EP0360331B1 - Fabric treatment composition - Google Patents
Fabric treatment composition Download PDFInfo
- Publication number
- EP0360331B1 EP0360331B1 EP89202298A EP89202298A EP0360331B1 EP 0360331 B1 EP0360331 B1 EP 0360331B1 EP 89202298 A EP89202298 A EP 89202298A EP 89202298 A EP89202298 A EP 89202298A EP 0360331 B1 EP0360331 B1 EP 0360331B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fabric
- alkyl
- benzimidazolyl
- carbamate
- treatment composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 0 CC1(*)CCC2NC=*C2CC1 Chemical compound CC1(*)CCC2NC=*C2CC1 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
Definitions
- This invention relates to a fabric treatment composition for treating fabrics during the rinse step of a fabric laundry process, and to a method for using said composition.
- the invention relates to a fabric treatment composition comprising a fabric-softening material, which is preferably a cationic fabric softening material and an antimicrobial agent.
- benzimidazolyl-alkyl-carbamates when combined with fabric-softening materials into a fabric treatment composition, are particularly effective in inhibiting fungal growth on fabrics which have been rinsed with said fabric treatment composition.
- a fabric treatment composition comprising a softening material and a benzimidazolyl-alkyl-carbamate.
- the softening material comprises a cationic fabric softener.
- Benzimidazolyl-alkyl-carbamates are well-known fungicides for use in agriculture. It has also been suggested in Japanese patent application 49 093 537 (Yoshitomi) to treat textiles with a composition containing Me-2-benzimidazole-carbamate in a solvent. This treatment, however, requires a separate processing step for applying the benzimidazolyl-alkyl-carbamate and a further separate processing step for removing the undesirable solvent compound.
- benzimidazolyl-alkyl-carbamate as used in a textile treatment composition of the invention is preferably of the following formula: wherein:
- benzimidazolyl-alkyl-carbamate substances are: benzimidazolyl-methyl-carbamate, benzimidazolyl-ethyl-carbamate, 5-ethyl-benzimidazolyl-ethyl-carbamate, benzimidazolyl-isopropyl-carbamate, 4-ethyl-benzimidazolyl-isopropyl-carbamate, 4-propyl-benzimidazolyl-isopropyl-carbamate, 4-butyl-benzimidazolyl-isopropyl-carbamate, 4-isobutyl-benzimidazolyl-isopropyl-carbamate, benzimidazolyl-ethylmethoxy-carbamate, 4-ethyl-benzimidazolyl-ethylmethoxy-carbamate, 5-ethyl-benzimidazolyl-ethylmethoxy-carbamate,
- the preferred benzimidazolyl-alkyl-carbamate is benzimidazolyl-methyl-carbamate.
- Intace® B 350 (75% carbendazim ex Intace
- Intace® B 300 (100% carbendazim ex Intace).
- antimicrobial substances may be incorporated in a fabric treatment composition according to the invention.
- antimicrobial substances are meant both antibacterial and antifungal products. Examples of such material are formaldehyde, halogenated phenols, nitrated mono- or polyalcohols and antimicrobial surface-active tensides.
- benzimidazolyl-alkyl-carbamates Particularly suitable for use in conjunction with benzimidazolyl-alkyl-carbamates are tetra-methylthiuramdisulphid, 1-methylol-2-thiono-2-dihydrobenzthiazol, N-dimethyl-N′-phenyl-(N′-fluordichloromethyl-thio) sulfphamid and 3-isothiazolone compounds such as for instance described in US-A-4,424,134.
- the amount of additional antimicrobial substances in the textile treatment composition is less than two times the amount of benzimidazolyl-alkyl-carbamate.
- the fabric softening materials may be selected from cationic, nonionic, amphoteric or anionic fabric softening materials.
- Suitable amphoteric fabric conditioning material for use in a composition according to the invention are fabric substantive amphotheric materials forming a particulate dispersion at a concentration of less than 1 g/l at at least one temperature between 0 and 100°C. Preferably at at least one temperature between 10 and 90 °C, more preferred between 20 and 80 °C.
- a fabric substantive amphoteric material is preferably an amphoteric or zwitterionic tertiary or quaternary ammonium compound having either one single long hydrocarbyl side chain or two long hydrocarbyl chains.
- amphoteric or zwitterionic ammonium compounds having two long hydrocarbyl chains is particularly preferred for many reasons including costs, ease of processing and better stability and performance.
- Suitable amphoteric materials are for example disclosed in EP-A-0332270.
- hydrocarbyl chain refers to linear or branched alkyl or alkenyl chains optionally substituted or interrupted by functional groups such as -OH,-O-,-CONH-, and -COO-.
- amphoteric fabric substantive materials are water insoluble and have a solubility in water at pH 2.5 at 20°C of less than 10 g/l.
- the HLB of the amphoteric fabric substantive material is preferably less than 10.0.
- Suitable cationic fabric softener materials for use in a composition according to the present invention are cationic materials which are water-insoluble in that the material has a solubility in water at pH 2.5 and 20°C of less than 10 g/l.
- Highly preferred materials are cationic quaternary ammonium salts having two C12-24 hydrocarbyl chains.
- R1 and R2 represent hydrocarbyl groups from 12 to 24 carbon atoms
- R3 and R4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms
- X is an anion, preferably selected from halide, methyl sulfate and ethyl sulfate radicals.
- quaternary softeners include ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; di(coconut) dimethyl ammonium chloride.
- Ditallow dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, di(coconut) dimethyl ammonium chloride and di(coconut) dimethyl ammonium methosulfate are preferred.
- Suitable materials also include dialkyl ethoxyl methyl ammonium methosulphate based on soft fatty acid, dialkyl ethoxyl methyl ammonium methosulphate based on hard fatty acid, and a material in which R3 and R4 represent methyl, R1 is C13 ⁇ 15, R2 is CH2CH2OCOR, Where R is stearyl, and X is methosulphate.
