[go: up one dir, main page]

WO1997039097A1 - Granules de blanchiment a base d'acide amido- et imidoperoxycarboxylique - Google Patents

Granules de blanchiment a base d'acide amido- et imidoperoxycarboxylique Download PDF

Info

Publication number
WO1997039097A1
WO1997039097A1 PCT/EP1997/001459 EP9701459W WO9739097A1 WO 1997039097 A1 WO1997039097 A1 WO 1997039097A1 EP 9701459 W EP9701459 W EP 9701459W WO 9739097 A1 WO9739097 A1 WO 9739097A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
surfactant
group
bleach
peroxycarboxylic acid
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.)
Ceased
Application number
PCT/EP1997/001459
Other languages
English (en)
Inventor
Philip Alan Block
Samuel Qcheng Lin
Robert Madeira Andrews
Scott David Manske
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.)
Unilever NV
Original Assignee
Unilever NV
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 US08/699,314 external-priority patent/US5770551A/en
Application filed by Unilever NV filed Critical Unilever NV
Priority to AU22903/97A priority Critical patent/AU2290397A/en
Publication of WO1997039097A1 publication Critical patent/WO1997039097A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the invention concerns bleach granules, compositions and a method for cleaning colored fabrics without causing localized dye damage.
  • Peroxyacid granulation has been the subject of much research.
  • the literature has described a variety of ways to improve chemical stability, prolong storage life and enhance releasability.
  • US Patent 5,049,298 inhibits peroxyacid decomposition through co-granulation with a hydratable inorganic material.
  • Diperoxydodecanedioic acid (“DPDA”) and N,N- phthaloylaminoperoxycaproic acid (“PAP”) are typical of the peroxyacids.
  • DPDA diperoxydodecanedioic acid
  • PAP N,N- phthaloylaminoperoxycaproic acid
  • Binders such as lauric acid or sodium dodecylbenzene sulphonate (“LAS”) are added to enhance cohesiveness.
  • US Patent 4,909,953 stabilizes amidoperoxyacids, especially the monononylamide of peroxysuccinic acid (“NAPSA”) and the monononylamide of peroxyadipic acid (“NAPAA”) by contact with a phosphate buffer solution.
  • a related disclosure is US Patent 5,055,218 which describes bleach granules of NAPAA and linear alkyl benzene sulfonate paste.
  • US Patent 4,126,573 reports avoidance of fabric dye damage by forming granules having a peroxyacid particle as an inner core surrounded by an outer coating of a surfactant compound.
  • the process involves dissolving a surfactant such as LAS in water followed by dispersing finely divided DPDA and subsequent drying of the mixture.
  • a surfactant such as LAS
  • DPDA finely divided DPDA
  • This technology area is crowded for reasons that small process or formulation changes can have significant impact upon the resultant bleach particles.
  • Most of the related art has focused upon stabilizing peroxy acid against decomposition. Relatively little attention has been given to the equally serious problem of localized dye damage.
  • Amido- and imidoperoxy acids are generally more storage stable than their equivalent non-nitrogen containing analogues. However they do suffer from the localized dye damage problem. The problem occurs during hand or machine washing when high concentrations of dissolved peracid come into contact with fabric surfaces prior to agitation. Previous attempts to control the problem through particle size and co-granulated/binder systems have generally been unsuccess ul .
  • a bleach granule including from 20 to 100% by weight of an intimate mixture of :
  • a surfactant (ii) a surfactant, the peroxycarboxylic acid and surfactant being present in a weight ratio from 20:0 to 1:20.
  • a bleach composition including:
  • a bleach granule including from 20 to 100% by weight of an intimate mixture of : (i) an amido or imido C 4 -C 30 peroxycarboxylic acid and (ii) a surfactant, the peroxycarboxylic acid an surfactant being present in a weight ratio from 20:1 to 1:20; and
  • a method for bleaching a stained substrate including contacting the stained substrate in an aqueous medium with a bleach granule formed from 60 to 100% by weight of an intimate mixture of an amido or imido C 4 -C 30 peroxycarboxylic acid and a surfactant, the peroxycarboxylic acid and surfactant being dosed into a weight ratio from 20:1 to 1:20, the bleach granule being dosed into the aqueous medium to provide peroxycarboxylic acid at a level from 0.05 to 100 ppm active oxygen.
  • a method for preparing a bleach granule is also provided involving the steps of :
  • the process is best performed either in the absence or with relatively small amounts of water. These amounts will usually be less than the combined amounts of peroxycarboxylic acid and surfactant, most especially amounts less than 15% by weight .
  • Peroxyacids of the present invention may be selected from mono- or di- percarboxylic amido or imido acids.
  • the mono- percarboxylic acids are of the general formula:
  • R is selected from the group consisting of C ⁇ -C ⁇ alkyl, C ⁇ -C ⁇ cycloalkyl and C 6 -C 12 aryl radicals;
  • R 1 is selected from the group consisting of hydrogen, C ⁇ -C 16 alkyl, C ⁇ C ⁇ cycloalkyl and C 6 -C 12 aryl radicals
  • R 2 is selected from the group consisting of hydrogen, C 1 -C 16 alkyl, C x -C 16 cycloalkyl and C 6 -C 12 aryl radicals and a carbonyl radical that can form a ring together with R;
  • R 3 is selected from the group consisting of C x -C 16 alkylene
  • M is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, ammonium and alkanolammonium cations and radicals.
  • the di-percarboxylic acids of the present invention may be of the general formula:
  • R 4 is selected from the group consisting of C 1 -C 12 alkylene ,
  • R 5 is selected from the group consisting of hydrogen, C ⁇ C ⁇ alkyl and C 6 -C 12 aryl radicals and a carbonyl radical that can form a ring together with R 3 ;
