 1,4 phenylene or 1,4 phenylene substituted with at least one group selected from Ci-C₁₈ alkyl, Cι-C₁₈ alkoxy, halogen (preferably F) or-S0₃Na the Cι-C₁₈ alkylene chains or 1,4 phenyl chains being optionally interrupted by -O- . Particularly preferred linking groups are alkylene groups of general formula (V) :

-(CH₂)p (V) where p is in the range 2-18, more preferably 2-12.

The perfluoroalkyl amphiphilic compounds for use in the present invention may be straight chain perfluoroalkyl glucamides (where R=H or methyl) or branched perfluoroalkyl glucamides, where R is an alkyl group. Straight chain perfluoralkyl glucamides are known from EP-A-0255443 , but branched chain perfluoroalkyl glucamides are novel and a further subject of the present invention.

In general formula (I) , R is an alkyl or alkenyl group, which is suitably straight but may be branched. It may have from 1-18 carbon atoms, more preferably 1-12 carbon atoms, and most preferably 1-8 carbon atoms. It may be substituted, for example with OH or halogen atoms.

Particularly preferred perfluoroalkyl glucamides of use in the present invention comprise perfluoroalkyl glucamides of general formula (VI) :

R_f-CH₂CH₂(CH₂)_πCON(R)CH₂(CHOH)₄CH₂OH, in which: (VI)

R=CH₃ , n=0 , R_f=C₄F₈Cl , C₆F₁₂C1 , C₄F₉ , C₆F₁₃ or C₈F₁₇

R= -CH₃ , n=2 , R_f is -C₆F₁₃ ,

R= -CH₃ , n=8 , R =C₄F₉ or -C₄F₈C1 ,

R_f=-C₈F₁₇ , n=0 , R=C₃H₇ , C₄H₉ , C₆H₁₃ , C₈H₁₇ , C₁₀H₂₁ , or C₂H₄OH

The last class are novel compounds according to the present invention . Method of Preparation of Perfluoroalkyl Glucamides

Perfluoroalkyl glucamides according to the present invention may be manufactured by the process disclosed in EP-A-0255443. Alternatively, the novel method of synthesis of the present invention may be used.

The novel synthesis route according to the present invention employs an amidation reaction between an ester derivative of a perfluoroalkyl compound and N-alkyl glucamine .

Suitable ester derivatives can be obtained by any suitable method. Preferably, ester derivatives are methyl esters.

The ester derivatives may however be obtained by reacting a perfluoroalkyl halide with an alkenoic acid ester under suitable conditions:

R_fY+CH₂=CH . B . C0₂Ri → R_fCH₂CH₂-B-C0₂Rι

wherein R_f has the meaning given above

B is a linking group which may be selected from the same group from which linking group A is selected, and

Ri has the meaning set out above .

Preferably, Ri is methyl. Preferably, the linking group B is -(CH₂)_n-, wherein n is in the range 0-16, preferably 0-10.

Y is a halogen atom, preferably iodine. Halogen derivatives of perfluoroalkyl groups are available in the art and can be obtained from Acros Organics or Fisher Scientific Company.

N-alkyl glucamines are available in the art from Aldrich Company.

Alternatively, they can be synthesised by reducing glucose in the presence of primary amine . For example, the following reaction may be used:

glucose + RNH₂ → RNHCH₂ (CHOH) ₄CH₂OH

wherein R has the meaning set out above .

The reduction is suitably carried out by hydrogenation in the presence of a suitable catalyst, for example Raney Nickel .

Fabric Care Compositions

The present invention is suitable for use in industrial or domestic fabric wash compositions, fabric conditioning compositions and compositions for both washing and conditioning fabrics (so-called through the wash conditioner compositions) . The present invention can also be applied to industrial or domestic non-detergent based fabric care compositions, for example spray-on compositions.

Perfluoroalkyl amphiphilic compounds are suitably present in the fabric care compositions of the present invention at levels in excess of 0.2% by weight, preferably greater than 0.4% by weight. They are preferably present at levels less than 1.5% by weight and preferably less than 1.2% by weight .

Fabric Wash Compositions

Fabric wash compositions according to the present invention may be in any suitable form, for example powdered, tableted powders, liquid or solid detergent bars.

Fabric wash compositions according to the present invention comprise a fabric wash detergent material selected from non-soap anionic surfactant, nonionic surfactants, soap, amphoteric surfactants, zwitterionic surfactants and mixtures thereof .