- Ditallow dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, di(coconut alkyl) dimethyl ammonium chloride and di(coconut alkyl) dimethyl ammonium methosulfate are preferred.
- R5 being tallow, which is available from Stepan under the tradename Stepantex VRH 90 and where R8, R9 and R10 are each alkyl or hydroxyalkyl groups containing from 1 to 4 carbon atoms, or a benzyl group.
- R6 and R7 are each an alkyl or alkenyl chain containing from 11 to 23 carbon atoms, and X ⁇ is a water soluble anion.
- hydrocarbylimidazolinium salts believed to have the formula: wherein R13 is a hydrocarbyl group containing from 1 to 4, preferably 1 or 2 carbon atoms, R11 is a hydrocarbyl group containing from 8 to 25 carbon atoms, R14 is an hydrocarbyl group containing from 8 to 25 carbon atoms and R12 is hydrogen or an hydrocarbyl containing from 1 to 4 carbon atoms and A ⁇ is an anion, preferably a halide, methosulfate or ethosulfate.
- Preferred imidazolinium salts include 1-methyl-1-(tallowylamido-) ethyl -2-tallowyl- 4,5-dihydro imidazolinium methosulfate and 1-methyl-1-(palmitoylamido)ethyl -2-octadecyl-4,5- dihydroimidazolinium chloride.
- Other useful imidazolinium materials are 2-heptadecyl-1-methyl-1- (2-stearylamido)ethyl-imidazolinium chloride and 2-lauryl-1-hydroxyethyl-1-oleyl-imidazolinium chloride.
- Also suitable herein are the imidazolinium fabric softening components of US patent No 4 127 489.
- Representative commercially available materials of the above classes are the quaternary ammonium compounds Arquad® 2HT (ex AKZO); Noramium® M2SH (ex CEKA); Aliquat 2HT (Trade Mark of General Mills Inc), Stepantex Q185 (ex Stepan); Stepantex VP85 (ex Stepan); Stepantex VRH90 (ex Stepan); Synprolam® FS (ex ICI) and the imidazolinium compounds Varisoft 475 (Trade Mark of Sherex Company, Columbus Ohio) and Rewoquat W7500 (Trade Mark of REWO).
- compositions according to the invention may also possibly in addition to the above mentioned softening agents, one or more amine softening materials.
- R15 is a C6 to C24, hydrocarbyl group
- R16 is a C1 to C24 hydrocarbyl group
- R17 is a C1 to C10 hydrocarbyl group.
- Suitable amines include those materials from which the quaternary ammonium compounds disclosed above are derived, in which R15 is R1, R16 is R2 and R17 is R3.
- the amine is such that both R15 and R16 are C6-C20 alkyl with C16-C18 being most preferred and with R17 as C1 ⁇ 3 alkyl, or R15 is an alkyl or alkenyl group with at least 22 carbon atoms and R16 and R12 are C1 ⁇ 3 alkyl.
- these amines are protonated with hydrochloric acid, orthophosphoric acid (OPA), C1 ⁇ 5 carboxylic acids or any other similar acids, for use in the fabric conditioning compositions of the invention.
- R18 is a C6 to C24 hydrocarbyl group
- R19 is an alkoxylated group of formula -(CH2CH2O) y H, where y is within the range from 0 to 6
- R20 is an alkoxylated group of formula -(CH2CH2O) z H where z is within the range from 0 to 6 and m is an integer within the range from 0 to 6, and is preferably 3.
- m it is preferred that R18 is a C16 to C22 alkyl and that the sum total of z and y is within the range from 1 to 6, more preferably 1 to 3.
- m is 1, it is preferred that R18 is a C16 to C22 alkyl and that the sum total of x and y and z is within the range from 3 to 10.
- Ethomeen® Ex Armour
- Ethoduomeen® Ex Armour
- the amines of type (ii) or (iii) are also protonated for use in the fabric conditioning compositions of the invention.
- R22 and R23 are divalent alkenyl chains having from 1 to 3 carbons atoms
- R24 is an acyclic aliphatic hydrocarbon chain having from 15 to 21 carbon atoms.
- a commercially available material of this class is Ceranine® HC39 (ex Sandoz).
- compositions according to the invention may also contain nonionic fabric-softening agents.
- Suitable nonionic fabric-softening agents include glycerol esters, such as glycerol monostearate, fatty alcohols, such as stearyl alcohol, alkoxylated fatty alcohols, fatty acids, lanolin and derivatives thereof.
- Suitable materials are disclosed in European Patent Applications 88 520 (Unilever), 122 141 (Unilever) and 79 746 (Procter & Gamble). Prefererably, such materials are included at a level within the range of from 0.5% to 10% by weight of the composition.
- compositions can also contain one or more optional ingredients selected from non-aqueous solvents such as C1-C4 alkanols and polyhydric alcohols, pH-buffering agents such as weak acids, e.g. phosphoric, benzoic or citric acids (the compositions preferably have a pH of less than 6.0 more preferred between 2.0 and 5.0), rewetting agents, viscosity modifiers such as electrolytes, included at levels from about 20 to 6000 ppm, aluminium chlorohydrate, antigelling agents, perfumes especially body odour reducing perfumes, perfume carriers, hydrocarbons, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, anti-shrinking agents, anti-wrinkle agents, soil-release agents, antioxidants, anti-corrosion agents, preservatives such as Bronopol (Trade Mark), a commercially available
- Silicones can be included in the compositions as the ironing aid, re-wetting agent or the antifoaming agent.
- Suitable silicones for use in the compositions according to the invention include predominantly linear polydialkyl or alkylaryl siloxanes in which the alkyl groups contain one to five carbon atoms.
- the siloxanes can be amido- or amino-substituted. When the siloxane is amine-substituted the amine group may be quaternised.
- compositions according to the invention may take a variety of forms. They may for example be liquids containing an aqueous base.
