+

WO1997013413A1 - Dispersions aqueuses contenant des derives d'amidon hydrolyses - Google Patents

Dispersions aqueuses contenant des derives d'amidon hydrolyses Download PDF

Info

Publication number
WO1997013413A1
WO1997013413A1 PCT/EP1995/004016 EP9504016W WO9713413A1 WO 1997013413 A1 WO1997013413 A1 WO 1997013413A1 EP 9504016 W EP9504016 W EP 9504016W WO 9713413 A1 WO9713413 A1 WO 9713413A1
Authority
WO
WIPO (PCT)
Prior art keywords
fat
dispersion
hydrolysed starch
gelling
continuous
Prior art date
Application number
PCT/EP1995/004016
Other languages
English (en)
Inventor
Charles Rupert Telford Brown
Malcolm Glyn Jones
Ian Timothy Norton
Jeffrey Underdown
Original Assignee
Unilever N.V.
Unilever Plc
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 Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to AU38412/95A priority Critical patent/AU3841295A/en
Publication of WO1997013413A1 publication Critical patent/WO1997013413A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/015—Reducing calorie content; Reducing fat content, e.g. "halvarines"
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/003—Compositions other than spreads
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/60—Salad dressings; Mayonnaise; Ketchup
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • A23L29/35—Degradation products of starch, e.g. hydrolysates, dextrins; Enzymatically modified starches

