EP0812907A1 - Laundry bleaching with improved safety to fabrics - Google Patents

Laundry bleaching with improved safety to fabrics Download PDF

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Publication number
EP0812907A1
EP0812907A1 EP96870074A EP96870074A EP0812907A1 EP 0812907 A1 EP0812907 A1 EP 0812907A1 EP 96870074 A EP96870074 A EP 96870074A EP 96870074 A EP96870074 A EP 96870074A EP 0812907 A1 EP0812907 A1 EP 0812907A1
Authority
EP
European Patent Office
Prior art keywords
fabrics
hydroperoxide
composition
bleaching
compositions
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.)
Withdrawn
Application number
EP96870074A
Other languages
German (de)
English (en)
French (fr)
Inventor
Valerio Del Duca
Stefano Scialla
Giulia Ottavia Bianchetti
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP96870074A priority Critical patent/EP0812907A1/en
Priority to CN97196849A priority patent/CN1226296A/zh
Priority to SK1690-98A priority patent/SK169098A3/sk
Priority to JP10501743A priority patent/JPH11513082A/ja
Priority to HU0003883A priority patent/HUP0003883A2/hu
Priority to PL97330474A priority patent/PL330474A1/xx
Priority to CA002258101A priority patent/CA2258101A1/en
Priority to PCT/US1997/009965 priority patent/WO1997047800A1/en
Priority to US09/202,247 priority patent/US6019797A/en
Priority to AU33833/97A priority patent/AU3383397A/en
Priority to BR9709775A priority patent/BR9709775A/pt
Priority to CZ984056A priority patent/CZ405698A3/cs
Publication of EP0812907A1 publication Critical patent/EP0812907A1/en
Withdrawn legal-status Critical Current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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • 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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

