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EP0517762B1 - Process for treatment of textiles - Google Patents

Process for treatment of textiles Download PDF

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Publication number
EP0517762B1
EP0517762B1 EP91905036A EP91905036A EP0517762B1 EP 0517762 B1 EP0517762 B1 EP 0517762B1 EP 91905036 A EP91905036 A EP 91905036A EP 91905036 A EP91905036 A EP 91905036A EP 0517762 B1 EP0517762 B1 EP 0517762B1
Authority
EP
European Patent Office
Prior art keywords
lipase
rinse
rinsing
rinse liquor
washing
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
Application number
EP91905036A
Other languages
German (de)
French (fr)
Other versions
EP0517762A1 (en
Inventor
Per Falholt
Erik Gormsen
Peter Rosholm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novo Nordisk AS
Original Assignee
Novo Nordisk AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DK53090A external-priority patent/DK53090D0/da
Priority claimed from DK148990A external-priority patent/DK148990D0/en
Application filed by Novo Nordisk AS filed Critical Novo Nordisk AS
Publication of EP0517762A1 publication Critical patent/EP0517762A1/en
Application granted granted Critical
Publication of EP0517762B1 publication Critical patent/EP0517762B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the invention relates to a process for treatment of textiles by use of a lipase.
  • Treatment of soiled or unsoiled textiles normally comprises washing with a detergent containing anionic and/or nonionic surfactant, followed by rinsing and drying. It belongs to the prior art that lipase can be incorporated into the detergent to improve the removal of fat soiling (EP 130,064, EP 214,761, US 4,810,414).
  • a non-dusting granulate containing a cellulase can be added to a main wash detergent composition in order to reduce the harshness of the laundry (US 4,435,307), that proteases are useful in detergent compositions in order to remove proteinaceous stains (US 3,723,250), and that amylases are useful in detergent compositions in order to remove starchy stains (US 3,627,688 and 4,548,727).
  • a given enzyme may be incompatible with a given detergent composition due to unsatisfactory activity and stability of the enzyme, and this imposes some limitations in the choice of enzyme and detergent formulation. It is the object of the invention to provide an alternative method of using a lipase in textile treatment, so as to obtain efficient lipolytic effects for a given lipase dosage while avoiding the above limitations.
  • a lipase provides a better lipolytic effect when used in the rinse liquor than when used as a constituent of the main wash composition.
  • the effect is particularly pronounced after repeated cycles of washing, rinsing and drying.
  • Detergent is essentially absent during rinsing, and thus compatibility problems are avoided.
  • the lipase may advantageously be added in the last rinse step together with a cationic surfactant.
  • the invention provides a process for treatment of textiles by use of a lipase, which is used in a rinse liquor for a rinsing step after washing, characterized by the fact that the lipase is producible by means of Humicola lanuginosa or Pseudomonase cepacia.
  • the lipase is used in the rinse liquor for the rinsing step after washing, together with a fabric softening agent and/or an antistatic agent.
  • the fabric softening agent and/or the antistatic agent is a cationic surfactant.
  • the cationic surfactant may be a dialkyl dimethyl ammonium chloride or an alkyl imidazoline methosulfate.
  • the enzyme is used in the rinse liquor for a second or later rinsing step, preferably in the last rinsing step. In this manner an even better enzymatic effect is observed.
  • the concentration of lipase in the rinse liquor is in the range of 0.001 to 5, preferably 0.01 to 2 mg pure lipase protein per liter of rinse liquor. At a concentration below 0.001 mg pure lipase protein per liter of rinse liquor no significant lipase effect can be observed, and at a concentration above 5 mg pure lipase protein per liter of rinse liquor the lipase cost will be unreasonably high.
