WO1997025354A1 - Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee - Google Patents

Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee Download PDF

Info

Publication number
WO1997025354A1
WO1997025354A1 PCT/IB1995/001171 IB9501171W WO9725354A1 WO 1997025354 A1 WO1997025354 A1 WO 1997025354A1 IB 9501171 W IB9501171 W IB 9501171W WO 9725354 A1 WO9725354 A1 WO 9725354A1
Authority
WO
WIPO (PCT)
Prior art keywords
guar
acid
viscosity
product
processed
Prior art date
Application number
PCT/IB1995/001171
Other languages
English (en)
Inventor
William Ewing Swartz
Graig Alan Hoppe
James Thomas Elfstrum
Original Assignee
Rhone-Poulenc Inc.
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 Rhone-Poulenc Inc. filed Critical Rhone-Poulenc Inc.
Priority to BR9510685A priority Critical patent/BR9510685A/pt
Priority to PCT/IB1995/001171 priority patent/WO1997025354A1/fr
Priority to JP52501597A priority patent/JP2001504516A/ja
Priority to EP95944707A priority patent/EP0871674A1/fr
Priority to CA002242239A priority patent/CA2242239A1/fr
Priority to AU48404/96A priority patent/AU4840496A/en
Publication of WO1997025354A1 publication Critical patent/WO1997025354A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
    • A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
    • A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/238—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seeds, e.g. locust bean gum or guar gum
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
    • A23G2200/06—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing beet sugar or cane sugar if specifically mentioned or containing other carbohydrates, e.g. starches, gums, alcohol sugar, polysaccharides, dextrin or containing high or low amount of carbohydrate

Definitions

  • This invention relates to the provision of
  • guar particulate to provide a relatively homogeneous, uniform, stable product for application in the food industry, providing in aqueous solution a reliable viscosity under controlled conditions capable of efficient conversion into processing aids, thickeners, binders, stabilizers and viscosity builders to augment food products such as sauces, salad dressings, cheeses and cheese products, providing reproducible texture and mouth eel, among other desirable organoleptic properties.
  • the product as processed in accordance with the inventive principles more fully described herein is free of unacceptable ash levels providing a visually and
  • the product provides a rich source of dietary fiber without excessive viscosity as is
  • Guar is derived from the endosperm of the leguminous plant Cvamopsis tetra ⁇ onolobus ( inue) Taub o J n or Cvamopsis Psoraloides ( Lami) D. c. ( Fam. Legiimi ⁇ osae ) ;
  • Guar seeds comprise a seed coat or hull, a pair of tough endosperm sections, referred to as 'guar splits' , which contain the gum and the embryo.
  • 'guar splits' a pair of tough endosperm sections, referred to as 'guar splits' , which contain the gum and the embryo.
  • the splits are ground and processed to provide a gum or gum precursor.
  • the splits may be processed to recover components thereof which may include all membrane, inorganic salts, and the predominant galactomannan, polysaccharide as well as associated proteinaceous material and water insoluble gels.
  • the patentee still employs upwards of 60 percent of water in the reaction mixture, and utilizes a pH above 12, with a min mum of 150 parts by weight of aqueous alkali.
  • the resulting wet solids may be 0 partially neutralized to a pH below about 11, e.g., pH 9 (Example 9) .
  • free-flowing particulate mechanically processed guar endosperm is subjected to aqueous processing under acidic conditions with minimal aqueous dilution and hence controlled, limited hydration and relatively high shear to produce a converted guar product of modified rheological characteristics.
  • a functionally modified guar product for food use comprising low ash, a shorter texture than conventional guar products and exhibiting a novel low viscosity profile especially at about 1% concentration or less under conditions of conventional refrigeration ranging to mildly elevated temperatures in food compositions such as sauces, salad dressings and the like.
  • the absolute acid level is relatively low in comparison to direct acid refining of whole hydrated guar splits as practiced in the art such that degradation leading to ash levels unacceptable in food use is controlled and minimized. Even at relatively low acid levels it may nevertheless be desirable to provide a fully neutralized product, hence for this purpose reaction with alkali to effect neutralization may be employed to minimize salt levels.
  • Fig. I (Effect of Acid on Guar Modification) is a plot of Viscosity (cps) as the abscissa and hydration time (minutes) evidencing change in rheological characteristic in accordance with the invention.
  • the native guar may be simply purified, i.e., split with hull removed or dehulled and screened one or more times to remove detritus, and then ground to a particulate ranging from a coarse granular material to a fine powder. Coarser materials tend to disperse more readily, whereas finer grinds are more rapidly hydrated.
  • the guar starting material employed is at least 66% galactomannan and exhibits compositional elements consistent with the Food Chemicals Codex 3d Ed. (1981), p.141 incorporated herein by reference; specifically after processing it contains no more ash than exceeds 1 to 1.5% by weight of the guar.
  • Course gums passing through a 40 mesh screen but minimally through a 100 mesh screen; and fine gums defined as those containing a predominance of particles passing through a 200 mesh screen, can be used to prepare a satisfactory product. It will be understood that sources of guar may be mixed such that a certain bimodal distribution may result, for example, where a coarse grind and fine powder are used together.
  • Guar gums of varying initial viscosity, reflective of variations in molecular weight, composition, and degree of branching are readily available, in the range of 1000 to 6000 cps measured as a 1% solution (Brookfield RVF viscometer, spindle 3 or 4, 20 rpm). While any guar gum starting material may be employed, Uniguar 40 available from Rhone Poulenc with a viscosity of 2000 cps or Dycol 4000 FC, also available from Rhone Poulenc with a typical viscosity of 4000 cps (both viscosities determined as a 1% (w/w) solution using a Brookfield RVF viscometer (Spindle 3, 20 rpm) is preferred.
  • the guar is introduced to a high shear mixing zone containing or to which is added an aqueous acidic medium with or without alcohol.
  • an aqueous acidic medium with or without alcohol Preferably, acid with a limited amount of water with or without alcohol is gradually added to the guar under conditions of high shear agitation.
  • the rate of addition may be empirically selected to minimize clumping or the formation of gummy particles and may be affected by the rate of shear or the advance of the material to be treated, all of which is easily determined by one skilled in the art.
  • high shear mixing it is intended to denote a mixing process in a contained zone including stirring under conditions to effect in adjacent zones of the substrate being worked the application of differential forces, (as, differential velocity) between said zones, which may be in laminar or turbulent flow.
  • differential forces may be effected by the geometry of the stirring blade, the clearance of the blade member with the container or fixed or moveable obstructions in the container and the velocity of the stirrer, and will naturally be affected by the temperature of the system relative to the viscosity characteristics of the stirred medium. Under conditions of high velocity, low clearances and/or high viscosity, high shear mixing expressed in units of reciprocal seconds is readily achieved.
  • the treatment regimen is selected to maintain a high solids system with minimum moisture level; in addition, the acid addition is adjusted to maintain pH yet avoid undesirable formation of ash from the action of excess acid.
  • a prototypical/batch system employed a Cuisinart food processor with the basic cutting blade providing shear to the mixing zone containing about 500 grams of guar gum granulate and acid (2N HCl 1:6 dilution of 12 N HCL in ethanol) was added at a rate of about 5 ml/min. to a total of 10 to 35 ml with continuous mixing; after the completion of acid addition, the system was agitated for another 10 to 15 seconds.
  • any high shear mixer may be utilized in an open or closed system under ambient conditions. Some increase in temperature as a consequence of the work performed will be experienced but generally normal heat dissipation is readily achieved without cooling.
  • Any mineral acid may be utilized such as hydrochloric, sulfuric or nitric acid but hydrochloric is preferred for retention of favorable color; phosphoric acid or other food acceptable acids are naturally preferred for regulated applications.
  • a more concentrated acid source is desirable in the range of 2 to 3N but will depend in part on the amount of material being processed, and particle size.
  • the processed guar is then treated at an elevated temperature or a period of time to provide a product of selected viscosity when redispersed in an aqueous medium.
  • the material may be heat treated in a circulating oven for a period from one minute to several hours at a temperature of 30 to 180°C preferably 50 to 130°C.
  • the time of treatment will depend largely upon the nature of the native guar gum with longer treatment times usually associated with higher viscosity materials. Generally, it is preferred to avoid higher temperatures concomitant however with reasonable processing times.
  • treatment is continued for a period and under conditions to provide a product ⁇ which when dried, then redispersed in ambient water at 1 percent concentration, will evidence a selected initial viscosity of from 0 to 2500 centipoise, preferably from 0 to 1500 cps; and most preferably from 0 to 1000 cps.
  • a fully neutralized product preferably from 0 to 1500 cps; and most preferably from 0 to 1000 cps.
  • it can be convenient to use a high shear mixer to facilitate this step.
  • As with the acid treatment gradual addition is preferable to control exposure of the product to the alkali. It has also been found preferable to utilize the alkali in the form of a caustic ethanolic solution.
  • the level of retained moisture may be excessive relative to storage or use PCMB95/01171
  • the functionally modified guar of the present invention may be used alone or with other gums such as locust bean gum, carrageenan, xanthan or tar gum, starch or gelatin in a wide variety of food products such as ice cream, pie fillings, icings and frostings, pet foods, frozen novelties, whipped toppings, sour cream and yogurt products, sauces, cream soups, salad dressings, cottage cheese dressings, egg substitutes and dipping batters.
  • the product may also be derivatized where food acceptable substituents are employed.
  • compositions may employ food acceptable salts of mono-, di- or trivalent cations, preservatives such as sodium benzoate, citric acid or sorbic acid, or ion sequestering agent such as citric, tartaric or orthophosphoric acids.
  • preservatives such as sodium benzoate, citric acid or sorbic acid, or ion sequestering agent such as citric, tartaric or orthophosphoric acids.
  • the product may be dried and stored then, when converted to gel or sol form by hydration in cold or warm water systems, the thixotropic viscous colloidal dispersion thus formed may be used directly in food compositions.
  • the viscosity developed 1 is somewhat shear sensitive at low concentration and is dependent on temperature, concentration, pH, ionic strength as well as the induced agitation.
  • Viscosities may be measured by a rotational, shear type viscometer 5 capillary viscometer at low concentrations and extrusion rheometers at higher concentrations. Typically viscosity is measured by a Brookfield RVT Viscometer (Brookfield Engineering Laboratories, Stoughton, MA 02072) at 20 rpm using spindle 3.
  • Brookfield RVT Viscometer Brookfield Engineering Laboratories, Stoughton, MA 02072
  • the viscosity profile generally provided an envelope of curves with similar viscosity development 5 from a base line of lower viscosity for higher level of acid treatment.
  • Uniguar 80 was processed in a similar manner to Example I, except that the acid component was 35 ml 2N HCL in 80% ethanol. Aliquots of resulting material were heated at
  • Example II 100 g of Dycol 4000 FC available from Rhone Poulenc Food Ingredients and having a viscosity of 4110 cps (Brookfield RVF, Spindle 3, 20 rpm, 25°) was processed as set forth in Example I except that 7 ml of various concentrations of HCL in 80% ethanol were utilized, ranging from 0.5N to 2.ON. Each of the samples was then heated in a 90°C oven for 15 minutes. Viscosity values after hydration at 1% for 2 hours are set forth in Table IV. Viscosity results for untreated and similarly treated Uniguar 80 with 2N HCL is given for comparative purposes.
  • the viscosity variance (925-1375 cps) is believed to be due to the lag time at temperatures above ambient before the neutralization step occurred. Ash levels are all within acceptable limits.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Food Science & Technology (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Nutrition Science (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Seeds, Soups, And Other Foods (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Cette invention concerne des produits à base de guar fonctionnellement modifié, destinés particulièrement à des applications de catégorie alimentaire, qui se caractérisent par une viscosité réduite, une faible teneur en cendres et une forte teneur en fibres et que l'on prépare par traitement à fort cisaillement dans des conditions acides et à température élevée.
PCT/IB1995/001171 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee WO1997025354A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR9510685A BR9510685A (pt) 1996-01-05 1996-01-05 Guar modificado preparado por tratamento de cisalhamento elevado sob condições acidacas em temperatura elevada
PCT/IB1995/001171 WO1997025354A1 (fr) 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee
JP52501597A JP2001504516A (ja) 1996-01-05 1996-01-05 機能的に改良されたグアール
EP95944707A EP0871674A1 (fr) 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee
CA002242239A CA2242239A1 (fr) 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee
AU48404/96A AU4840496A (en) 1996-01-05 1996-03-20 Modified guar, prepared by high shear treatment under acidic conditions at elevated temperature

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/IB1995/001171 WO1997025354A1 (fr) 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee
CA002242239A CA2242239A1 (fr) 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee

Publications (1)

Publication Number Publication Date
WO1997025354A1 true WO1997025354A1 (fr) 1997-07-17

Family

ID=25680345

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB1995/001171 WO1997025354A1 (fr) 1996-01-05 1996-01-05 Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee

Country Status (4)

Country Link
EP (1) EP0871674A1 (fr)
AU (1) AU4840496A (fr)
CA (1) CA2242239A1 (fr)
WO (1) WO1997025354A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974100A (zh) * 2010-11-22 2011-02-16 沈阳工业大学 一种复合改性瓜尔胶及其制备方法
US8536325B2 (en) 2009-02-05 2013-09-17 Alcon Research, Ltd. Process for purifying guar
US9175249B2 (en) 2009-07-07 2015-11-03 Alcon Research, Ltd. Ethyleneoxide butyleneoxide block copolymer compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346556A (en) * 1965-10-14 1967-10-10 Marine Colloids Inc Treatment of manno galactan gums
JPH03290196A (ja) * 1990-04-04 1991-12-19 Meiji Seika Kaisha Ltd 低粘性難消化性多糖類の製造法およびそれを含有する食品
WO1993010156A1 (fr) * 1991-11-13 1993-05-27 Chemische Fabrik Grünau Gmbh Procede en continu de decomposition d'heteropolysaccharides
WO1993015116A1 (fr) * 1992-01-31 1993-08-05 The Dow Chemical Company Procede de reduction de la viscosite de gommes glucidiques naturelles
DE4344156A1 (de) * 1993-12-23 1995-06-29 Gruenau Gmbh Chem Fab Verfahren zum Abbau von Polygalaktomannanen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346556A (en) * 1965-10-14 1967-10-10 Marine Colloids Inc Treatment of manno galactan gums
JPH03290196A (ja) * 1990-04-04 1991-12-19 Meiji Seika Kaisha Ltd 低粘性難消化性多糖類の製造法およびそれを含有する食品
WO1993010156A1 (fr) * 1991-11-13 1993-05-27 Chemische Fabrik Grünau Gmbh Procede en continu de decomposition d'heteropolysaccharides
WO1993015116A1 (fr) * 1992-01-31 1993-08-05 The Dow Chemical Company Procede de reduction de la viscosite de gommes glucidiques naturelles
DE4344156A1 (de) * 1993-12-23 1995-06-29 Gruenau Gmbh Chem Fab Verfahren zum Abbau von Polygalaktomannanen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9207, Derwent World Patents Index; AN 92-051440, XP002014228 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8536325B2 (en) 2009-02-05 2013-09-17 Alcon Research, Ltd. Process for purifying guar
US9175249B2 (en) 2009-07-07 2015-11-03 Alcon Research, Ltd. Ethyleneoxide butyleneoxide block copolymer compositions
CN101974100A (zh) * 2010-11-22 2011-02-16 沈阳工业大学 一种复合改性瓜尔胶及其制备方法

Also Published As

Publication number Publication date
EP0871674A1 (fr) 1998-10-21
CA2242239A1 (fr) 1997-07-17
AU4840496A (en) 1997-08-01

Similar Documents

Publication Publication Date Title
US7462232B2 (en) Microcrystalline cellulose compositions
US5422134A (en) Gelling agent
DE69230266T2 (de) Fett-Ersatz
DE69502725T2 (de) Texturmittel mit nahrungsmittelqualität aus amylosereichen stärketeilchen und verfahren zu seiner herstellung
US5614243A (en) Starch-based texturizing agents and method of manufacture
DE69936726T2 (de) Stabilisierungssubstanz auf basis von schnell peptisierender mikrokristalliner zellulose
US4159982A (en) Protein/starch complex
EP1155081B1 (fr) Composition a base d'emulsifiant d'amidon a forte teneur en amylose et procedes de fabrication correspondants
US6048563A (en) Reduced viscosity, low ash modified guar and process for producing same
CA2351319A1 (fr) Gomme gellane native a poids moleculaire reduit
JP2023134684A (ja) 高い加工耐性を有するアルファ化澱粉、ならびにその製造及び使用方法
Akesowan Viscosity and gel formation of a konjac flour from Amorphophallus oncophyllus
JPH06335365A (ja) 微細セルロース含有食品組成物
USH1394H (en) Method of preparing reduced fat spreads
WO1997025354A1 (fr) Guar modifie, prepare par traitement a fort cisaillement dans des conditions acides et a temperature elevee
EP0664084A1 (fr) Pate pour produit alimentaire, procede de production et produit alimentaire la contenant
GB2323092A (en) Water-continuous spread
AU702501B2 (en) Pourable salad dressing
JPS62126937A (ja) 繊維状食品の製法
AU2002333232B2 (en) Fat-emulsions
JP2001504516A (ja) 機能的に改良されたグアール
JPH0339065A (ja) 低カロリーマヨネーズ様食品
GB1602505A (en) Process for making an edible complex of casein and starch
Imeson et al. Microcrystalline cellulose
JPH08154599A (ja) ファーセレランを含有する食品用ペースト、その製造方法及びそれを含む食品

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

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

Ref document number: 2242239

Country of ref document: CA

Ref document number: 2242239

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/A/1998/005446

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1995944707

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1995944707

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: 1995944707

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1995944707

Country of ref document: EP