  • the present invention relates to the bleaching of fabrics.
  • Peroxygen bleach-containing compositions have been described in laundry applications as laundry detergents, laundry additives or even laundry pretreaters.
  • peroxygen bleach-containing compositions in laundry treatment applications to boost the removal of encrustated stains/soils which are otherwise particularly difficult to remove, such as grease, coffee, tea, grass, mud/clay-containing soils and the like.
  • peroxygen bleach-containing compositions may damage fabrics, resulting in loss of tensile strength, especially when used in pretreatment application, i.e. when applied directly (neat) onto the fabrics, and left to act onto said fabrics for prolonged periods of time before washing the fabrics.
  • US 5,284,597 discloses a composition for treating soft surfaces, essentially carpets, which comprise amongst other things tertiary alkyl hydroperoxide.
  • the compositions are said to be safer to colors.
  • BE 831.277 discloses the bleaching of textiles with the help of a mixtures of bleach activators, one of which being from the class of triazine hydroperoxides. Triazine hydroperoxides are said to be potentially damaging to the colors of fabrics. '277 does not discuss the problem of safety to fabrics.
  • US 3,753,915 discloses the bleaching of fabrics with a granular composition comprising salts of hydroperoxides. '915 does not discuss the problem of safety to fabrics.
  • the present invention encompasses the use of hydroperoxides for the bleaching of fabrics, for reducing the loss of tensile strength in said fabrics.
  • the present invention further encompasses processes of bleaching fabrics, starting from a liquid composition comprising a hydroperoxide.
  • the processes include the steps of contacting said fabrics with the liquid bleaching composition neat or diluted, and subsequently rinsing said fabrics.
  • the fabrics are "pretreated"
  • the composition is applied neat on the fabrics, and the fabrics are subsequently washed in a normal wash cycle.
  • the present invention encompasses the use of a hydroperoxide as a bleaching agent in a process of bleaching fabrics for reducing the loss of tensile strength in said fabrics.
  • the present invention is based on the finding that fabric damage resulting in tensile strength loss is reduced, when a composition comprising a hydroperoxide, or mixtures thereof, is used to bleach fabrics, as compared to the same composition where hydrogen peroxide is used instead of hydroperoxide.
  • the tensile strength in a fabric may be measured by stretching said fabric until it breaks.
  • the force needed to break the fabric is the "Ultimate Tensile Stress” and may be measured with a stress-strain INSTRON ® machine available from INSTRON.
  • the loss of tensile strength is the difference between the tensile strength of a fabric taken as a reference, i.e. a fabric which has not been bleached, and the tensile strength of the same fabric after having been bleached. A tensile strength loss of zero means that no fabric damage is observed.
  • the liquid compositions suitable to be used according to the present invention comprise a hydroperoxide, or mixtures thereof, as the bleaching agent.
  • Suitable hydroperoxides for use herein include alkyl hydroperoxides and organomineral hydroperoxides.
  • Suitable alkyl hydroperoxides for use herein are according to the formula in which each R1, R2 and R3 is, independently, a hydrogen atom or a hydrocarbon radical having from 1 to 30 carbon atoms.
  • the hydrocarbon radical can be a linear or a cyclic hydrocarbon chain, and the linear and the cyclic hydrocarbon chain can be straight or branched, saturated or unsaturated.
  • two of the R groups can be part of the same cyclic hydrocarbon.
  • One or more R groups in the above formula can be a single or condensed aromatic radical, alkyl-aryl radical or cycloalkyl-aryl radical.
  • R radicals can also be substituted by heteroatoms or group of heteroatoms, such as hydroperoxide (-OOH) groups, halogen atoms, hydroxy groups, nitrates, suphonyls, nitro groups, ethers, carboxylic groups and esters. All these groups can also be present as substituents of one or more positions of the R radicals.
  • heteroatoms or group of heteroatoms such as hydroperoxide (-OOH) groups, halogen atoms, hydroxy groups, nitrates, suphonyls, nitro groups, ethers, carboxylic groups and esters. All these groups can also be present as substituents of one or more positions of the R radicals.
  • Preferred alkyl hydroperoxides for use herein are tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide, di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydroperoxide.
  • Suitable organomineral hydroperoxides for use herein are according to the formula R m M(OOH) n where M is a metal atom like Si, Sn, Ge or Sb and R is a radical defined as R1, R2, R3 above.
  • Preferred organomineral hydroperoxides for use herein are (CH 3 ) 3 SiOOH, (C 6 H 5 ) 2 CH 3 SiOOH, (C 6 H 5 ) 3 SiOOH, (n-C 6 H 13 ) 3 SiOOH, (CH 3 ) 3 SnOOH, (C 6 H 5 ) 3 Sb(OOH) 2 .
  • Most preferred for use herein are (CH 3 ) 3 SiOOH, (C 6 H 5 ) 3 SiOOH.
  • compositions herein comprise from 0.01% to 5.0%, preferably 0.015% to 4.0%, most preferably from 0.02% to 2.0% of available oxygen provided by said hydroperoxide.
  • compositions to be used according to the present invention must be liquids.
  • liquid includes “pasty” compositions, and liquid compositions herein preferably have a viscosity of from 5 cps to 10000 cps at 50 rpm shear rate and at 20°c temperature.