  • R 6 is selected from the group consisting of hydrogen, C x -C 16 alkyl and C 6 -C 12 aryl radicals and a radical that can form a
  • R 3 is selected from the group consisting of C ⁇ -C ⁇ alkylene ,
  • n 1 and n" each are an integer chosen such that the sum thereof is 1
  • m and m' each are an integer chosen such that the sum thereof is 1;
  • M is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, ammonium and alkanolammonium cations and radicals.
  • the most preferred peroxyacids are N,N- phthaloylaminoperoxycaproic acid (PAP) ; monononylamide of either peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA) ; and N,N' -terephthaloyl-di (6-aminoperoxycaproic acid) (TPCAP) .
  • Amounts of the amido or imido peroxycarboxylic acid in the granule may range from 25 to 95%, preferably from 40 to 80% by weight .
  • Intimately mixed with the amido or imido peroxyacids will be a surfactant to ensure against dye damage to colors on the cloth subjected to bleaching.
  • the surfactant may be naturally derived, such as soap or certain synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
  • the total level of the surfactant in the granule may range up to 90% by weight, preferably being from 1% to 50%, most preferably from 8 to 20%.
  • the synthetic anionic surfactants will be water- soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
  • the preferred anionic surfactants are sodium (C 1:l -C 15 ) alkylbenzene sulphonates and sodium (C 16 -C 18 ) alkyl sulfates.
  • the acid form of sulfuric and sulfonic surfactants have proved effective.
  • Illustrative is the linear secondary alkyl C 10 -C 15 benzene sulfonic acid, found more effective than its sodium salt form.
  • nonionic surfactants are the alkyl polyglucosides, fatty acid sugar amides (e.g. methyl glucamides) and C 18 -C 8 alkyl di-C ⁇ C-, alkyl tertiary amine oxides or C 18 -C 12 fatty amidopropyl di-C ⁇ C ? alkyl tertiary amine oxides, the amine oxides being preferred.
  • the ratio of peroxycarboxylic acid to surfactant will usually range from 20:1 to 1:20, preferably from 10:1 to 1:1, optimally from 2:1 to 7:1 by weight.
  • Bleach granulations of this invention may optionally contain at least one granulate adjunct such as a stabilizer, exotherm control agent or binder.
  • the stabilizers may be phosphate or phosphonate chelants (e.g. Dequest ® ) and ethylenediaminetetraacetic acid. Amounts of these materials may range from 0.1 to 20% by weight of the granule. Exotherm control agents may be included to prevent autodecomposition of the peroxyacid. Amounts of the exotherm control agent may range from 1 to 80% by weight. Suitable examples of such agents are boric acid, citric acid and hydrated inorganic salts (e.g. magnesium sulfate) . In certain instances it is advantageous not to include hydrated inorganic salts such as sodium sulfate, at least in amounts limited to below 10% by weight.
  • hydrated inorganic salts such as sodium sulfate
  • Binders for the granule may be fatty acids (e.g. lauric acid) , polyacrylates and mixtures of these. Amounts of binder may range from 0.1 to 10% by weight.
  • Bleach compositions of the present invention which incorporate the bleach granules will also include a builder.
  • Builders may be selected from calcium sequestrant materials, precipitating materials, calcium ion-exchange materials and mixtures thereof. Illustrative are sodium or potassium tripolyphophosphate, sodium carbonate, sodium citrate, tartrate mono- and di- succinates, oxydisuccinate, crystalline or amorphous alumino silicates (i.e. zeolites) and mixtures thereof.
  • Amounts of the builder may range from 1 to 80% by weight, preferably from 10 to 60%. Fabrics and other stained substrates may be cleaned by dispersal of the bleach granule in an aqueous medium.
  • the bleach granule should be dosed at levels to achieve peroxycarboxylic acid concentrations that range from 0.05 to 100 ppm, preferably from 2 to 50 ppm in the medium.
  • the amount of builder may range from about 0.1 to 3.0 grams per liter of aqueous medium.
  • a series of granules according to the present invention were prepared by mixing the peroxycarboxylic acid bleach known as PAP with dimethyl C 16 alkyl amine oxide.
  • PAP peroxycarboxylic acid bleach
  • dimethyl C 16 alkyl amine oxide was formulated at 50% while the level of amine oxide to PAP was varied in weight ratio.
  • the granules further included approximately 1% binder (secondary alkane sulfonate and polyacrylic acid) with the remainder of the composition being citric acid.
  • a mixture of the bleach granule and a commercial detergent powder were placed at the center of a sulfur dye test cloth of either black or prune color.
  • a piece of cotton ballast was rolled into a tube and placed on top of the bleach granules. The sides of the test cloth were then raised so that the granules sat within a valley of the test cloth, with the ballast cloth tube entrapping the granules.
  • This bundle was then placed in the bottom of a terg-o-tometer pot, with the remaining pieces of ballast cloths placed on top. Water was slowly added to the pot. A soak period of 30 minutes at 25°C was followed by 2 minutes of agitation (100 rpm) . The target active oxygen level was 5 ppm.
  • the test cloths were then rinsed and air dried. This test was meant to simulate entrapment of the bleach granule/detergent at the bottom of a hand wash bowl or in a washing machine. Wash conditions and materials are as outlined below.
  • the reflectance of the dye damage monitor cloths was measured using the Colorgard System /05 (manufacturer: BYK Gardner), set to the CIE Lab scale; where is a measure of the
  • subscript f represents the fabric after application of the PAP containing detergent
  • subscript i represents the untreated fabric