Definitions

  • the invention relates to aqueous dispersions with hydrolysed starch derivatives. More in particular the invention relates to edible aqueous dispersions containing hydrolysed starch derivatives of low Dextrose Equivalent (DE) as a gelling agent.
  • DE Dextrose Equivalent
  • EP-A-398 411 spreads comprising gelatin at 1-7.5 times its critical gelling concentration and optionally another gelling agent such as e.g. hydrolysed starch derivatives below the critical concentration are described.
  • the hydrolysed starch described in particular is Paselli SA2, which is a maltodextrin having a DE of at least 2, and which is used e.g at 2% level, in combination with gelatin above its critical concentration of about 1 wt% on the aqueous phase.
  • Paselli SA2 which is a maltodextrin having a DE of at least 2
  • gelatin above its critical concentration of about 1 wt% on the aqueous phase.
  • the present invention provides a dispersion comprising an edible fat phase and an aqueous phase containing a hydrolysed starch derivative with a Dextrose Equivalent (DE) of below 2 and at least one gelling agent other than that, wherein the hydrolysed starch derivative is present at or above its critical concentration.
  • DE Dextrose Equivalent
  • hydrolysed starch derivatives are to be understood products obtained by the hydrolysis (using e.g. acid and/or enzymes as catalysts) of starch, but also similar gelling products obtained by synthesis e.g. by enzymatic synthesis in vitro catalysed by the enzyme phosphorylase. Gelling hydrolysed starch products obtained by hydrolysing vegetable starch are preferred. Sometimes it is preferred to remove glucose and/or di- and/or lower polysaccharides from the hydrolysate by fractionation.
  • derivatives also comprises chemically modified products e.g. obtained by esterifying some of the free hydroxyl groups with acetyl groups.
  • Suitable starches are mentioned in, e.g., US 4,510,166 and/or EP 554 818.
  • a hydrolysed starch derivative to be used according to the present invention suitably has a DE between 0.2 and 1.8, more preferably between 0.4 and 1.6 e.g. from 0.5 to 1.2.
  • Hydrolysed starch derivatives which can be used in the practice of the present invention are e.g. product
  • the structuring of the dispersion is obtained when applied in amounts as set forth in the claims, the total amount of starch derivative can be kept relatively low, which, in addition to the advantages thereof for taste also provides cost advantages.
  • the DE-value of the hydrolysed starch derivatives can be determined by various method.
  • the DE values quoted below have been determined by NMR-spectroscopy as described by Gidley, M J in Carbohydrate Research 139, (1985) 85-93 in an article entitled Quantification of the structural features of starch polysaccharides by NMR spectroscopy. It has been established that the data so obtained are in reasonable agreement with the classical "wet chemistry" method described by Nelson, N and Somogyi, M in Journal of Biological Chemistry, 153. 160 and 175 , 61.
  • the NMR-method is the yardstick employed below.
  • the critical concentration of a gelling agent is the concentration at which that gelling agent will start to form a gel.
  • the critical concentration is to be calculated from measu ⁇ rements of the shear modulus of a series of samples con ⁇ taining different concentrations of said gelling agent as described in Br. Polymer J. . 17 (1985) , 164.
  • the critical concentration of a specific gelling agent in the aqueous phase of the present dispersion is determined in an aqueous system of a similar composition, with the proviso that no other gelling agents are present, and in which system concentration and water content are varied in order to establish the critical concentration.
  • the dispersion of the invention comprises a gelling agent other than the hydrolysed starch of DE ⁇ 2.
  • a gelling agent other than the hydrolysed starch of DE ⁇ 2.
  • Such gelling (not being hydrolysed starch derivatives) agents can be, e.g. gelatin, pectin, alginate, gellan, a carrageenan, fur- celleran etc.
  • synergystic gels i.e. components which are gelling agents when applied in the presence of particular other ingredients, e.g. xanthan, logust bean gum, in the presence of k-carrageenan, and gelling agents such as heat set protein gels are applicable.
  • alginate, gelatin and/or pectin in combination with a gelling hydrolysed starch of low DE-value is preferred.
  • at least one of the gelling agents is present at a concentration at or above its critical gelling concentration.
  • the critical concentration of a combination of gelling agents is to be determined, this is done in a manner analogous to the procedure described outlined above, and whereby the composition of gelling agents considered as if it consisted of one single gelling agent. Accordingly, the composition of gelling agents is kept constant, and the weight concentration thereof is varied as if it consisted of one single gelling agent.
  • the preparation of the dispersions according to this invention a rapid formation of crystal structures can be obtained, and, hence, the preparation of these dispersions provide an advantage in the filling of the containers when compared to the prior art dispersions which crystallize slower.
  • This rapid crystallization in its turn furthermore provides an improved product stability, as the conditions at which the products are set can be controlled better when compared to slower crystallizing dispersions. Accordingly, the invention allows to prepare products of a more constant quality when produced at commercial scale.
  • the present invention provides aqueous dispersions which are in particular advantageous when applied for the preparation of spreads, such as margarines and the like.
  • dispersion comprising an edible fat phase and an aqueous phase are to be understood as to comprise fat- continuous as well as water-continuous systems.
  • the dispersion may be a fat continuous spread or a water continuous spreads.
  • Dispersions such as very low fat spreads e.g. containing 20% or less of fat, zero fat spreads and spoonable dressings are particularly preferred.
  • "Zero" fat spreads generally contain up to 7 wt% of fat, and are suitably water continuous dispersions.
  • the dispersion of the present invention comprises less than 70 wt% fat, and preferably less than 65 wt% fat.
  • the level of fat in the dispersion of the present invention is equal or less than 45 wt% fat, and preferably less than 25 wt% fat.
  • a dispersion is provided herein the level of fat is from 0 to 15 wt%, more preferred 0.5 to 10 wt% calculated on the dispersion.
  • the rheological properties of spreads, in particular zero fat spreads are disclosed in detail in EP-A-0, 298 , 561 page 7, lines 46 to page 8, line 31.
  • the dispersion provided is a dispersion which is water- continuous and has a fat-level of less than 20 wt%.
  • Important dispersions according to the present invention are water-continuous, (very) low fat spreads containing 0.5 to 20 wt% of fat and dressings containing 0-10 wt% of fat.
  • the dispersion of the invention may very well contain an emulsifier at the levels of 0.01 to 2 wt% calculated on the weight amount of oil.
  • a highly preferred embodiment of the present invention is a spread which contains an emulsifier at the levels of 0.01 to 2 wt% calculated on the weight amount of oil.
  • the emulsifier system may e.g.
  • sorbitan esters of fatty acids comprise mono- diglycerides, citric acid esters of monogly ⁇ cerides, diacetyltartaric acid esters of monoglycerides, poly-glycerol esters of fatty acids, polyoxyethylene sorbitan esters of fatty acids, sucrose esters of fatty acids, stearoyl lactylates, sorbitan esters of fatty acids, lecithin and mixtures thereof.
  • the present invention is very useful in a specific group of water-continuous dispersions viz. "spoonable" creams and dressings and the preparation thereof, this type of products is well-known in the United Kingdom.