Suitable anionic surfactants are well known to the person skilled in the art and include alkyl benzene sulphonate, primary and secondary alkyl sulphates, particularly C₈-C₁₅ primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl sulphosuccinates; ether carboxylates; isethionates; sarcosinates; fatty acid ester sulphonates and mixtures thereof. The sodium salts are generally preferred.

Nonionic surfactants are also well known to the person skilled in the art and include primary and secondary alcohol ethoxylates, especially C₈-C₂₀ aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Cιo-C₁₅ primary and secondary aliphatic alcohol ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide) . Mixtures of nonionic surfactant may be used.

Detergent compositions suitable for use in domestic or industrial automatic fabric washing machines generally contain anionic non-soap surfactant or nonionic surfactant, or combinations of the two in suitable ratio, as will be known to the person skilled in the art, optionally together with soap.

Many suitable detergent-active compounds are available and fully described in the literature, for example in "Surface- Active Agents and Detergents", Volumes I and II, by Schwartz, Perry & Berch.

Anionic surfactant is suitably present at a level of from 5 wt% to 50 wt%, preferably 10 wt%-40 wt% based on the fabric treatment composition. Nonionic surfactant is suitably present at a level of 1-20 wt%, preferably 5-15 wt%.

The total amount of surfactant present will depend upon the intended end use and may be as high as 60 wt% for example in a composition for washing fabrics by hand. In compositions for machine washing of fabric, an amount of from 5 to 40 wt% is generally appropriate.

Detergency Builder

The detergent compositions of the invention will generally also contain one or more detergency builders. The total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.

Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever ) ; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble) ; and layered silicates as disclosed in EP 164 514B (Hoechst) . Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.

The detergent compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.

The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:

0.8-1.5 Na₂0. Al₂0₃. 0.8-6 Si0₂

These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5- 3.5 Si0₂ units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily be reaction between sodium silicate and sodium aluminate, as amply described in the literature.

Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof .

The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. The zeolite builder incorporated in the compositions of the invention may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.

Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.

Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboyxmethyloxysuccinates , carboxymethyloxymalonates , dipicolinates, hydroyxethyliminodiacetates, alkyl- and alkenylmalonates and succinates, ; and sulphonated fatty acid salts. This list is not intended to be exhaustive.

Especially preferred organic builders are citrates, suitable used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.

Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.

Bleach Components

Detergent compositions according to the invention may also suitably contain a peroxy bleach system for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.

Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates . Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate .

Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) .

The compositions may further comprise a photobleach system as described, for example, in EP-A-0035470. Fabric Softening Composition

The fabric treatment composition of the present invention may be a fabric conditioning composition or it may comprise fabric conditioner.

Fabric Softening Compound

The fabric softening compound is preferably a cationic nonionic or anionic fabric softening compound.

The fabric softening compound may be a quaternary ammonium material comprising a polar head group and one or two alkyl or alkenyl chains. The fabric softening compound may also be a nonionic fabric softening compound such as a fabric softening oil, a fabric softening silicone composition or a fabric softening ester composition such as sugar esters.

Particularly preferably, the fabric softening compound has two long chain alkyl or alkenyl chains with an average chain length greater than C₁₄, more preferably each chain has an average chain length greater than C₁₄, more preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C₁₈.

It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.

It is highly preferred if the fabric softening compounds are substantially water-insoluble. Substantially insoluble fabric softening compounds in the context of this invention are defined as fabric softening compounds having a solubility less than 1 x 10^" wt% in demineralised water at 20°C, preferably the fabric softening compounds have a solubility less than 1 x 10^" , most preferably the fabric softening compounds have a solubility at 20°C in demineralised water from 1 x 10^" to 1 x 10^"6.

Well known species of substantially water-insoluble quaternary ammonium compounds having the formula:

R¹ R^J

wherein R¹ and R² represent hydrocarbyl groups having from 12 to 24 carbon atoms; R³ and R represent hydrocarbyl groups containing 1 to 4 carbon atoms; and X is an anion, preferably selected from halide, methyl sulphate and ethyl sulphate groups are preferred.

Representative examples of these quaternary softeners include di (tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride; di (hydrogenated tallow alkyl) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; di (hydrogenated tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl diethyl ammonium chloride; di (coconut alkyl) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride and di (hydrogenated tallow alkyl) dimethyl ammonium chloride (Arquad 2HT Trade Mark) .

Other preferred softeners contain esters or amide links, for example those available under the trade names Accosoft 580, Varisoft 222, and Stepantex.

Particularly preferred fabric softening compounds are water-insoluble quaternary ammonium materials which comprise a compound having two C_12-18 alkyl or alkenyl groups connected to the molecule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present. The preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula:

R¹

(CH₂)_n-T-R²

wherein each R group is independently selected from C_1-4 alkyl, hydroxyalkyl or C_2-4 alkenyl groups; and wherein each R group is independently selected from C_8-28 alkyl or alkenyl groups; O O

II II

T is -C-O- or -0-C-; X is any suitable anion and n is an integer from 0-5. Particularly preferred is di (ethyl ester) dimethyl ammonium chloride (DEEDMAC) .

A second preferred type of quaternary ammonium material can be represented by the formula :

OOCR²

(R!)₃N⁺ — (CH₂), CH X^"

CH₂OOCR²

wherein R_l7 n, X^" and R₂ are as defined above.

It is advantageous for environmental reasons if the quaternary ammonium material is biologically degradable

Preferred materials of this class such as 1,2 bis [hardened tallowoyloxy] -3-trimethylammonium propane chloride and their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers) . Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-hardened tallowoyloxy-2-hydroxy trimethylammonium propane chloride.

The fabric softening agent may also be a polyol ester quat (PEQ) as described in EP 0 638 639 (Akzo) . Other Ingredients

The compositions of the invention can also contain one or more optional ingredients, selected from pH buffering agents, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, anti- shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.

The present invention may be in the form of a dilute or concentrated aqueous solution or suspension, for example as described in WO 97/15651, WO 95/27769. Alternatively, the fabric softening composition may be in the form of a powder for use in the rinse cycle of an automatic washing machine. Alternatively, the fabric softening composition may be in the form of a sheet comprising fabric conditioning compositions for use in a tumble dryer, for example as disclosed in WO 95/27777.

Fabric wash detergent compositions according to the present invention may further include through the wash softening material, such as cationic fabric softener.

Non-Detergent-Based Fabric Care Products

The present invention can also be used in non-detergent- based fabric care products. For example, the product may comprise the stain removal system as the principal ingredient. For example, non-detergent based compositions may comprise solutions of the stain removal system of the present invention in a suitable solvent, such as isopropanol, alcohol etc. The compositions may comprise aerosol or spray-on compositions. They may be in the form of sticks, bars, dab-on compositions, for example absorbed into sponges for application to the surface etc.

The present invention will be further described by way of example only with reference to the following examples.

Examples

Reference example 1 - preparation of N- alkyl glucamine RNHCH₂ (CHOH) ₄CH₂OH

A solution of D-glucose (50 mmol) , an alkylamine (55 mmol) and Raney Nickel (3 grams) in 160 ml of methanol was hydrogenated at 11 atm pressure and 60°C for 12 hours. The Raney Nickel catalyst was removed by filtration and the solution was concentrated to crystalise out the product.

The results for different alkylamines are set out in Table 1 below.

Reference Example 2 - General Preparative Method for N- alkyl perfluoro alkylglucamide (R_fCH₂CH₂CON (R) CH₂ (CHOH) ₄CH₂OH)

N-alkyl glucamine (RNHCH₂ (CHOH) ₄CH₂OH) in 10 ml anhydrous CH₃OH was heated to 70-80°C in a nitrogen atmosphere before addition of RfCH₂CH₂COOCH₃ and NaOCH₃(0.05 mmol, 0.955 M) . Reaction was continued at 70-80°C for 20 hours. Additional methanol was added to dissolve the solids. Then, Dowex (trade mark) resin (H ) was added and stirred for 30 minutes. After removal of the resin and solvent, the residue was purified by column chromatography (eluted with trichloromethane, followed by a 1:9 by volume mixture of methanol and trichloromethane) . Further purification by recrystallisation yielded products as white solids.

Test method - oil repellency

In order to evaluate oil repellency, the following test was used. Polyester and cotton test cloths of size 4.0 cm x 4.0 cm were used.

Polyester was pre-treated with IN Na₂C0₃ and boiled for 15 minutes. It was then washed with distilled water until neutral. It was boiled again in distilled water for 15 minutes, after which it was dried in a 65 °C oven for 30 minutes .

The cotton cloth was treated similarly except that it was boiled for 30 minutes with sodium carbonate instead of 15 minutes .