  • the compositions to be used herein are aqueous.
  • Said aqueous compositions have a pH as is of from 2 to 11, preferably from 3 to 10 and more preferably from 3.5 to 9.5 when optimum chemical stability for the hydroperoxides has been observed.
  • the pH of the compositions can be adjusted for instance by using organic or inorganic acids, or alkalinizing agents.
  • compositions used in the present invention may further comprise any surfactant including nonionic, anionic, cationic, zwitterionic and/or amphothereic surfactants.
  • compositions used in the present invention preferably further comprise a nonionic surfactant, or mixtures thereof.
  • the compositions used in the present invention comprise from 0.1% to 50% by weight of the total composition of said nonionic surfactant, or mixtures thereof, preferably from 0.3 % to 30 % and more preferably from 0.4 % to 25 %.
  • Suitable nonionic surfactants to be used herein are fatty alcohol ethoxylates and/or propoxylates which are commercially available with a variety of fatty alcohol chain lengths and a variety of ethoxylation degrees. Indeed, the HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Surfactant catalogues are available which list a number of surfactants, including nonionics, together with their respective HLB values.
  • Suitable chemical processes for preparing the nonionic surfactants for use herein include condensation of corresponding alcohols with alkylene oxide, in the desired proportions. Such processes are well known to the man skilled in the art and have been extensively described in the art. As an alternative, a great variety of alkoxylated alcohols suitable for use herein is commercially available from various suppliers.
  • nonionic surfactants Particularly suitable to be used herein as nonionic surfactants are hydrophobic nonionic surfactants having an HLB (hydrophilic-lipophilic balance) below 16, preferably below 15, more preferably below 12, and most preferably below 10. Those hydrophobic nonionic surfactants have been found to provide good grease cutting properties.
  • HLB hydrophilic-lipophilic balance
  • Preferred hydrophobic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB below 16 and being according to the formula RO-(C 2 H 4 O) n (C 3 H 6 O) m H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 alkyl benzene chain, and wherein n+m is from 0 to 20 and n is from 0 to 15 and m is from 0 to 20, preferably n+m is from 1 to 15 and, n and m are from 0.5 to 15, more preferably n+m is from 1 to 10 and, n and m are from 0 to 10.
  • the preferred R chains for use herein are the C 8 to C 22 alkyl chains.
  • Dobanol R 91-2.5 or Lutensol R TO3, or Lutensol R AO3, or Tergitol R 25L3, or Dobanol R 23-3, or Dobanol R 23-2, or mixtures thereof.
  • Dobanol R surfactants are commercially available from SHELL.
  • Lutensol R surfactants are commercially available from BASF and these Tergitol R surfactants are commercially available from UNION CARBIDE.
  • compositions to be used herein further comprise an anionic surfactant, or mixtures thereof.
  • Said anionic surfactants act as wetting agent, i.e. in laundry application they wet the stains on the fabrics, especially on hydrophilic fabrics, and thus help the hydroperoxide perform its bleaching action thereby contributing to improved laundry performance on bleachable stains.
  • anionic surfactants allow to obtain clear compositions even when said compositions comprise hydrophobic ingredients such as hydrophobic surfactants.
  • the compositions to be used herein comprise from 0.1 % to 20 % by weight of the total composition of said anionic surfactant, or mixtures thereof, preferably from 0.2 % to 15 % and more preferably from 0.5 % to 13 %.
  • anionic surfactants are well-known in the art and have found wide application in commercial detergents. These anionic surfactants include the C8-C22 alkyl benzene sulfonates (LAS), the C8-C22 alkyl sulfates (AS), unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates (AES) and the C10-C18 alkyl alkoxy carboxylates.
  • LAS C8-C22 alkyl benzene sulfonates
  • AS C8-C22 alkyl sulfates
  • unsaturated sulfates such as oleyl sulfate
  • C10-C18 alkyl alkoxy sulfates AES
  • the neutralising cation for the anionic synthetic sulfonates and/or sulfates is represented by conventional cations which are widely used in detergent technology such as sodium, potassium or alkanolammonium.
  • Preferred herein are the alkyl sulphate, especially coconut alkyl sulphate having from 6 to 18 carbon atoms in the alkyl chain, preferably from 8 to 15, or mixtures thereof.
  • compositions for use herein may further comprise a foam suppressor such as 2-alkyl alkanol, or mixtures thereof, as a highly preferred optional ingredient.
  • a foam suppressor such as 2-alkyl alkanol, or mixtures thereof, as a highly preferred optional ingredient.
  • Particularly suitable to be used in the present invention are the 2-alkyl alkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 and a terminal hydroxy group, said alkyl chain being substituted in the ⁇ position by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and more preferably 3 to 6.
  • compositions suitable to be used herein comprise from 0.05 % to 2 % by weight of the total composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.1 % to 1.5 % and most preferably from 0.1 % to 0.8 %.
  • compositions herein may further comprise a variety of other optional ingredients such as builders, stabilisers, chelants, soil suspenders, dye transfer agents, radical scavengers, solvents, brighteners, perfumes, and dyes.