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

On décrit un granule de blanchiment dont 20 à 100 % représentent un mélange intime d'un acide amido- ou imidoperoxy C2-C30, et d'un tensioactif, dans un rapport pondéral compris entre 20:1 et 1:20. Les peroxyacides que l'on préfère sont l'acide N,N-phtaloylaminoperoxycaproïque (PAP), le monononylamide, soit de l'acide peroxysuccinique (NAPSA), soit de l'acide peroxyadipique (NAPAA), et l'acide N,N'-térephtaloyl-di(6-aminoperoxycaproïque) (TPCAP). La présence du tensioactif empêche l'agent de blanchiment qu'est le peroxyacide d'abîmer localement les couleurs. On décrit également des compositions de blanchiment ainsi qu'un procédé de nettoyage d'un substrat taché, à l'aide de ce granule de blanchiment.
PCT/EP1997/001459 1996-04-12 1997-03-20 Granules de blanchiment a base d'acide amido- et imidoperoxycarboxylique Ceased WO1997039097A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU22903/97A AU2290397A (en) 1996-04-12 1997-03-20 Amido- and imido- peroxycarboxylic acid bleach granules

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US1532396P 1996-04-12 1996-04-12
US60/015,323 1996-04-12
US08/699,314 US5770551A (en) 1996-08-19 1996-08-19 Amido- and imido- peroxycarboxylic acid bleach granules
US08/699,314 1996-08-19

Publications (1)

Publication Number Publication Date
WO1997039097A1 true WO1997039097A1 (fr) 1997-10-23

Family

ID=26687237

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/001459 Ceased WO1997039097A1 (fr) 1996-04-12 1997-03-20 Granules de blanchiment a base d'acide amido- et imidoperoxycarboxylique

Country Status (2)

Country Link
AU (1) AU2290397A (fr)
WO (1) WO1997039097A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999061572A1 (fr) * 1998-05-29 1999-12-02 Unilever Plc Procede et produit de traitement pour tisses
EP1760141A1 (fr) * 2005-09-06 2007-03-07 SOLVAY (Société Anonyme) Peroxycarboxylique acide granulé enveloppé, procédé de préparation et utilisation dans la blanchissage, le blanchiment et la désinfection
US7531498B2 (en) 2003-06-13 2009-05-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Peroxycarboxylic acid-based bleach compositions having a long shelf life