The test cloths were then each immersed in a methanol or ethanol solution of perfluoroalkyl glucamide for 1 hour and then taken out of the methanol or ethanol solution and dried at 40°C for 30 minutes.

Oil repellency was measured at 15°C using a red-coloured oil (cooking oil flavoured with chilli) . A 0.01 ml oil droplet was applied to the treated fabric surface. Effectiveness of repellency was assessed by determining how quickly the droplet spread.

There is no repellency if the droplet permeates the fabric quickly. The fabric has weak repellency if the droplet spreads slowly and high repellency if the droplet maintains a high contact angle .

Results

The synthesis methods were used to synthesise compounds according to the following formulae:

RfCH₂CH₂CON(R)CH₂(CHOH)₄CH₂OH (1)

R_f = -C₄F₉, R = -CH₃ (a)

Rf = -C₆Fi3, R = -CH₃ (b)

R_f = -C₈F₁₇, R = -CH₃ (c)

R_f = -C₈F₁₇, R = -C₃H₇ (d)

Rf = -C₈F₁₇, R = -C₄H₉ (e)

R_f = -CjjFπ, R = -C₆H₁₃ (f) Rf = - C₈F₁₇ , R = - C₈H₁₇ (g)

Rf = - C₈Fi₇ , R = C₁₀H₂₁ (h)

Oil repellency of fabric treated with various quantities of the compounds was tested on polyester and cotton fabric . Results for compounds la and lc are shown in Tables 2 and 3.

Table 2 Oil Repellency of Polyester Fabric Treated with RfCH₂CH₂CON(CH₃) CH₂ (CHOH) ₄CH₂OH (la-lc)

Table 3 Oil Repellency of Cotton Fabric Treated with R_fCH₂CH₂CON(CH₃) CH₂ (CHOH) ₄CH₂OH (la-lc)

The results show that high oil repellency can be obtained on polyester fabric with all of the compounds when they are deposited from a 0.5 or 1 wt% solution in methanol. The oil repellency effect is greater for the longer chain length perfluoroalkyl group. High oil repellency can be obtained with compounds having longer perfluoroalkyl chains on cotton. Perfluoroalkyl chains with greater than 6 carbon atoms are preferred.

The results at various concentrations for compounds (d) - (g) are shown in Table 4 and 5 which demonstrate the effect of the chain length of the alkyl group substituted on the nitrogen atom.

Table 4 Oil Repellency of Polyester Fabrics with C₈F₁₇CH₂CH₂CON (R) CH₂ (CHOH) ₄CH₂OH

Table 5 Oil Repellency of Cotton Fabrics with C₈F₁₇CH₂CH₂CON (R) CH₂ (CHOH) ₄CH₂OH

The results demonstrate that weak oil repellency can be obtained with a wide variety of chain lengths over a variety of concentrations of compound in ethanol . High oil repellency can be obtained with N-substituted alkyl chain lengths of 8 or below at 0.5% compound in ethanol. Even better results are obtained with cotton.

For comparison, the oil repellency test was carried out with the following compounds which are not according to the invention:

fluorocarbon surfactant - C₈F₁₇S0₃K

linear alkyl benzene sulphonate

alkyl glucamide C₇H₁₅CON (CH₃) CH₂ (CHOH) ₄CH₂OH (MEGA) Different solvents had to be used in order to dissolve the reference samples to treat the fabric uniformly. The results are shown in Table 6.

Table 6 Oil Repellency of Polyester Fabric Treated with Reference Samples

It can be seen that LAS and MEGA provide no oil repellency even at relatively high concentration in solvent . Fluorinated surfactant provides weak soil repellency at very high concentrations in solvent.

Test Method - Water Repellency

Polyester and cotton test cloths of 4.0cm by 4.0cm were used.

The polyester was pre-treated with IN NaC0₃ and boiled for 15 minutes . It was then washed with distilled water until neutral . It was boiled again in distilled water for 15 minutes after which it was dried in a 65°C oven for 30 minutes .

The cotton cloth was treated similarly except that it was boiled for 30 minutes with sodium carbonate instead of 15 minutes . The test cloths were then each immersed in an ethanol solution of perflouro alkyl glucamide for one hour. The test cloths were dried at 40°C for 30 minuets. Water repellency was measured at room temperature using coloured water. The persistence of a 0.01 ml water droplet on the fabric determined the effectiveness of repellency. If the droplet permeates the fabric quickly, there is no repellency. If the droplets spread slowly, repellency is weak. If the droplet maintains a high contact angle, repellency is high.