- compositions according to the invention may be in the form of a powder, creams, pastes, a block or a tablet. Suitable types of blocks and tablets are disclosed in European Patent Specification EP-A-255 779 (Unilever).
- the total level of the fabric softening material and the benzimidazolyl-alkyl-carbamate is preferably from 1 to 30% by weight.
- the weight of the fabric-softening agent is preferably from 1 to 20% and the weight of the benzimidazolyl-alkyl-carbamate is preferably from 0.05 to 10%, more preferably from 0.1 to 5%, most preferably from 0.5 to 1.5%.
- the weight ratio of softening agent to benzimidazolyl-alkyl-carbamate is preferably between 10:1 and 100:1, more preferably around 20:1.
- Preferably more than 50 wt % of the softening materials are cationic softening materials.
- compositions When the compositions are in the form of powders, blocks or tablets, they may contain means for restraining the release of the cationic fabric-softening agent and benzimidazolyl-alkyl-carbamate in water, such as paraffin and tallow alcohol.
- suitable materials are disclosed in the European Patent Specification EP-A-255 779 (Unilever).
- the compositions may also contain an electrolyte to aid dispersion of the cationic fabric-softening agent and the benzimidazolyl-alkyl-carbamate, after the release inhibitor has ceased to have effect, and an antifoam material.
- a suitable antifoam granule may be of the type described in our European Patent Specification EP-A-94 250.
- the compositions are preferably added to a large volume of water to form a liquor with which the fabrics to be treated are contacted.
- the liquor can be formed by adding the fabric treatment composition to water during the rinse stage of a hand-washing process.
- the composition can be added by hand or by way of an automatic dispensing device to rinse water in the tub of a washing machine of the type which is common in Europe, that is a machine in which the fabrics are rinsed in a tub which is filled with rinse water, agitated to achieve efficient rinsing and then drained.
- a washing machine of the type which is common in Europe, that is a machine in which the fabrics are rinsed in a tub which is filled with rinse water, agitated to achieve efficient rinsing and then drained.
- the total concentration of the fabric-softening agent and the benzimidazolyl-alkyl-carbamate in the rinse liquor will be between 30 and 500 ppm.
- the compositions can be used in a washing machine which is designed in such a manner that the fabrics are rinsed in running water.
- a washing machine which is designed in such a manner that the fabrics are rinsed in running water.
- the fabrics will normally have been previously washed in the same tub of the machine, or they may be placed in the tub specifically for rinsing.
- the running water When previously washed, they will have at least some of the wash liquor containing a detergent active still adsorbed on or otherwise associated with them, the running water then serving to flush this wash liquor out of the fabrics.
- the rinse water running into the tub will be substantially free of any detergent actives.
- the composition can be added to the fabrics in the tub before the rinse water flows into the tub, simultaneously with the rinse water or part-way through the rinse cycle.
- Aqueous compositions were prepared according to the formulations in the following tables.
- the compositions were prepared by co-melting the cationic fabric-softening agent and benzimidazolyl-alkyl-carbamate at 80°C.
- the co-melt thus formed was added to water at 80°C to form a dispersion.
- the benzimidazolyl-alkyl-carbamate was post-dosed to a dispersion containing the cationic fabric-softening agent.
- compositions were tested by the following method.
- Tablets comprising 8 g sodium bicarbonate, 2 g Adogen and 0.4 g carbendazim (Intace B 300) were prepared and compared with tablets comprising 8 g sodium bicarbonate and 2 g Adogen®.
- Pieces of 50/50 resinated polyester cotton fabrics and pieces of a 100% cotton poplin fabric were washed in a Japanese washing machine at room temperature with 31 g of a commercially available wash powder. After a 1 minute spin to separate the wash liquor, the fabrics were rinsed for ten minutes in running water. One tablet was added and the rinse continued for a further 5 minutes. After line drying, the treated fabrics were assessed for microbial activity as in Example 1.
- aqueous compositions were prepared as in examples 1-6 and tested on cotton as in these examples.
- the carbendazim used was Intace B300. These examples again show a reduction in fungal growth when carbendazim is added to fabric softening compositions of the invention.
- Product Fungal Growth A Niger Penicillium 17.
- Water 50 18. 7.56% Stepantex VRH 90 50 50 19. 7.56% Stepantex VRH 90 + 1.0% Carbendazim 0-10 5 20.
- DTTMAPC (1,2 ditallow oxytrimethylammonium propane chloride) 50 50 21.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
- This invention relates to a fabric treatment composition for treating fabrics during the rinse step of a fabric laundry process, and to a method for using said composition. In particular, the invention relates to a fabric treatment composition comprising a fabric-softening material, which is preferably a cationic fabric softening material and an antimicrobial agent.
- It is known that fungal growth can develop on fabrics stored under certain physiological conditions, such as in a humid atmosphere or where there is poor air circulation. These growths can damage the fabrics by causing them to discolour. The fabrics can also develop an unpleasant smell. It has been found that the discolouration or staining of the fabrics is difficult to remove either by normal laundering or after treatment with a strong bleaching agent.
- It has previously been proposed (EP-A-86 423, Henkel KGaA) to incorporate specific antimicrobial substances in fabric treatment compositions.
- We have now surprisingly discovered that benzimidazolyl-alkyl-carbamates, when combined with fabric-softening materials into a fabric treatment composition, are particularly effective in inhibiting fungal growth on fabrics which have been rinsed with said fabric treatment composition.
- The incorporation of benzimidazolyl-alkyl-carbamates in textile treatment compositions according to the invention has also been found advantageous in that benzimidazolyl-alkyl-carbamates are:
- 1. effective against a wide range of micro-organisms, particularly fungi;
- 2. active during the life of the product;
- 3. of low mammalian toxicity and non-toxic to humans at the concentrations used;
- 4. colourless and odourless;
- 5. effective at low concentrations;
- 6. inexpensive and easy to apply;
- 7. resistant to sunlight;
- 8. not affecting fabric handle or strength;
- 9. compatible with water-repellent and flame-retardant agents, dyes and other textile auxiliaries; and
- 10. do not sensitize the fabric to damage by light or other influences.