  • spokeable the rheological parameters of creams, emulsions etc are defined in P. Sherman, Emulsion Science, Academic Press 1968, the term spoonable is not defined therein. According to our definition, a spoonable cream or dressing should display the following rheological behaviour at 5°C.
  • the yield value (also called yield stress) should be more than 50 Pa extrapolated from shear rates between 1-300 s ⁇ l (Bingham) ;
  • the Bingham viscosity should be less than 500 mPas between shear rates of 100-300 s "1 ;
  • the failure to stress should occur at a strain of less than 0.5 radians, preferably less than 0.1 radians.
  • Yield values and Bingham viscosities are determined utilising the Carrimed Rheometer. Measurements are performed at 5°C, using 4° cone and plate geometry with a gap setting of 1 mm. The shear stress is increased from zero at a rate of 60 Pa/min, and shear rates are measured until values in excess of 600 s '1 are achieved. The experiment is then terminated. A graph of shear stress vs shear rate is plotted, and a straight line fitted to the curve between the shear rates of 100-300 s 1 . The slope of this line is the Bingham viscosity.
  • the dispersion provided is a spread wherein the fat phase is based on highly unsaturated vegetable oils.
  • the zero fat spreads according to the invention are plastic in the sense that they can be spread onto bread without tearing the bread.
  • plastic spreads will have a stress strain relation with a maximum stress occurring at strain of 0.001-0.5, more preferred 0.01 to 0.3, the maximum stress at this strain being 0.01-100 kPa, more preferred 0.01 to 60 kPa and with a ratio of plastic stress and the maximum stress of 0.1 to 1.
  • a suitable method for determining these values is given in EP 298 561.
  • spreads of the invention may comprise a number of optional ingredients such as flavouring, salt, preservatives, acidifier ⁇ , vitamins, colouring materials etc.
  • the level of salt is from 0 - 4 wt%, more preferred 0.1 to 3 wt%, most preferred 0.2 to 2 wt%.
  • Preservatives, especially in the case of spreads are preferably incorporated at a level of 0 - 4 wt%, more preferred 0.01 to 2 wt%, most preferred 0.05 to 0.15 wt%.
  • Especially preferred is the use of potassium sorbate.
  • a preferred colouring material is ⁇ -carotene; preferred levels of colouring material are from 0 - 1 wt%, more preferred 0.01 to 0.2 wt% .
  • Acidifiers especially in the case of dressings, may be incorporated to bring the pH of the product to the desired level, preferably the pH of the product is from 3 to 10, more preferred 3.5 to 7.
  • a suitable pH-adjuster is for example lactic acid, citric acid or sodium bicarbonate.
  • proteins Another optional ingredient for spreads and dressings according to the present invention which may be present in compositions of the invention are proteins.
  • the protein level (including gelatin) in spreads of the invention i ⁇ from 0 to 15 wt%, more preferred, 2 to 6 wt%, most preferred 2.5 to 4 %.
  • dairy proteins Another option is to include dairy proteins, specifically to improve and enhance flavour release and oral texture.
  • the protein is partially a vegetable protein, especially soy bean protein.
  • suitable weight ratios of animal protein to vegetable protein may for example be from 10 : 1 to 1 : 10.
  • the dispersion of the invention for example a spread may further contain small particles such as herbs and vegetables.
  • the total level thereof will generally be less than 10 wt%.
  • Spreads of the preferred invention will generally comprise fairly high levels of water, say from 30 to 88 wt% of the composition, more preferred 40 to 80 wt% , most preferred 50 to 70 wt% .
  • Water may be incorporated as such, or as part of the other ingredients such as milk etc.
  • Such spreads may be fat-continuous in the sense that they comprise a continuous fat phase. Fat-continuous spreads can readily be distinguished from water-continuous spreads by means of conductivity measurements.
  • Fat continuous dispersions of the invention can suitably be used as bread spreads to replace e.g. margarine or halvarine, but they can also suitable be used as flavoured spread, for example cheese spreads, meat spreads, nut spreads, sweet spreads or vegetable spreads.
  • Spreads of the invention may be prepared by any suitable method for the preparation of fat-continuous spread products.
  • a preferred method however involves the mixing of the ingredients, optionally followed by pasteurisation followed by cooling in one or more scraped surface heat exchangers (A-units) to a temperature of 0 to 10 °C, optionally followed by processing through one or more
  • this process is conducted in such a manner that the water-continuous composition is maintained at a temperature below the gel setting temperature for at least 100 seconds prior to the formation of the fat-continuous dispersion. More preferably cooling regime and residence time employed till the formation of the fat-continuous dispersion are such that under quiescent conditions a gel having a shear storage modulus of more than 50 Pa. , preferably of more than 70 Pa., is formed.
  • the process can be conducted in such a way that the water-continuous composition is converted to small gelled aqueous pieces having a volume weighted mean diameter of less than 150 ⁇ m(microns) prior to the formation of the fat-continuous dispersion.
  • this process can be conducted in such a way that the water-continuous composition after having been converted to small gelled aqueous beads is combined with a separate fat-continuous stream to form a fat-continuous dispersion.
  • the hydrolysed starch derivative was added to water at 80°C, stirred for 10 minutes, then cooled to 60° and all other further ingredients were added.
  • the mixture was passed into an A-unit having an exit temperature of 80°C to pasteurize; the mixture was then cooled down by passage (at 30 g/min) through a series of two A-units, passed through a C-unit and then another A-unit (exit temperature from each unit was 5°C) and finally packed into tubs.
  • a very good starch-continuous product was obtained, which had a favourable texture and flavour perception together with a very low calorie content.
  • a spoonable fat-free dressing was prepared from the following ingredients.
  • the pectin was dissolved in deionised water at 85°C.
  • Calcium chloride solution was added to form calcium pectate, followed by the addition of hydrolysed starch derivative and then the remaining dry ingredients such as salt, sucrose and flavour followed.
  • the pH was adjusted to 3.8 with acetic acid and the mixture was cooled through a MicroVotator® A-unit operating at a shaft speed of 3800 rpm, to an exit temperature of 12°C.
  • the product was then cooled and sheared through further A- and C-units to a final temperature of 5°C.
  • the throughput for the process was 50 g/min.
  • a spoonable fat-free mayonnaise with a smooth texture was obtained.
  • the product showed plastic rheology and was opaque/translucent due to the presence of hydrolysed starch derivative and no titanium dioxide needed to be incorporated.
  • the product satisfied the required parameters for a spoonable cream/dressing set out above and had a calorie content which was extremely low.
  • a spread containing 20 wt% of a continuous fat phase and 80 wt% of a dispersed gelled aqueous phase was prepared from a water-continuous emulsion obtained by admixing an oil phase and an aqueous phase of the following composition: Oil phase: fat blend containing 20% soya bean oil,
  • the water-continuous emulsion obtained after mixing of the above two phases at 50°C was pasteurized at 80°C and subsequently (at 50 g/min) passed through two scraped surface heat exchangers (A-units) and two crystallisers (C- units) provided with cooling jackets and filled into tubs. Inversion of the water-continuous emulsion to a fat- continuous dispersion was obtained in the second C-unit.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Molecular Biology (AREA)
  • Edible Oils And Fats (AREA)

Abstract

La présente invention concerne une dispersion comestible dont moins de 50 % en poids est constitué d'une phase grasse comestible et d'une phase aqueuse gélifiée contenant un dérivé d'amidon hydrolysé faisant office de gélifiant et présentant un Equivalent Dextrose inférieur à 2. De préférence, le dérivé d'amidon hydrolysé présente un Equivalent Dextrose se situant entre 0,2 et 1,5, de préférence un Equivalent Dextrose se situant entre 0,4 et 0,9. Cette dispersion est avantageuse lorsque le dérivé d'amidon hydrolysé est présent avec un autre gélifiant au moins et que l'un au moins des gélifiants est présent en une concentration atteignant ou dépassant la concentration critique de gélification. On obtient des résultats particulièrement bons lorsque le dérivé d'amidon hydrolysé est présent à un niveau supérieur à sa concentration critique de gélification et que l'un au moins des autres gélifiants atteint un niveau inférieur à sa concentration critique de gélification.
PCT/EP1995/004016 1994-10-10 1995-10-11 Dispersions aqueuses contenant des derives d'amidon hydrolyses WO1997013413A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38412/95A AU3841295A (en) 1994-10-10 1995-10-11 Aqueous dispersions with hydrolysed starch derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP94307403 1994-10-10

Publications (1)

Publication Number Publication Date
WO1997013413A1 true WO1997013413A1 (fr) 1997-04-17

Family

ID=8217873

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004016 WO1997013413A1 (fr) 1994-10-10 1995-10-11 Dispersions aqueuses contenant des derives d'amidon hydrolyses

Country Status (2)

Country Link
AU (1) AU3841295A (fr)
WO (1) WO1997013413A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703062B1 (en) * 1998-08-06 2004-03-09 Lipton, Division Of Conopco, Inc. Low-fat food emulsions having controlled flavor release and processes therefor
JP2007302767A (ja) * 2006-05-10 2007-11-22 Futamura Chemical Co Ltd 易ゲル化デンプン部分分解物
JP2013215164A (ja) * 2012-04-11 2013-10-24 Unitec Foods Co Ltd ドレッシングおよびドレッシングタイプ調味料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009291A (en) * 1974-03-25 1977-02-22 General Foods Corporation Cold water soluble stable bulked starch
US4510166A (en) * 1984-01-19 1985-04-09 National Starch And Chemical Corporation Converted starches for use as a fat- or oil-replacement in foodstuffs
EP0480531A1 (fr) * 1990-10-10 1992-04-15 Koninklijke Brinkers Margarinefabrieken B.V. Procédé de préparation d'un produit à tartiner contenant de la lactoprotéine et/ou protéine végétable ainsi qu'un agent épaississant et une installation apte à être utilisée dans ce procédé
EP0554818A2 (fr) * 1992-02-07 1993-08-11 National Starch and Chemical Investment Holding Corporation Purification des polysaccharides
EP0605217A2 (fr) * 1992-12-28 1994-07-06 Kraft Foods, Inc. Pâte à tartiner sans matière grasse

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009291A (en) * 1974-03-25 1977-02-22 General Foods Corporation Cold water soluble stable bulked starch
US4510166A (en) * 1984-01-19 1985-04-09 National Starch And Chemical Corporation Converted starches for use as a fat- or oil-replacement in foodstuffs
EP0480531A1 (fr) * 1990-10-10 1992-04-15 Koninklijke Brinkers Margarinefabrieken B.V. Procédé de préparation d'un produit à tartiner contenant de la lactoprotéine et/ou protéine végétable ainsi qu'un agent épaississant et une installation apte à être utilisée dans ce procédé
EP0554818A2 (fr) * 1992-02-07 1993-08-11 National Starch and Chemical Investment Holding Corporation Purification des polysaccharides
EP0605217A2 (fr) * 1992-12-28 1994-07-06 Kraft Foods, Inc. Pâte à tartiner sans matière grasse

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703062B1 (en) * 1998-08-06 2004-03-09 Lipton, Division Of Conopco, Inc. Low-fat food emulsions having controlled flavor release and processes therefor
JP2007302767A (ja) * 2006-05-10 2007-11-22 Futamura Chemical Co Ltd 易ゲル化デンプン部分分解物
JP2013215164A (ja) * 2012-04-11 2013-10-24 Unitec Foods Co Ltd ドレッシングおよびドレッシングタイプ調味料

Also Published As

Publication number Publication date
AU3841295A (en) 1997-04-30

Similar Documents

Publication Publication Date Title
US5501869A (en) Fat-free tablespread and method of making
US5158798A (en) Low-calorie fat substitute
AU667701B2 (en) Water-continuous emulsions based on polysaccharides
US5308639A (en) Low calorie fat substitute
US5626901A (en) No and low fat salad dressing compositions
US5846592A (en) Low fat spread
AU684476B2 (en) Low fat spread
CA2253854C (fr) Graisse tartinable en emulsion eau dans l'huile
CA2045214C (fr) Emulsion eau-huile et procede de preparation connexe
EP0994658B1 (fr) Emulsions aqueuses continues, consommables et coulantes
US5656323A (en) Low fat spread
US5302408A (en) Edible plastified dispersion
CA1340090C (fr) Dispersion plastifiee consommable
AU649575B2 (en) Low fat spreads and dressings
US5652011A (en) Low fat spreads and dressings
US5508056A (en) Low fat spread
WO1997013413A1 (fr) Dispersions aqueuses contenant des derives d'amidon hydrolyses
EP0049705A1 (fr) Produit à tartiner comestible à faible teneur en graisse et procédé pour sa fabrication
WO2005004642A1 (fr) Produits a faible teneur en matiere grasse a phase huileuse continue
CA2082543C (fr) Tartinades et sauces a faible teneur en graisses
CA2150086A1 (fr) Margarine a faible teneur en matieres grasses

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

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

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

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: 97514655

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载