Results

Perflouro alkyl glucamides (c) - (h) defined in the oil repellency tests were used. The results at various concentrations in the ethanol are shown in the Tables 7 below:

Table 1 Water Repellency on Cotton

Table 8 Water Repellency on Polyester

It can be seen that perfluoalkyl glucamides do not do not provide water repellency for cotton, but do provide water repellency for polyester at concentrations up to 0.5 weight percent .

Test-Stability of N-Alkyl Perfluoroalkyl Glucamides

Samples of N-Alkyl perfluoroalkl glucamides were stored at room temperature for three years. Stability was assessed by comparing NMR, ESI and IR spectra before and after storage. Good stability of the compounds was demonstrated by these spectra.

Test-Deposition of the N-Alkyl Perfluoroakyl Glucamides on Fabric

A detergent solution comprising 0.6 grams of linear alkyl benzene sulfonate, 0.6 grams per litre of sodium tripolyphosphate, 0.3 grams of sodium carbonate and 1.5 grams of sodium sulphate at room temperature was prepared. Perfluoroakyl glucamides were dissolved at a level of 0.1 wt% in this detergent solution.

Test cloths were prepared by the same method as used in the oil and water repellency tests. The cloths were immersed in ten ml of the detergent solution containing 0.1% perflouralkyl glucamide at room temperature for 1 hour and then washed under agitation in 200ml of distilled water for ten minutes. The deposition of N-perfluoroalkyl glucamide was assessed by measuring oil repellency after washing and drying . Tests were repeated for N-alkyl perfluoalkyl glucamides having alkyl chain lengths from Cι-C₁₀. All showed significant oil repellency on cotton and polyester after washing once with water. The oil repellency did not decrease after washing once more with water. Perfluoroalkyl glucamides deposit well on to fabric and are not easily rinsed off.

Claims

CLAIMS :

1. Fabric treatment compositions comprising a perfluoroalkyl amphiphilic compound of general formula (I) .

R_f-A-C(O) -N(R) -CH₂- (CHOH)₄CH₂OH (I)

wherein:

R_f is a group of the formula (II) :

(C_mX_2m+1)- (II)

where m = an integer in the range 3-12, preferably

6-10, and X is a halogen atom, wherein at least 50% of the halogen atoms X are fluorine atoms and the reminder are chlorine or bromine atoms,

A is a divalent linking group, and

R is a hydrogen atom or a Cι -Cιs alkyl or alkenyl group .

2. A fabric treatment composition according to claim 1, wherein the perfluoroalkyl group R_f is of general formula C_qF_2q-H- or C_qF_2qCl-,

wherein q is an integer in the range 3-12, preferably 4-18, more preferably 6-12 and most preferably 8-10.

3. A fabric treatment composition according to claim 1 or 2, wherein the divalent linking group A is selected from Ci-C₁₈ (optionally substituted) alkylene, 1,4 phenylene, 1,4 phenylene substited with at least one group selected from alkyl, alkoxy, F or S0₃Na, the C]_.-C₁₈ alkenyl chains or 1,4 phenylene chains being optionally interrupted by -0-.

4. A fabric treatment composition according to any preceding claim, selected from fabric wash compositions, fabric conditioning compositions, compositions for both washing and conditioning fabrics and non-detergent based fabric care compositions.

5. Use of a perfluoroalkyl amphiphilic compound according to general formula (I) according to claim 1, in a method of cotton fabric treatment, to give oil and soil repellency to the cotton fabric.

6. Use of perfluoroalkyl amphiphilic compound according to general formula (1) according to claim 1, in a method of polyester fabric treatment, to give oil, soil and water repellency to the polyester fabric.

7. A method of treating fabric comprising applying a fabric treatment composition comprising a perfluoroalkyl amphiphilic compound of general formula (I) according to claim 1 to the fabric.

8. A perfluoroalkyl amphiphilic compound of general formula (III) :

R_f-A-C(O) -N(R) -CH₂- (CHOH)₄-CH₂OH, (III)

wherein R_f and A have the meanings in relation to general formula I above and R is a Cι~C₁₈ alkyl or alkenyl group .

9. A method of synthesising the perfluoroalkyl compound of general formula (I) of claim 1, comprising the step of reacting with N-alkyl glucamine a compound of general formula (IV) :

R_f-A-C(O) -O Ri

Wherein R_f and A have the meanings given in relation to general formula I above and Ri is an alkyl group.