  • the lipases which can be used in the invention are lipases producible by means of Humicola lanuginosa (US 4,810,414) and Pseudomonas cepacia (WO 89/04361).
  • the lipase activity unit, LU is defined in AF 95/5, which is available on request from Novo Nordisk A/S, Novo allé, DK-2880 Bagsvaerd, Denmark, this publication being published before March 1, 1990.
  • a cationic surfactant effective for fabric after-treatment is used together with the lipase in the process according to the invention.
  • cationic surfactants are known in the art.
  • One example is quaternary ammonium salts such as dialkyl (C16-C18) dimethyl ammonium chloride, alkyl (C32-C36) trimethyl ammonium chloride or alkyl (C8-C18) dimethyl benzyl ammonium chloride (ABDAC); and alkyl imidazolinium methyl sulphate.
  • the invention uses a lipase in the rinsing stage of a conventional treatment process for soiled or unsoiled fabrics comprising washing, rinsing and drying.
  • the rinsing stage generally comprises 2-5 subsequent steps of rinsing with water, usually 3 or 4 steps.
  • the lipase is added together with a cationic surfactant (e.g. 0.1-0.5 g/l).
  • the lipase is preferably added in the second or a later rinsing step, and most preferably in the last rinsing step, where the detergent concentration is lowest (thus minimizing any incompatibility problems between detergent and lipase) and where it can conveniently be added together with the cationic surfactant, if such cationic surfactant is used in the process according to the invention.
  • Conventional rinsing conditions can be used, e.g. 10-30°C water, 1-20 minutes at near-neutral pH (e.g. 5-9) depending on the use of cationic surfactant.
  • the rinsing agent used in the process according to the invention is stabilized against microbial infection, preferably by incorporation of a stabilizing agent known in the art.
  • a stabilizing agent known in the art.
  • examples are inorganic salts (such as NaCI), sugars (such as sucrose and glucose), polyols (such as glycerol, propylene glycol and sorbitol) and alcohols (such as ethanol and iso-propanol). These are generally effective in amounts above 10%, especially above 20%.
  • organic acids such as benzoic, sorbic, propionic, lactic and formic
  • stabilizing agents are antioxidants (such as sulphur dioxide), 1,2-benz-iso-thiazolin-3-on (BIT) and parabens. Some of these may also serve to improve enzyme stability.
  • Further additives may be incorporated to improve enzyme stability or physical stability of the rinsing agent.
  • Examples are CaCl2 (e.g. 0.1-0.5%) or 0.5-5% of lower alcohol (such as ethanol or iso-propanol, preferably used together with a larger amount of a polyol).
  • the rinsing agent ordinarily is preferably essentially devoid of anionic and nonionic surfactant (total amount of these below 5%, most preferably below 2%).
  • the rinsing agent may be in solid (e.g. as non-dusting granules) or liquid form (e.g. aqueous). It may be formulated by incorporating lipase into known softening/antistatic compositions based on cationic surfactants.
  • the content of cationic surfactant is preferably 1-50%, especially 5-50% (% as active material).
  • the lipase used in the examples is from Humicola lanuginosa produced according to US 4,810,414 or from Pseudomonas cepacia produced according to WO 89/04361.
  • Example 2 The performance evaluation was carried out as described in Example 1, the only difference being that other kinds of cationics were used in combination with the Humicola lanuginosa lipase and that the lipase dosage was varied between 0 and 3000 LU per litre.
  • the cationics used were:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Detergent Compositions (AREA)
  • Liquid Crystal (AREA)
  • Liquid Crystal Display Device Control (AREA)
  • Control Of Indicators Other Than Cathode Ray Tubes (AREA)
  • Shift Register Type Memory (AREA)
  • Control Of El Displays (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