- Thus, according to the invention there is provided a fabric treatment composition comprising a softening material and a benzimidazolyl-alkyl-carbamate. Preferably the softening material comprises a cationic fabric softener.
- Benzimidazolyl-alkyl-carbamates are well-known fungicides for use in agriculture. It has also been suggested in Japanese patent application 49 093 537 (Yoshitomi) to treat textiles with a composition containing Me-2-benzimidazole-carbamate in a solvent. This treatment, however, requires a separate processing step for applying the benzimidazolyl-alkyl-carbamate and a further separate processing step for removing the undesirable solvent compound.
-
- R¹
- is a C₁₋₄ alkyl, alkoxy or phenoxy alkyl; and
- R²
- is a C₁₋₄ alkyl, hydrogen, nitrogen or halogen.
- Particular examples of suitable benzimidazolyl-alkyl-carbamate substances are: benzimidazolyl-methyl-carbamate, benzimidazolyl-ethyl-carbamate, 5-ethyl-benzimidazolyl-ethyl-carbamate, benzimidazolyl-isopropyl-carbamate, 4-ethyl-benzimidazolyl-isopropyl-carbamate, 4-propyl-benzimidazolyl-isopropyl-carbamate, 4-butyl-benzimidazolyl-isopropyl-carbamate, 4-isobutyl-benzimidazolyl-isopropyl-carbamate, benzimidazolyl-ethylmethoxy-carbamate, 4-ethyl-benzimidazolyl-ethylmethoxy-carbamate, 5-ethyl-benzimidazolyl-ethylmethoxy-carbamate, benzimidazolyl-ethylethoxy-carbamate, benzimidazolyl-ethyl-propoxy-carbamate, benzimidazolyl-ethylphenoxy-carbamate, 4-ethyl-benzimidazolyl-ethylphenoxy-carbamate and 5-ethyl-benzimidazolyl-ethylphenoxy-carbamate.
- The preferred benzimidazolyl-alkyl-carbamate is benzimidazolyl-methyl-carbamate.
- It is also possible to employ mixtures of different benzimidazolyl-alkyl-carbamates.
- Particularly preferred is the use of Intace® B 350 (75% carbendazim ex Intace), and Intace® B 300 (100% carbendazim ex Intace).
- Other antimicrobial substances may be incorporated in a fabric treatment composition according to the invention. By antimicrobial substances are meant both antibacterial and antifungal products. Examples of such material are formaldehyde, halogenated phenols, nitrated mono- or polyalcohols and antimicrobial surface-active tensides.
- Particularly suitable for use in conjunction with benzimidazolyl-alkyl-carbamates are tetra-methylthiuramdisulphid, 1-methylol-2-thiono-2-dihydrobenzthiazol, N-dimethyl-N′-phenyl-(N′-fluordichloromethyl-thio) sulfphamid and 3-isothiazolone compounds such as for instance described in US-A-4,424,134. Generally, the amount of additional antimicrobial substances in the textile treatment composition is less than two times the amount of benzimidazolyl-alkyl-carbamate.
- The fabric softening materials may be selected from cationic, nonionic, amphoteric or anionic fabric softening materials.
- Suitable amphoteric fabric conditioning material for use in a composition according to the invention are fabric substantive amphotheric materials forming a particulate dispersion at a concentration of less than 1 g/l at at least one temperature between 0 and 100°C. Preferably at at least one temperature between 10 and 90 °C, more preferred between 20 and 80 °C. For the purpose of this invention a fabric substantive amphoteric material is preferably an amphoteric or zwitterionic tertiary or quaternary ammonium compound having either one single long hydrocarbyl side chain or two long hydrocarbyl chains. From these compounds the use of amphoteric or zwitterionic ammonium compounds having two long hydrocarbyl chains is particularly preferred for many reasons including costs, ease of processing and better stability and performance. Suitable amphoteric materials are for example disclosed in EP-A-0332270.
- In this specification the expression hydrocarbyl chain refers to linear or branched alkyl or alkenyl chains optionally substituted or interrupted by functional groups such as -OH,-O-,-CONH-, and -COO-.
- Preferably the amphoteric fabric substantive materials are water insoluble and have a solubility in water at pH 2.5 at 20°C of less than 10 g/l. The HLB of the amphoteric fabric substantive material is preferably less than 10.0.
- Suitable cationic fabric softener materials for use in a composition according to the present invention are cationic materials which are water-insoluble in that the material has a solubility in water at pH 2.5 and 20°C of less than 10 g/l. Highly preferred materials are cationic quaternary ammonium salts having two C12-24 hydrocarbyl chains.
- Well-known species of substantially water-insoluble quaternary ammonium compounds have the formula
wherein R₁ and R₂ represent hydrocarbyl groups from 12 to 24 carbon atoms; R₃ and R₄ represent hydrocarbyl groups containing from 1 to 4 carbon atoms; and X is an anion, preferably selected from halide, methyl sulfate and ethyl sulfate radicals. - Representative examples of these quaternary softeners include ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; di(coconut) dimethyl ammonium chloride.
- Ditallow dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, di(coconut) dimethyl ammonium chloride and di(coconut) dimethyl ammonium methosulfate are preferred.
- Suitable materials also include dialkyl ethoxyl methyl ammonium methosulphate based on soft fatty acid, dialkyl ethoxyl methyl ammonium methosulphate based on hard fatty acid, and a material in which R₃ and R₄ represent methyl, R₁ is C₁₃₋₁₅, R₂ is CH₂CH₂OCOR, Where R is stearyl, and X is methosulphate. Ditallow dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, di(coconut alkyl) dimethyl ammonium chloride and di(coconut alkyl) dimethyl ammonium methosulfate are preferred.
- Other preferred cationic compounds include those materials as disclosed in EP-A-239,910 (P&G).
- Other preferred materials are the materials of formula
R₅ being tallow, which is available from Stepan under the tradename Stepantex VRH 90
and
where R₈, R₉ and R₁₀ are each alkyl or hydroxyalkyl groups containing from 1 to 4 carbon atoms, or a benzyl group. R₆ and R₇ are each an alkyl or alkenyl chain containing from 11 to 23 carbon atoms, and X⁻ is a water soluble anion. These materials and their method of preparation are described in US-A-4,137,180 (LEVER BROTHERS). - Another class of preferred water-insoluble cationic materials are the hydrocarbylimidazolinium salts believed to have the formula:
wherein R₁₃ is a hydrocarbyl group containing from 1 to 4, preferably 1 or 2 carbon atoms, R₁₁ is a hydrocarbyl group containing from 8 to 25 carbon atoms, R₁₄ is an hydrocarbyl group containing from 8 to 25 carbon atoms and R₁₂ is hydrogen or an hydrocarbyl containing from 1 to 4 carbon atoms and A⁻ is an anion, preferably a halide, methosulfate or ethosulfate. - Preferred imidazolinium salts include 1-methyl-1-(tallowylamido-) ethyl -2-tallowyl- 4,5-dihydro imidazolinium methosulfate and 1-methyl-1-(palmitoylamido)ethyl -2-octadecyl-4,5- dihydroimidazolinium chloride. Other useful imidazolinium materials are 2-heptadecyl-1-methyl-1- (2-stearylamido)ethyl-imidazolinium chloride and 2-lauryl-1-hydroxyethyl-1-oleyl-imidazolinium chloride. Also suitable herein are the imidazolinium fabric softening components of US patent No 4 127 489.
- Representative commercially available materials of the above classes are the quaternary ammonium compounds Arquad® 2HT (ex AKZO); Noramium® M2SH (ex CEKA); Aliquat 2HT (Trade Mark of General Mills Inc), Stepantex Q185 (ex Stepan); Stepantex VP85 (ex Stepan); Stepantex VRH90 (ex Stepan); Synprolam® FS (ex ICI) and the imidazolinium compounds Varisoft 475 (Trade Mark of Sherex Company, Columbus Ohio) and Rewoquat W7500 (Trade Mark of REWO).
- The compositions according to the invention may also possibly in addition to the above mentioned softening agents, one or more amine softening materials.
- The term "amine" as used herein can refer to
- (i) amines of formula
- (ii) amines of formula
- (iii) imidazolines of formula
- (iv) condensation products formed from the reaction of fatty acids with a polyamine selected from the group consisting of hydroxy alkylalkylenediamines and dialkylenetriamines and mixtures thereof. Suitable materials are disclosed in European Patent Application 199 382 (Procter and Gamble).
- When the amine is of the formula I above, R₁₅ is a C₆ to C₂₄, hydrocarbyl group, R₁₆ is a C₁ to C₂₄ hydrocarbyl group and R₁₇ is a C₁ to C₁₀ hydrocarbyl group. Suitable amines include those materials from which the quaternary ammonium compounds disclosed above are derived, in which R₁₅ is R₁, R₁₆ is R₂ and R₁₇ is R₃. Preferably, the amine is such that both R₁₅ and R₁₆ are C₆-C₂₀ alkyl with C₁₆-C₁₈ being most preferred and with R₁₇ as C₁₋₃ alkyl, or R₁₅ is an alkyl or alkenyl group with at least 22 carbon atoms and R₁₆ and R₁₂ are C₁₋₃ alkyl. Preferably these amines are protonated with hydrochloric acid, orthophosphoric acid (OPA), C₁₋₅ carboxylic acids or any other similar acids, for use in the fabric conditioning compositions of the invention.
- When the amine is of formula II above, R₁₈ is a C₆ to C₂₄ hydrocarbyl group, R₁₉ is an alkoxylated group of formula -(CH₂CH₂O)yH, where y is within the range from 0 to 6, R₂₀ is an alkoxylated group of formula -(CH₂CH₂O)zH where z is within the range from 0 to 6 and m is an integer within the range from 0 to 6, and is preferably 3. When m is 0, it is preferred that R₁₈ is a C₁₆ to C₂₂ alkyl and that the sum total of z and y is within the range from 1 to 6, more preferably 1 to 3. When m is 1, it is preferred that R₁₈ is a C₁₆ to C₂₂ alkyl and that the sum total of x and y and z is within the range from 3 to 10.
- Representative commercially available materials of this class include Ethomeen® (ex Armour) and Ethoduomeen® (ex Armour).
- Preferably the amines of type (ii) or (iii) are also protonated for use in the fabric conditioning compositions of the invention.
- When the amine is of type (iv) given above, a particularly preferred material is
where R₂₂ and R₂₃ are divalent alkenyl chains having from 1 to 3 carbons atoms, and R₂₄ is an acyclic aliphatic hydrocarbon chain having from 15 to 21 carbon atoms. A commercially available material of this class is Ceranine® HC39 (ex Sandoz). - The compositions according to the invention may also contain nonionic fabric-softening agents. Suitable nonionic fabric-softening agents include glycerol esters, such as glycerol monostearate, fatty alcohols, such as stearyl alcohol, alkoxylated fatty alcohols, fatty acids, lanolin and derivatives thereof. Suitable materials are disclosed in European Patent Applications 88 520 (Unilever), 122 141 (Unilever) and 79 746 (Procter & Gamble). Prefererably, such materials are included at a level within the range of from 0.5% to 10% by weight of the composition.
- The compositions can also contain one or more optional ingredients selected from non-aqueous solvents such as C₁-C₄ alkanols and polyhydric alcohols, pH-buffering agents such as weak acids, e.g. phosphoric, benzoic or citric acids (the compositions preferably have a pH of less than 6.0 more preferred between 2.0 and 5.0), rewetting agents, viscosity modifiers such as electrolytes, included at levels from about 20 to 6000 ppm, aluminium chlorohydrate, antigelling agents, perfumes especially body odour reducing perfumes, perfume carriers, hydrocarbons, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, anti-shrinking agents, anti-wrinkle agents, soil-release agents, antioxidants, anti-corrosion agents, preservatives such as Bronopol (Trade Mark), a commercially available form of 2-bromo-2-nitropropane-1,3-diol, to preserve the fabric treatment composition, dyes, bleaches and bleach precursors, drape-imparting agents, antistatic agents and ironing aids.
- Silicones can be included in the compositions as the ironing aid, re-wetting agent or the antifoaming agent. Suitable silicones for use in the compositions according to the invention include predominantly linear polydialkyl or alkylaryl siloxanes in which the alkyl groups contain one to five carbon atoms. The siloxanes can be amido- or amino-substituted. When the siloxane is amine-substituted the amine group may be quaternised.
- These optional ingredients, if added, are each present at levels up to 5% by weight of the composition.
- The compositions according to the invention may take a variety of forms. They may for example be liquids containing an aqueous base.
- Alternatively, the compositions according to the invention may be in the form of a powder, creams, pastes, a block or a tablet. Suitable types of blocks and tablets are disclosed in European Patent Specification EP-A-255 779 (Unilever).
- When the compositions are in the form of liquid products, the total level of the fabric softening material and the benzimidazolyl-alkyl-carbamate is preferably from 1 to 30% by weight. Based on the total weight of the composition, the weight of the fabric-softening agent is preferably from 1 to 20% and the weight of the benzimidazolyl-alkyl-carbamate is preferably from 0.05 to 10%, more preferably from 0.1 to 5%, most preferably from 0.5 to 1.5%. The weight ratio of softening agent to benzimidazolyl-alkyl-carbamate is preferably between 10:1 and 100:1, more preferably around 20:1. Preferably more than 50 wt % of the softening materials are cationic softening materials.
- When the compositions are in the form of powders, blocks or tablets, they may contain means for restraining the release of the cationic fabric-softening agent and benzimidazolyl-alkyl-carbamate in water, such as paraffin and tallow alcohol. Other suitable materials are disclosed in the European Patent Specification EP-A-255 779 (Unilever). The compositions may also contain an electrolyte to aid dispersion of the cationic fabric-softening agent and the benzimidazolyl-alkyl-carbamate, after the release inhibitor has ceased to have effect, and an antifoam material. A suitable antifoam granule may be of the type described in our European Patent Specification EP-A-94 250.
- In use, the compositions are preferably added to a large volume of water to form a liquor with which the fabrics to be treated are contacted. The liquor can be formed by adding the fabric treatment composition to water during the rinse stage of a hand-washing process.
- Alternatively, the composition can be added by hand or by way of an automatic dispensing device to rinse water in the tub of a washing machine of the type which is common in Europe, that is a machine in which the fabrics are rinsed in a tub which is filled with rinse water, agitated to achieve efficient rinsing and then drained. Generally, the total concentration of the fabric-softening agent and the benzimidazolyl-alkyl-carbamate in the rinse liquor will be between 30 and 500 ppm.
- Alternatively, the compositions, especially when being in the form of a tablet or block, can be used in a washing machine which is designed in such a manner that the fabrics are rinsed in running water. With a machine of this type, the fabrics will normally have been previously washed in the same tub of the machine, or they may be placed in the tub specifically for rinsing. When previously washed, they will have at least some of the wash liquor containing a detergent active still adsorbed on or otherwise associated with them, the running water then serving to flush this wash liquor out of the fabrics. The rinse water running into the tub will be substantially free of any detergent actives. The composition can be added to the fabrics in the tub before the rinse water flows into the tub, simultaneously with the rinse water or part-way through the rinse cycle.
- The invention will now be illustrated by the following non-limiting examples. In these examples, all parts and percentages are by weight. Where commercially available materials are referred to, the percentages quoted are those of the active detergent therein.
- Aqueous compositions were prepared according to the formulations in the following tables. The compositions were prepared by co-melting the cationic fabric-softening agent and benzimidazolyl-alkyl-carbamate at 80°C. The co-melt thus formed was added to water at 80°C to form a dispersion. In examples containing 2.5 and 5.0% carbendazim respectively, the benzimidazolyl-alkyl-carbamate was post-dosed to a dispersion containing the cationic fabric-softening agent.
- The compositions were tested by the following method.
- Two pieces of a 50/50 resinated polyester cotton fabric and two pieces of a 100% cotton poplin fabric (each measuring 20 cm x 20 cm) were washed at 50°C with 5 grams of a commercially available washing powder, Persil® Automatic, in a litre of water in a tergotometer. After the wash liquor was separated, the fabrics were rinsed twice with a litre of demineralised water. 2 ml of an aqueous test composition was added to the second rinse. After line drying, the treated fabrics were assessed, as follows, to evaluate the microbial activity present.
- Two pieces, each measuring 5 cm x 5 cm, were cut from each piece of treated fabric. Both pieces were placed on Petri dishes containing nutrient agar. 0.1 ml of an inoculum of either Aspergillus niger or Penicillium spores was spotted onto the centre of each piece. Care was taken not to allow the inoculum to spread onto the surrounding agar. The inoculum concentration was 10⁸ spores ml⁻¹. The plates were incubated at 28°C and evaluation of fungal growth assessed after 3 days.
- The scale used to assess fungal growth was:
- 0
- = No growth on fabric.
- 10
- = very slight growth.
- 20
- = Visible, light, patchy growth.
- 30
- = Moderate growth on whole sample.
- 40
- = Heavy growth on most of sample.
- 50
- = Completely overgrown.
- Owing to discolouration of the fabric, caused by spore inoculum, a fungal growth score of 0 is never attained. A score of less than 10 is indicative of no growth.
EXAMPLE N° Reference 50/50 POLYESTER COTTON COTTON POPLIN A. niger Penicillium A. niger Penicillium Water 41 39 50 49 1. 5% Arquad 2HT 40 37 44 49 2. 5% 2HT + 0.1% C* 35 28 40 15 3. 5% 2HT + 0.25% C 30 30 35 < 10 4. 5% 2HT + 0.50% C 25 < 10 30 < 10 5. 5% 2HT + 2.5% C 18 < 10 < 10 < 10 6. 5% 2HT + 5.0% C < 10 < 10 < 10 < 10 * C = Carbendazim (Intace B 350) - The results show that even if carbendazim is incorporated in a fabric treatment composition containing Arquad 2HT, at low levels, such as 0.1%, there is a significant reduction in fungal growth.
- Compositions according to the following tables were prepared as described in Example 1. Fabrics were evaluated as described for Example I. The following results were obtained.
EXAMPLE N° 50/50 POLYESTER COTTON COTTON POPLIN A. niger Penicillium A. niger Penicillium Water 50 47.5 50 50 7. 5% Arquad 2HT 37.5 35 50 50 8. 5% Arquad 2HT + 0.5% C* 25 < 10 30 < 10 9. 5% Arquad 2HT + 0.5% K** 32.5 42.5 42.5 47.5 10. 5% Arquad 2HT + 10% A*** 25 25 47.5 47.5 11. 5% Arquad 2HT + 0.5% P**** 35 35 50 50 * C = Carbendazim (Intace B 350) ** K = Kathon® (2-n-octyl-4-isothiazolin-3-one ex Rohm & Haas) *** A = Actifresh® L 8110, which comprises benzyl-alkyl-bis(hydroxy alkyl)ammonium, ex British Sanitized **** P = Preventol® R 89 (alkyl dimethyl benzyl ammonium chloride, ex Bayer) - These examples clearly show the surprisingly better performance of textile treatment compositions comprising benzimidazolyl-alkyl-carbamate antimicrobial substances.
- Tablets comprising 8 g sodium bicarbonate, 2 g Adogen and 0.4 g carbendazim (Intace B 300) were prepared and compared with tablets comprising 8 g sodium bicarbonate and 2 g Adogen®.
- Pieces of 50/50 resinated polyester cotton fabrics and pieces of a 100% cotton poplin fabric were washed in a Japanese washing machine at room temperature with 31 g of a commercially available wash powder. After a 1 minute spin to separate the wash liquor, the fabrics were rinsed for ten minutes in running water. One tablet was added and the rinse continued for a further 5 minutes. After line drying, the treated fabrics were assessed for microbial activity as in Example 1.
- The results were the following:
Fabric Treatment Fungal Growth Aspergillus Penicillium 50/50 Polycotton Control* 40-45 40 100% Cotton poplin Control 50 50 50/50 PC Softener + 0.4 g Carb. < 10 < 10 100% CP Softener + 0.4 g Carb. < 10 < 10 * Control = Tablet containing Adogen and NaHCO₃. - The following aqueous compositions were prepared as in examples 1-6 and tested on cotton as in these examples. The carbendazim used was Intace B300. These examples again show a reduction in fungal growth when carbendazim is added to fabric softening compositions of the invention.
Product Fungal Growth A Niger Penicillium 17. Water 50 50 18. 7.56% Stepantex VRH 90 50 50 19. 7.56% Stepantex VRH 90 + 1.0% Carbendazim 0-10 5 20. 5% DTTMAPC (1,2 ditallow oxytrimethylammonium propane chloride) 50 50 21. 5% DTTMAPC + 1% Carbendazim 0-10 0 22. 5% Imidazolinium (Rewoquat W7500H) 50 50 23. 5% Imidazolinium + 1.0% Carbendazim 0-5 0 24. 10.8% Dihardened tallow dimethyl ammonium chloride (DHTMAC) 2.7% Hardened tallow fatty acid 40 50 25. 10.8% DHTMAC 2.7% Hardened tallow fatty acid 1.0% Carbendazim 20 0-10 26. 6% DHTDMAC 50 50 27. 6% DHTDMAC + 1.0% Aluminium Chlorohydrate (ACH) 50 50 28. 6% DHTDMAC + 1.0% ACH + 1.0% Carbendazim 10 0 29. 3.8% DHTDMAC 1.9% Ceranine HC39 (ex Sandoz) 1.9% DHTM amine oxide (Lilaminox® M44, ex Berol Nobel) 0.38% Orthophosphoric Acid 50 50 30. 3.8% DHTDMAC 1.9% Ceranine HC39 1.9% DHTM Amine Oxide 0.38% Orthophosphoric acid + 1.0% Carbendazim 30 10-15
Claims (6)
- Fabric treatment composition comprising a fabric-softening material and a benzimidazolyl-alkyl-carbamate.
- Fabric treatment composition according to Claim 1 characterised in that it comprises:
1 - 30% by weight of the fabric-softening material, and
0.1 - 5% by weight of the benzimidazolyl-alkyl-carbamate. - Fabric treatment composition according to claim 1 comprising a cationic fabric softening material.
- Fabric treatment composition according to Claim 1, characterised in that it further comprises at least one other antimicrobial substance.