  • the liquid bleaching composition comprising the hydroperoxide needs to be contacted with the fabrics to be bleached.
  • This can be done either in a so-called “pretreatment mode", where the composition is applied neat onto said fabrics before the fabrics are rinsed, or washed then rinsed, or in a "soaking mode” where the liquid composition is first diluted in an aqueous bath and the fabrics are immersed and soaked in the bath, before they are rinsed, or in a "through the wash mode", where the liquid composition is added on top of a wash liquor formed by dissolution or dispersion of a typical laundry detergent.
  • the composition to perform the processes herein is in the form of a liquid as opposed to a solid or a gas.
  • the process comprises the steps of applying said liquid composition in its neat form onto said fabrics, or at least soiled portions thereof, and subsequently rinsing, or washing then rinsing said fabrics.
  • the neat compositions can optionally be left to act onto said fabrics for a period of time ranging from 1 min. to 1 hour, before the fabrics are rinsed, or washed then rinsed, provided that the composition is not left to dry onto said fabrics.
  • stains it may be appropriate to further rub or brush said fabrics by means of a sponge or a brush, or by rubbing two pieces of fabrics against each other.
  • the process comprises the steps of diluting said liquid composition in its neat form in an aqueous bath so as to form a diluted composition, i.e., a composition comprising from 0.0001% to 0.2%, preferably 0.0002% to 0.02% of available oxygen provided by said hydroperoxide.
  • a diluted composition i.e., a composition comprising from 0.0001% to 0.2%, preferably 0.0002% to 0.02% of available oxygen provided by said hydroperoxide.
  • the fabrics are then contacted with the aqueous bath comprising the liquid composition, and the fabrics are finally rinsed, or washed then rinsed.
  • the fabrics are immersed in the aqueous bath comprising the liquid composition, and also preferably, the fabrics are left to soak therein for a period of time ranging from 30 minutes to 48 hours, preferably from 1 hour to 24 hours.
  • the liquid composition is used as a so-called laundry additive.
  • the aqueous bath is formed by dissolving or dispersing a conventional laundry detergent in water.
  • the liquid composition in its neat form is contacted with the aqueous bath, and the fabrics are then contacted with the aqueous bath containing the liquid composition. Finally, the fabrics are rinsed.
  • compositions herein can be packaged in a variety of containers including conventional bottles, bottles equipped with roll-on, sponge, brusher or sprayers, or sprayers.
  • this composition is applied neat on the stained portion of a fabric and left to act thereon for 5 minutes. Then the fabric is washed with a conventional detergent and rinsed.
  • this composition is contacted with an aqueous bath formed by dissolution of a conventional detergent in water. Fabrics are then contacted with the aqueous bath comprising the liquid detergent, and the fabrics are rinsed.
  • This composition can also be used in a pretreatment mode, where it is poured neat on the stains on the fabrics, and left to act for 5 minutes, and the fabrics are washed.
  • This composition can be used in a pretreatment mode, or in a bleaching-through-the-wash mode, as described in examples 1 and 2. It can also be used in a soaking mode, where 100 ml of the liquid compositions are diluted in 10 liters of water. The fabrics are then contacted with this aqueous bath containing the composition, and left to soak therein for a period of time of 24 hours. The fabrics are eventually rinsed.
  • This composition is used in a pretreatment mode, as described in the examples above.
  • This composition is used in a pretreatment mode as described in the previous examples.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
EP96870074A 1996-06-10 1996-06-10 Laundry bleaching with improved safety to fabrics Withdrawn EP0812907A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP96870074A EP0812907A1 (en) 1996-06-10 1996-06-10 Laundry bleaching with improved safety to fabrics
CN97196849A CN1226296A (zh) 1996-06-10 1997-06-06 具有改善的织物安全性的洗衣漂白
SK1690-98A SK169098A3 (en) 1996-06-10 1997-06-06 Laundry bleaching with improved safety to fabrics
JP10501743A JPH11513082A (ja) 1996-06-10 1997-06-06 布地に対する安全性が改良された洗濯漂白
HU0003883A HUP0003883A2 (hu) 1996-06-10 1997-06-06 Textíliákat jobban kímélő, mosodai, fehérítő eljárás
PL97330474A PL330474A1 (en) 1996-06-10 1997-06-06 Method of brightening washed laundry with increased protection of fabrics
CA002258101A CA2258101A1 (en) 1996-06-10 1997-06-06 Laundry bleaching with improved safety to fabrics
PCT/US1997/009965 WO1997047800A1 (en) 1996-06-10 1997-06-06 Laundry bleaching with improved safety to fabrics
US09/202,247 US6019797A (en) 1996-06-10 1997-06-06 Laundry bleaching with improved safety to fabrics
AU33833/97A AU3383397A (en) 1996-06-10 1997-06-06 Laundry bleaching with improved safety to fabrics
BR9709775A BR9709775A (pt) 1996-06-10 1997-06-06 Branqueamento para lavanderia com aperfeiçoada segurança para os tecidos
CZ984056A CZ405698A3 (cs) 1996-06-10 1997-06-06 Použití hydroperoxidu a způsob bělení a zpracovávání tkanin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96870074A EP0812907A1 (en) 1996-06-10 1996-06-10 Laundry bleaching with improved safety to fabrics

Publications (1)

Publication Number Publication Date
EP0812907A1 true EP0812907A1 (en) 1997-12-17

Family

ID=8226150

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96870074A Withdrawn EP0812907A1 (en) 1996-06-10 1996-06-10 Laundry bleaching with improved safety to fabrics

Country Status (11)

Country Link
EP (1) EP0812907A1 (zh)
JP (1) JPH11513082A (zh)
CN (1) CN1226296A (zh)
AU (1) AU3383397A (zh)
BR (1) BR9709775A (zh)
CA (1) CA2258101A1 (zh)
CZ (1) CZ405698A3 (zh)
HU (1) HUP0003883A2 (zh)
PL (1) PL330474A1 (zh)
SK (1) SK169098A3 (zh)
WO (1) WO1997047800A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6019797A (en) * 1996-06-10 2000-02-01 Procter & Gamble Company Laundry bleaching with improved safety to fabrics
US6242408B1 (en) 1998-11-25 2001-06-05 Dow Corning Corporation Stable bleaching agents containing bis(organosilyl)peroxides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB680623A (en) * 1948-08-12 1952-10-08 American Cyanamid Co Improvements in or relating to the treatment of wool and wool-containing textile materials
US2757207A (en) * 1951-03-20 1956-07-31 Hercules Powder Co Ltd alpha, alpha-dimethylnaphthylmethyl hydroperoxides
US3746646A (en) * 1970-04-22 1973-07-17 Colgate Palmolive Co Detergent washing composition
WO1992017634A1 (en) * 1991-03-28 1992-10-15 Interface, Inc. Method for removing stains from carpet and textiles

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9012001D0 (en) * 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
CA2085642A1 (en) * 1991-12-20 1993-06-21 Ronald Hage Bleach activation
US5284597A (en) * 1992-12-23 1994-02-08 S. C. Johnson & Son, Inc. Aqueous alkaline soft-surface cleaning compositions comprising tertiary alkyl hydroperoxides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB680623A (en) * 1948-08-12 1952-10-08 American Cyanamid Co Improvements in or relating to the treatment of wool and wool-containing textile materials
US2757207A (en) * 1951-03-20 1956-07-31 Hercules Powder Co Ltd alpha, alpha-dimethylnaphthylmethyl hydroperoxides
US3746646A (en) * 1970-04-22 1973-07-17 Colgate Palmolive Co Detergent washing composition
WO1992017634A1 (en) * 1991-03-28 1992-10-15 Interface, Inc. Method for removing stains from carpet and textiles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6019797A (en) * 1996-06-10 2000-02-01 Procter & Gamble Company Laundry bleaching with improved safety to fabrics
US6242408B1 (en) 1998-11-25 2001-06-05 Dow Corning Corporation Stable bleaching agents containing bis(organosilyl)peroxides
US6399559B1 (en) 1998-11-25 2002-06-04 Dow Corning Corporation Stable bleaching agents containing bis(organosilyl) peroxides

Also Published As

Publication number Publication date
AU3383397A (en) 1998-01-07
BR9709775A (pt) 1999-08-10
CZ405698A3 (cs) 1999-07-14
HUP0003883A2 (hu) 2001-04-28
PL330474A1 (en) 1999-05-24
JPH11513082A (ja) 1999-11-09
CA2258101A1 (en) 1997-12-18
SK169098A3 (en) 1999-07-12
CN1226296A (zh) 1999-08-18
WO1997047800A1 (en) 1997-12-18

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