In the process for treatment of textiles by use of an enzyme the enzyme is used in a rinse liquor for a rinsing step after washing. The rinsing agent is an enzyme preparation stabilized against microbial infection. Use of the enzyme in the process provides a better enzymatic effect when used in the rinse liquor than when used as a constituent of the main wash composition.

Description

    TECHNICAL FIELD
  • The invention relates to a process for treatment of textiles by use of a lipase.
  • BACKGROUND ART
  • Treatment of soiled or unsoiled textiles normally comprises washing with a detergent containing anionic and/or nonionic surfactant, followed by rinsing and drying. It belongs to the prior art that lipase can be incorporated into the detergent to improve the removal of fat soiling (EP 130,064, EP 214,761, US 4,810,414). Also, it belongs to the prior art that a non-dusting granulate containing a cellulase can be added to a main wash detergent composition in order to reduce the harshness of the laundry (US 4,435,307), that proteases are useful in detergent compositions in order to remove proteinaceous stains (US 3,723,250), and that amylases are useful in detergent compositions in order to remove starchy stains (US 3,627,688 and 4,548,727).
  • However, a given enzyme may be incompatible with a given detergent composition due to unsatisfactory activity and stability of the enzyme, and this imposes some limitations in the choice of enzyme and detergent formulation. It is the object of the invention to provide an alternative method of using a lipase in textile treatment, so as to obtain efficient lipolytic effects for a given lipase dosage while avoiding the above limitations.
  • STATEMENT OF THE INVENTION
  • We have found that, surprisingly, use of a lipase provides a better lipolytic effect when used in the rinse liquor than when used as a constituent of the main wash composition. The effect is particularly pronounced after repeated cycles of washing, rinsing and drying. Detergent is essentially absent during rinsing, and thus compatibility problems are avoided. The lipase may advantageously be added in the last rinse step together with a cationic surfactant.
  • DE 2 148 278 describes the use of a cellulase preparation containing lipase as one of the secondary activities and a cationic surfactant. However, this prior publication does only indicate the presence of lipase as a theoretical possibility and does not indicate the use of any specific lipases.
  • Accordingly, the invention provides a process for treatment of textiles by use of a lipase, which is used in a rinse liquor for a rinsing step after washing, characterized by the fact that the lipase is producible by means of Humicola lanuginosa or Pseudomonase cepacia.
  • In a preferred embodiment of the process according to the invention the lipase is used in the rinse liquor for the rinsing step after washing, together with a fabric softening agent and/or an antistatic agent. Hereby a satisfactory effect has been demonstrated.
  • In a preferred embodiment of the process according to the invention the fabric softening agent and/or the antistatic agent is a cationic surfactant. A satisfactory enzymatic effect is observed in this embodiment. The cationic surfactant may be a dialkyl dimethyl ammonium chloride or an alkyl imidazoline methosulfate.
  • In a preferred embodiment of the process according to the invention the enzyme is used in the rinse liquor for a second or later rinsing step, preferably in the last rinsing step. In this manner an even better enzymatic effect is observed.
  • In a preferred embodiment of the process according to the invention the concentration of lipase in the rinse liquor is in the range of 0.001 to 5, preferably 0.01 to 2 mg pure lipase protein per liter of rinse liquor. At a concentration below 0.001 mg pure lipase protein per liter of rinse liquor no significant lipase effect can be observed, and at a concentration above 5 mg pure lipase protein per liter of rinse liquor the lipase cost will be unreasonably high.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The lipases which can be used in the invention are lipases producible by means of Humicola lanuginosa (US 4,810,414) and Pseudomonas cepacia (WO 89/04361).
  • The lipase activity unit, LU, is defined in AF 95/5, which is available on request from Novo Nordisk A/S, Novo allé, DK-2880 Bagsvaerd, Denmark, this publication being published before March 1, 1990.
  • Cationic surfactants
  • According to a preferred embodiment of the invention a cationic surfactant effective for fabric after-treatment is used together with the lipase in the process according to the invention. Such cationic surfactants are known in the art. One example is quaternary ammonium salts such as dialkyl (C₁₆-C₁₈) dimethyl ammonium chloride, alkyl (C₃₂-C₃₆) trimethyl ammonium chloride or alkyl (C₈-C₁₈) dimethyl benzyl ammonium chloride (ABDAC); and alkyl imidazolinium methyl sulphate.
  • Textile treatment process
  • The invention uses a lipase in the rinsing stage of a conventional treatment process for soiled or unsoiled fabrics comprising washing, rinsing and drying. The rinsing stage generally comprises 2-5 subsequent steps of rinsing with water, usually 3 or 4 steps. In a preferred embodiment the lipase is added together with a cationic surfactant (e.g. 0.1-0.5 g/l). The lipase is preferably added in the second or a later rinsing step, and most preferably in the last rinsing step, where the detergent concentration is lowest (thus minimizing any incompatibility problems between detergent and lipase) and where it can conveniently be added together with the cationic surfactant, if such cationic surfactant is used in the process according to the invention. Conventional rinsing conditions can be used, e.g. 10-30°C water, 1-20 minutes at near-neutral pH (e.g. 5-9) depending on the use of cationic surfactant.
  • Rinsing agent
  • The rinsing agent used in the process according to the invention is stabilized against microbial infection, preferably by incorporation of a stabilizing agent known in the art. Examples are inorganic salts (such as NaCI), sugars (such as sucrose and glucose), polyols (such as glycerol, propylene glycol and sorbitol) and alcohols (such as ethanol and iso-propanol). These are generally effective in amounts above 10%, especially above 20%. Another example is organic acids (such as benzoic, sorbic, propionic, lactic and formic), which are generally effective in amounts of 0.01-2% at low pH (below 5). Other examples of stabilizing agents are antioxidants (such as sulphur dioxide), 1,2-benz-iso-thiazolin-3-on (BIT) and parabens. Some of these may also serve to improve enzyme stability.
  • Further additives may be incorporated to improve enzyme stability or physical stability of the rinsing agent. Examples are CaCl₂ (e.g. 0.1-0.5%) or 0.5-5% of lower alcohol (such as ethanol or iso-propanol, preferably used together with a larger amount of a polyol).
  • The rinsing agent ordinarily is preferably essentially devoid of anionic and nonionic surfactant (total amount of these below 5%, most preferably below 2%).
  • The rinsing agent may be in solid (e.g. as non-dusting granules) or liquid form (e.g. aqueous). It may be formulated by incorporating lipase into known softening/antistatic compositions based on cationic surfactants. The content of cationic surfactant is preferably 1-50%, especially 5-50% (% as active material).
  • EXAMPLES
  • The lipase used in the examples is from Humicola lanuginosa produced according to US 4,810,414 or from Pseudomonas cepacia produced according to WO 89/04361.
  • EXAMPLE 1 Effect of different lipases under the rinse process
  • Washing and rinsing tests are made as follows:
  • Fabric:
    Polyester/cotton (50/50) or cotton.
    Swatch size: 9x9 cm.
    Soiling:
    Lard/Sudan red (1000/0.75 w/w) is heated to 70°C, and 50 µl is spotted onto each swatch by a pipette. After application of stain, the swatches are heated in an oven for 30 minutes at 75°C.
    Washing:
    Terg-o-tometer (100 rpm).
    Commercial European detergent powder, 8 g/l in 18°dH water.
    pH not adjusted (approx. 10).
    30°C, 20 minutes.
    7 swatches per beaker containing 1 liter detergent solution.
    Rinsing:
    4-step rinse in Terg-o-tometer.
    1st-3rd rinse: 6 minutes in 1 l cold tap water.
    4th rinse: 10 minutes in 1 l tap water (22°C).
    Swatches squeezed by hand between each rinse.
    0 or 100 LU/I of lipase added in 4th rinse.
    0 or 0.20 g/l of Arquad 2HT-75 (dialkyl dimethyl ammonium chloride, 75% active matter, Akzo-Chemicals) added in 4th rinse.
    Drying:
    Line-drying (16 hours) at room temperature.
    Repeats:
    Washing, rinsing and drying of swatches repeated 3 times.
    Evaluation:
    After the 3rd wash.
    Reflectance is measured at 460 nm.
    Content of fatty matter is determined by Soxhlet extraction with chloroform for 5 hours.
  • It appears from the following tables that addition of lipase during the last rinse improves the removal of fatty matter, in relation to both lipases, both with and without cationic.
    Figure imgb0001
  • Effect of Humicola lanuginosa and of Pseudomonas cepacia lipase on lard/cotton swatches. The lipases were added initally under the 4th rinse step; no lipase was present during the washing process.
    Figure imgb0002
  • Effect of Humicola lanuginosa and of Pseudomonas cepacia lipase on lard/polyester-cotton swatches. The lipases were added initially under the 4th rinse step; no lipase was present during the washing process.
  • EXAMPLE 2 Lipase performance when used in combination with different cationic surfactants
  • The performance evaluation was carried out as described in Example 1, the only difference being that other kinds of cationics were used in combination with the Humicola lanuginosa lipase and that the lipase dosage was varied between 0 and 3000 LU per litre.
  • The cationics used were:
    • 1) Dodigen 1490 from Hoechst (dialkyl dimethyl ammonium chloride, 75% active matter)
    • 2) Empigen FRC75/S from Albright & Wilson (alkyl imidazoline methosulfate, 75% active matter)
      Figure imgb0003
    EXAMPLE 3 Lipase performance - comparison with prior art
  • Performance evaluation was carried out as described in Example 1. In this example the use of Humicola lanuginosa lipase in the rinse liquor (this invention) was compared to the use of the same enzyme in the main wash liquor (prior art). Lipase dosage was 100 LU/I.
    Figure imgb0004
  • EXAMPLE 4 Lipase stability in rinse preparations (after treatment preparations)
  • Figure imgb0005
  • The above mentioned lipase containing rinse preparations were stored at room temperature (20-22°C) for 240 days and the lipase activity was followed. The following results expressed as % relative activity were obtained:
    Figure imgb0006

Claims (5)

  1. Process for treatment of textiles by use of a lipase, which is used in a rinse liquor for a rinsing step after washing, wherein the lipase is producible by means of Humicola lanuginosa or Pseudomonas cepacia.
  2. Process according to Claim 1, characterized by the fact that the lipase is used in the rinse liquor for the rinsing step after washing, together with a fabric softening agent and/or an antistatic agent.
  3. Process according to Claim 2, characterized by the fact that the fabric softening agent and/or the antistatic agent is a cationic surfactant.
  4. Process according to Claims 1 - 3, wherein the lipase is used in the rinse liquor for a second or later rinsing step, preferably the last rinsing step.
  5. Process according to Claims 1 - 4, wherein the concentration of lipase in the rinse liquor is in the range 0.001 to 5, preferably 0.01 to 2 mg pure enzyme protein per liter of rinse liquor.
EP91905036A 1990-03-01 1991-02-28 Process for treatment of textiles Expired - Lifetime EP0517762B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DK530/90 1990-03-01
DK53090A DK53090D0 (en) 1990-03-01 1990-03-01
DK1489/90 1990-06-19
DK148990A DK148990D0 (en) 1990-06-19 1990-06-19 PROCEDURE FOR THE TREATMENT OF TEXTILE MATERIALS AND RULE FOR USE IN THE PROCEDURE

Publications (2)

Publication Number Publication Date
EP0517762A1 EP0517762A1 (en) 1992-12-16
EP0517762B1 true EP0517762B1 (en) 1993-12-08

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Application Number Title Priority Date Filing Date
EP91905036A Expired - Lifetime EP0517762B1 (en) 1990-03-01 1991-02-28 Process for treatment of textiles

Country Status (7)

Country Link
EP (1) EP0517762B1 (en)
JP (1) JP2878454B2 (en)
AT (1) ATE98296T1 (en)
DE (1) DE69100751T2 (en)
DK (1) DK0517762T3 (en)
ES (1) ES2047400T3 (en)
WO (1) WO1991013136A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290474A (en) * 1990-10-05 1994-03-01 Genencor International, Inc. Detergent composition for treating cotton-containing fabrics containing a surfactant and a cellulase composition containing endolucanase III from trichoderma ssp
US5650322A (en) * 1990-10-05 1997-07-22 Genencor International, Inc. Methods for stonewashing fabrics using endoglucanases
CA2093422C (en) * 1990-10-05 2001-04-03 Detergent compositions containing cellulase compositions deficient in cbh i type components
DE69133035T2 (en) * 1991-01-16 2003-02-13 The Procter & Gamble Company, Cincinnati Compact detergent compositions with highly active cellulases
US6251144B1 (en) 1992-06-12 2001-06-26 Genencor International, Inc. Enzymatic compositions and methods for producing stonewashed look on indigo-dyed denim fabric and garments
US5616553A (en) * 1993-08-12 1997-04-01 The Procter & Gamble Company Fabric conditioning compositions
US5599786A (en) * 1993-08-12 1997-02-04 The Procter & Gamble Company Cellulase fabric-conditioning compositions
EP0724624B1 (en) * 1993-10-22 1998-06-24 Unilever Plc Fabric conditioner composition
ES2251717T3 (en) 1994-03-08 2006-05-01 Novozymes A/S NEW ALKALINE CELLS.
DE69513816D1 (en) * 1994-04-29 2000-01-13 Procter & Gamble TISSUE-SOFTENING COMPOSITIONS CONTAINING CELLULASE
US5445747A (en) * 1994-08-05 1995-08-29 The Procter & Gamble Company Cellulase fabric-conditioning compositions
JPH11501689A (en) * 1995-03-03 1999-02-09 ザ、プロクター、エンド、ギャンブル、カンパニー Laundry composition containing dye fixative and cellulase
US8533881B2 (en) 2009-12-15 2013-09-17 Whirpool Corporation Method for dispensing an enzyme in a laundry treating appliance
EP2987848A1 (en) * 2014-08-19 2016-02-24 The Procter & Gamble Company Method of laundering a fabric
IT201600094671A1 (en) 2016-09-21 2018-03-21 Bolton Manitoba S P A OPTIMIZED WASHING MACHINE METHOD

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1368599A (en) * 1970-09-29 1974-10-02 Unilever Ltd Softening compositions
DK163591C (en) * 1985-10-08 1992-08-24 Novo Nordisk As PROCEDURE FOR TREATING A TEXTILE SUBSTANCE WITH A CELLULASE
GB8626357D0 (en) * 1986-11-04 1986-12-03 Reading University Of Treatment of wool textiles

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Publication number Publication date
ES2047400T3 (en) 1994-02-16
DK0517762T3 (en) 1994-04-18
WO1991013136A1 (en) 1991-09-05
DE69100751T2 (en) 1994-03-24
DE69100751D1 (en) 1994-01-20
EP0517762A1 (en) 1992-12-16
JP2878454B2 (en) 1999-04-05
ATE98296T1 (en) 1993-12-15
JPH05504367A (en) 1993-07-08

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