- Method for treating fabrics by rinsing the fabrics in an aqueous bath comprising a textile treatment composition comprising a fabric-softening material and a benzimidazolyl-alkyl-carbamate, wherein the concentration of the fabric softening material plus benzimidazolyl-alkyl-carbamate composition in the bath is from 30 to 500 ppm.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB888822206A GB8822206D0 (en) | 1988-09-21 | 1988-09-21 | Fabric treatment composition |
GB8822206 | 1988-09-21 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0360331A2 EP0360331A2 (en) | 1990-03-28 |
EP0360331A3 EP0360331A3 (en) | 1991-06-26 |
EP0360331B1 true EP0360331B1 (en) | 1995-03-22 |
Family
ID=10644018
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89202298A Expired - Lifetime EP0360331B1 (en) | 1988-09-21 | 1989-09-13 | Fabric treatment composition |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0360331B1 (en) |
JP (1) | JPH02112473A (en) |
KR (1) | KR950009497B1 (en) |
AU (1) | AU613792B2 (en) |
BR (1) | BR8904720A (en) |
CA (1) | CA1340358C (en) |
DE (1) | DE68921822T2 (en) |
ES (1) | ES2070168T3 (en) |
GB (1) | GB8822206D0 (en) |
MY (1) | MY105854A (en) |
PH (1) | PH27189A (en) |
TR (1) | TR24561A (en) |
ZA (1) | ZA897208B (en) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4993537A (en) * | 1973-01-06 | 1974-09-05 | ||
DE2459354C2 (en) * | 1974-12-16 | 1986-03-27 | Hoechst Ag, 6230 Frankfurt | SOFT SOFT CONDENSER CONCENTRATE WITH DISINFECTING PROPERTIES |
JPS57210068A (en) * | 1981-06-17 | 1982-12-23 | Asahi Chemical Ind | Production of polyurethane fiber having anti-fungal property |
DE3444068A1 (en) * | 1984-12-03 | 1986-06-05 | Henkel KGaA, 4000 Düsseldorf | AGENT AND METHOD FOR TREATING WASHED LAUNDRY |
-
1988
- 1988-09-21 GB GB888822206A patent/GB8822206D0/en active Pending
-
1989
- 1989-09-13 DE DE68921822T patent/DE68921822T2/en not_active Expired - Fee Related
- 1989-09-13 ES ES89202298T patent/ES2070168T3/en not_active Expired - Lifetime
- 1989-09-13 EP EP89202298A patent/EP0360331B1/en not_active Expired - Lifetime
- 1989-09-15 CA CA000611662A patent/CA1340358C/en not_active Expired - Fee Related
- 1989-09-19 KR KR1019890013429A patent/KR950009497B1/en not_active IP Right Cessation
- 1989-09-20 BR BR898904720A patent/BR8904720A/en not_active IP Right Cessation
- 1989-09-20 MY MYPI89001293A patent/MY105854A/en unknown
- 1989-09-20 AU AU41536/89A patent/AU613792B2/en not_active Ceased
- 1989-09-20 PH PH39258A patent/PH27189A/en unknown
- 1989-09-21 ZA ZA897208A patent/ZA897208B/en unknown
- 1989-09-21 JP JP1246230A patent/JPH02112473A/en active Pending
- 1989-09-21 TR TR89/0736A patent/TR24561A/en unknown
Also Published As
Publication number | Publication date |
---|---|
MY105854A (en) | 1995-02-28 |
DE68921822T2 (en) | 1995-07-13 |
KR900005010A (en) | 1990-04-13 |
JPH02112473A (en) | 1990-04-25 |
TR24561A (en) | 1991-11-22 |
BR8904720A (en) | 1990-05-01 |
ES2070168T3 (en) | 1995-06-01 |
AU613792B2 (en) | 1991-08-08 |
GB8822206D0 (en) | 1988-10-26 |
KR950009497B1 (en) | 1995-08-23 |
CA1340358C (en) | 1999-01-26 |
PH27189A (en) | 1993-04-16 |
AU4153689A (en) | 1990-03-29 |
ZA897208B (en) | 1991-05-29 |
DE68921822D1 (en) | 1995-04-27 |
EP0360331A2 (en) | 1990-03-28 |
EP0360331A3 (en) | 1991-06-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0404471B1 (en) | Fabric softening composition | |
EP0199382B1 (en) | Liquid fabric softener | |
CZ103397A3 (en) | Preparation for softening fabrics being added during washing into rinsing bath and containing chlorine entrapping substances | |
JPH0329908B2 (en) | ||
CZ2298A3 (en) | Biologically degradable preparations for softening fabrics and containing a smelling substance with prolonged effect | |
EP2007860B1 (en) | Rinse-added fabric treatment composition | |
US5723435A (en) | Rinse added fabric softener compositions containing antioxidants for sun-fade protection fabrics | |
EP0392764B1 (en) | Fabric conditioning article | |
EP0332270B2 (en) | Fabric conditioning composition | |
US4855072A (en) | Liquid fabric softener | |
EP1196521B1 (en) | Fabric care treatment composition and a method of treating fabric | |
US4844820A (en) | Liquid fabric softener comprising light-unstable red dye in protective package | |
EP0360331B1 (en) | Fabric treatment composition | |
EP0417987B1 (en) | Fabric softening | |
EP0409503B1 (en) | Fabric softening composition | |
EP0387064A2 (en) | Fabric conditioning | |
DE602004012965T2 (en) | Method of bleaching | |
EP0315126A2 (en) | Liquid softergent formulations having improved stability and softening properties | |
EP1290120B1 (en) | Fabric softening compositions containing cationic softeners and fatty amides | |
US20220033734A1 (en) | Fabric conditioner compositions | |
US6784152B2 (en) | Polyquat anionic scavengers for rinse cycle fabric softeners | |
EP1154068B1 (en) | Softener composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19910805 |
|
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UNILEVER PLC Owner name: UNILEVER N.V. |
|
17Q | First examination report despatched |
Effective date: 19940517 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 68921822 Country of ref document: DE Date of ref document: 19950427 |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2070168 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19960827 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970930 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970930 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20000807 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20000814 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000823 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000901 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20000914 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20000918 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010913 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010914 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010914 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020401 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20010913 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020501 |
|
EUG | Se: european patent has lapsed |
Ref document number: 89202298.9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020531 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20020401 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20020401 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20021011 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050913 |