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5049298A (en) * 1988-11-25 1991-09-17 Akzo Nv Process for the preparation of bleaching granules
US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid
EP0450587A2 (fr) * 1990-04-06 1991-10-09 Hoechst Aktiengesellschaft Granulés stables de peracides carboxyliques
US5098598A (en) * 1988-12-24 1992-03-24 Interox Chemicals Limited Percarboxylic acids
WO1992011238A2 (fr) * 1990-12-22 1992-07-09 Solvay Interox Limited Acides peroxycarboxyliques
WO1995003276A1 (fr) * 1993-07-26 1995-02-02 Unilever N.V. Acides amidoperoxycarboxyliques utilises pour le blanchiment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5049298A (en) * 1988-11-25 1991-09-17 Akzo Nv Process for the preparation of bleaching granules
US5098598A (en) * 1988-12-24 1992-03-24 Interox Chemicals Limited Percarboxylic acids
EP0450587A2 (fr) * 1990-04-06 1991-10-09 Hoechst Aktiengesellschaft Granulés stables de peracides carboxyliques
US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid
WO1991016411A1 (fr) * 1990-04-13 1991-10-31 The Procter & Gamble Company Granules decolorants contenant un amidoperoxyacide
WO1992011238A2 (fr) * 1990-12-22 1992-07-09 Solvay Interox Limited Acides peroxycarboxyliques
WO1995003276A1 (fr) * 1993-07-26 1995-02-02 Unilever N.V. Acides amidoperoxycarboxyliques utilises pour le blanchiment

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999061572A1 (fr) * 1998-05-29 1999-12-02 Unilever Plc Procede et produit de traitement pour tisses
US7531498B2 (en) 2003-06-13 2009-05-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Peroxycarboxylic acid-based bleach compositions having a long shelf life
EP1760141A1 (fr) * 2005-09-06 2007-03-07 SOLVAY (Société Anonyme) Peroxycarboxylique acide granulé enveloppé, procédé de préparation et utilisation dans la blanchissage, le blanchiment et la désinfection
WO2007028806A1 (fr) * 2005-09-06 2007-03-15 Solvay (Societe Anonyme) Granules d’acide peroxycarboxylique enduits, leur procede de fabrication, et leur utilisation dans des applications pour des detergents, des agents de blanchiment ou des desinfectants

Also Published As

Publication number Publication date
AU2290397A (en) 1997-11-07

Similar Documents

Publication Publication Date Title
KR930009821B1 (ko) 4급 암모늄 또는 포스포늄 페록시탄산의 전구물질 및 이를 함유하는 세제표백조성물
KR940010120B1 (ko) 표백화합물 및 조성물
US4756845A (en) Bleaching compositions
JPH0678556B2 (ja) 漂白活性化及び漂白組成物
US4199466A (en) Activated bleaching process and compositions therefor
US4225451A (en) Bleaching composition
CZ101595A3 (en) Granular detergents with protease and bleaching activity
GB1569258A (en) Bleaching compositions and processes
US5413733A (en) Amidooxy peroxycarboxylic acids and sulfonimine complex catalysts
US6007583A (en) Use of aminonitrile N-oxides as bleach activators
SE459500B (sv) Partikelformig tvaettmedelskomposition vilken innehaaller en peroxisyrafoerening som blekmedel och en hydroxikarboxylpolymer som blekmedelsstabilisator och kompositionens anvaendning vid blekning
US5770551A (en) Amido- and imido- peroxycarboxylic acid bleach granules
US8975219B2 (en) Fabric cleaning composition comprising hueing agent
US3756776A (en) Bleaching process and composition
BR0112852B1 (pt) composição detergente particulada para lavagem de roupa, e, composição particulada colorida para uso como uma composição para salpicos coloridos em uma composição detergente particulada para lavagem de roupa.
WO1997039097A1 (fr) Granules de blanchiment a base d'acide amido- et imidoperoxycarboxylique
JP3425227B2 (ja) 液体漂白剤組成物
US5672295A (en) Amido peroxycarboxylic acids for bleaching
JP2523817B2 (ja) 漂白剤及び漂白洗浄剤組成物
KR960007394B1 (ko) 표백제 함유세제 조성물
JPS62195100A (ja) 漂白性組成物
DE1961076A1 (de) Aktivatorkombination fuer Perverbindungen sowie fuer diese enthaltende Bleich-,Wasch- und Reinigungsmittel
KR100350924B1 (ko) 표백안정성을개선한표백제함유세제조성물
JPH0267399A (ja) 漂白洗剤組成物
JPH01245099A (ja) 漂白剤組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN YU AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97536683

Format of ref document f/p: F

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase