WO1996026252A1 - Solution aqueuse boree notamment pour l'adjuvantation de colle amylacee - Google Patents
Solution aqueuse boree notamment pour l'adjuvantation de colle amylacee Download PDFInfo
- Publication number
- WO1996026252A1 WO1996026252A1 PCT/FR1996/000292 FR9600292W WO9626252A1 WO 1996026252 A1 WO1996026252 A1 WO 1996026252A1 FR 9600292 W FR9600292 W FR 9600292W WO 9626252 A1 WO9626252 A1 WO 9626252A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- solution
- boron
- compound
- mixtures
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
Definitions
- the technical field of the present invention is that of the solubilization of boron compounds, in particular and without limitation with a view to the adjuvanting of starchy adhesives using boron compositions.
- the invention relates to the incorporation of boric acid and / or borates such as borax, in aqueous compositions, for example starchy compositions of the type of those used for the manufacture of starchy adhesives.
- boric acid and / or borates such as borax
- aqueous compositions for example starchy compositions of the type of those used for the manufacture of starchy adhesives.
- the latter are useful, in particular, in the paper / cardboard industry and more particularly for the manufacture of cardboard and cardboard packaging.
- the subject of the invention is a borated aqueous solution and its use eg for the adjuvanting of starchy glues, said solution being of the type of those comprising at least one amino compound, preferably aminohydroxylated, or alkylamine, and / or a polyhydroxylated compound.
- Boron or boracic products are derivatives of the chemical element boron (B) and we will refer to this meaning in this presentation.
- these derivatives are in particular boric acid and borates, such as for example borax pentahydrate, borax decahydrate, sodium pentaborate tetrahydrate, sodium metaborate octahydrate, potassium tetraborate, potassium pentaborate octahydrate.
- boric acid and borates such as for example borax pentahydrate, borax decahydrate, sodium pentaborate tetrahydrate, sodium metaborate octahydrate, potassium tetraborate, potassium pentaborate octahydrate.
- These commercial boron products are widely used as more or less active ingredients in compositions of all kinds, such as fertilizers, detergents, metallurgical cutting fluids, drugs, cosmetic products, or even products based on starch such as adhesives for paper / cardboard.
- starch glues you should know that they contain native starch and / or modified starch such as crosslinked starches. In order for them to develop their vehicle power, it is necessary to heat them in the presence of soda, so as to cause the bursting of all the starch grains. This forms a job in which the secondary starch is added.
- the latter defines the adhesive power of the glue, because the combination of temperature, generated by the grooved cylinders and the application of the glue on the cardboard, makes it possible to form a complex linked by the fact that the secondary starch has burst.
- One of the difficulties encountered by the applicators during the formation of the adhesive relates to the control of the viscosity. The latter must be carefully fixed so as to allow easy coating on the substrates to be bonded. It is thus known to use for this purpose boron adjuvants, having plasticizing, reinforcing, spinning and adhesion promoting effects (among others) vis-à-vis starch glue.
- the added boron product consists of borax powder, which is incorporated continuously or semi-continuously into the starch glue being formed.
- This powdery boreal form generates several drawbacks.
- borax powder poses storage problems since it has a tendency to take up water, hence caking phenomena.
- a clod product is difficult to handle, in particular because it no longer flows.
- the borax powder (possibly mottled) is liable to cause metering inaccuracies, due to blocking or jamming incidents which may occur in the powder supply means (hopper, worm) conventionally used. in continuous glue manufacturing processes.
- the borax powder mixes poorly with the starch glue in formation, which requires sophisticated stirring means and requires longer reaction or incorporation times.
- boric acid or hydrated borax in the form of a solution, since it is clear that the handling of a liquid and the intimate mixing of a liquid with a liquid are simpler than that of a solid.
- European patent application N ⁇ 326 247 describes a process for adding boric acid or borate to a starch glue in preparation.
- the borated liquid composition used in the invention according to this previous application comprises 25 to 35% by weight of boric acid or borate, 55 to 35% by weight of water and 20 to 30% by weight of monoethanolamine or d 'a polyhydroxy organic compound.
- Such compositions are relatively poor in active boron principle. It follows that the theoretical concentrations of boric anhydride ⁇ O 3 corresponding are even lower.
- US Patent No. 4,332,609 describes a boron fertilizer comprising a compound of boric acid with an alkanolamine. This document has nothing to do with, among other things, the use of boron liquid in the admixture of starch glue.
- one of the essential objectives of the invention is to provide a boron adjuvant, in particular, for starch glue, an adjuvant which is in stable liquid form and which is endowed with high efficiency per unit mass , with regard in particular to the functions of adhesion promoter, of plasticizer, and of cohesion enhancer, of the starchy adhesive.
- Another objective of the invention is to provide a liquid boron adjuvant in particular for starch glues, for decontaminating compositions of radioactive products, for biocidal compositions, or for polishing and waxing compositions which is easy to prepare and to handle.
- Another essential objective of the invention is to provide a boron liquid adjuvant in particular for starch glues, for decontaminating compositions of radioactive products, for biocidal compositions, or for polishing and waxing compositions which is economical, by the fact of using a single product for several actions.
- Another essential objective of the invention is to provide a replacement boron liquid adjuvant, in particular for starch glues, for decontaminating compositions of radioactive products, for biocidal compositions, or for polishing and waxing compositions, adjuvant in the form of a solution.
- Another essential objective of the invention is to provide a boron liquid adjuvant, in particular for starch glues, for decontaminating compositions of radioactive products, for biocidal compositions, or for polishing and waxing compositions, having at least one of the following properties: bactericide , anti-foam fungicide (among others).
- Another object of the invention is to provide a simple and inexpensive process for preparing the above-mentioned adjuvant.
- a borated aqueous solution in particular for the admixture of starchy glue, said solution comprising at least one amino compound (alkylamino and / or aminohydroxylated and / or arylamine) and / or an organic polyhydroxy compound.
- This solution is characterized: * in that it comprises: * a theoretical amount of B 2 O 3 , between 25 and 55, preferably between 25 and 45 and more preferably still between 32 and 38% by weight * at least one solubilized complex between at least one boron product and the amino compound, preferably aminohydroxylated and / or alkylamine and / or arylamine, and / or an organic polyhydroxylated compound,
- this solution can comprise at least one agent increasing the wettability of the solution preferably selected from the following compounds: methanol or 2-ethyl -hexylsulfate and mixtures thereof.
- the present invention also relates to the use of a borated aqueous solution, in particular that defined above, for the additive of starchy glue, said solution comprising at least one amino compound, preferably aminohydroxylated and / or alkylamine and / or a polyhydroxylated compound.
- organic characterized: in that it comprises an initial theoretical amount of B 2 O 3 between
- the Applicant has shown that the solubilization of the product or (solute) boron passes, on the one hand, by its transformation (initialization) into a complex with an aminohydroxylated compound and / or with an aminoalkylated compound and / or with an organic polyhydroxylated compound and, on the other hand, by its transformation into a borate very soluble in water, eg pentaborate for example of sodium.
- the borated aqueous solution can be free of amino products and / or of polyhydroxylated compounds and can comprise one or more additives, of the biocide (fungicide / bactericide) type, anti-foam, surfactant, etc.
- a liquid boron adjuvant formed by an aqueous solution according to the invention can perfectly be part of a continuous or semi-continuous mode of preparation, for example, of starch glue.
- a preparation immediately precedes the coating of the starchy adhesive on the supports to be bonded (paper, cardboard).
- the incorporation of the solution according to the invention takes place easily and once introduced, said solution mixes intimately with the starch mixture added with soda. This step is brief so that the starch glue is quickly endowed with the properties which the borated solution gives it: adhesiveness, viscosity (stringy texture) adapted, reinforcement of cohesion.
- borated aqueous solution according to the invention is stable on storage (several months at temperatures ranging from -5 ° C. to above 60 ° C.) and ideally does not have undissolved products, crystallized.
- the borated aqueous solution according to the invention increases the burst temperature of the starch glue (gelatinization temperature). It is clear that this opens the door to the use of starch originally having a low burst temperature.
- the aminohydroxylated compound is chosen from the following products: monoethanolamine, diethanolamine, triethanolamine and their mixtures (among others), the amino compound is chosen from the following products: hydrazine, diethylenetriamine, ethylenediamine and, between others, their mixtures and the organic polyhydroxy compound is chosen from the following products: glycerin, glucose, sorbitol, among others, and their mixtures.
- the aminohydroxylated compound may have a lowering effect on the pH of the solution which must be taken into account when regulating the pH.
- At least one strong mineral or organic base to adjust the pH between 7 and 8, in the borated aqueous solution considered.
- This base is preferably of hydroxylic nature, but even more preferably is chosen from the following products: NaOH, KOH, LiOH, among others, and their mixtures.
- This base is at least initially (during preparation) included in the solution. It is clear that thereafter at least part of this base reacts with the other solutes of the solution.
- the boron product is selected in the following list: boric anhydrides, boric acids, borates and their mixtures, the preferred compounds being the following: B 4 O 7 Na 2 , 10 H 2 O (Borax); B 4 O 7 Na 2 , 5H 2 O (Borax pentahydrate); B 4 O 7 Na 2 (anhydrous Borax); B (OH) 3 (boric acid), B 2 O 3 (boric anhydride); B ⁇ 0 O N0a 2 , 10H 2 O (sodium pentaborate); BO 2 Na, 4H 2 0 (sodium metaborate); B 10 O ⁇ 8 K 2 , 8 H 2 O (potassium pentaborate); B 4 ⁇ 7 K 2 , 4 H 2 O (potassium tetraborate); B 4 O 7 (NH 4 + ) 2 , 4 H 2 O (ammonium pentaborate) among others and their mixtures; the combination of boric acid with sodium hydroxide for the initialization of sodium
- Another characteristic but non-limiting parameter of the solution according to the invention is its density at 20 "C, which is preferably 1.4 ⁇ 0.4.
- the invention relates to a borated aqueous solution, capable of being used in the use described above and characterized in that the boron product consists of a mixture of at least one borate and of boric acid and / or IM-
- the borates are, for example, those described above.
- the solution comprises, in particular, at least one additive chosen from: anti-foaming agents, biocides, agents increasing resistance to humidity, dyes, ionic surfactants or not and their mixtures.
- the biocide is preferably selected from quaternary ammoniums and / or isothiazolinone derivatives.
- biocides in particular bactericides and / or fungicides, mention may be made of formalin, glutaraldehyde and aldehydes.
- the solution can also include other surfactants such as ethoxylated fatty acids, block copolymers with a cumene hydrotope, xylene sulfonate, or ionic or non-ionic surfactants, of 2-ethylhexylsulfate type or fatty alcohol. ethoxylated.
- the solution can also contain other ingredients of the keto-aldehyde resin type, dye, perfume, methanol type solvent.
- borated aqueous solution used in particular in the context of the use according to the invention, can correspond to the following composition:
- the preparation of the solution used in particular in the above-mentioned use consists in carrying out a solubilization in water of the solutes defined above and this, at a temperature preferably between 20 ° C. and 55 ° C.
- the aminohydroxylated and / or alkylamino and / or polyhydroxylated compound and, where appropriate, the strong base are advantageously firstly mixed in water, the boron product (s) then being incorporated and kneaded.
- At least part of the water constituting the solution is preheated (for example to 40 ° C.) and at least part of the amino and / or polyhydroxylated compounds are incorporated with stirring until a mixture is obtained homogeneous.
- the boron product (s) are then added to the medium with stirring.
- the boron products are formed by a mixture of borate and boric acid, the borate is advantageously introduced first.
- the present invention also relates to starch glue adjuvanted with the aid of the solution used in the use as described above.
- the invention also relates, among other things, to the use of the solution as defined above:
- Neobor or borax pentahydrate B 4 0 7 Na 2 , 5H 2 O.
- the aminohydroxylated products used are monoethanolamine, diethanolamine and triethanolamine.
- the polyhydroxy product used is glycerin.
- the amino product used is diethylenetriamine.
- the reaction can be represented by the equation: 2 NaOH + 10 H 3 BO 3 ⁇ (B 10 O 16 Na 2 , 10H 2 O) + 6 H 2 O.
- This step can be carried out with a sodium / boric acid weight ratio generally ranging from 2.0 to 2.4. It is preferable to use stoichiometric amounts for the two reacting bodies, so that the reaction leads to the formation of the maximum possible amount of sodium pentaborate.
- the sodium hydroxide can be replaced completely or in part by at least one sodium borate to form an aqueous solution of sodium pentaborate. The amino compound is then incorporated, which gives rise to an exothermic dilution reaction. step f)
- the borate is introduced first.
- the reaction temperature can generally range up to 95 ° C, but it is in practice between 40 and 50 "C in the preferred embodiment.
- EXAMPLE H CHARACTERIZED BA ⁇ ON SOLUIIONS ACCORDING TO TESTS 1 TO 16 AND WITH THE VANTATION OF AMYLACEOUS ADHESIVE USING SAID SOLUTIONS
- Viscosity measurements a.l Viscosity ORY ⁇ %
- test 9 in a Steinhall DF formulation, in replacement of the borax powder, weight-for-weight, makes it possible to obtain a preparation of comparable characteristics. Note that for a flow viscosity of the same order of magnitude (Lory and Steinhall), obtaining a slightly higher Brookfield viscosity by using test 9.
- the biocide is: SPX ACTICIDE marketed by THOR (Bl) RS ACID marketed by THOR (B2) 30% FORMOL (B3) or ACTICIDE B 20 marketed by THOR (B4).
- the inoculum used includes:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Detergent Compositions (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96904902A EP0811044B2 (fr) | 1995-02-24 | 1996-02-23 | Solution aqueuse boree notamment pour l'adjuvantation de colle amylacee |
| AT96904902T ATE196492T1 (de) | 1995-02-24 | 1996-02-23 | Borierte, wässrige lösung insbesondere als zusatz zum stärkeklebstoff |
| DE69610412T DE69610412T3 (de) | 1995-02-24 | 1996-02-23 | Borierte, wässrige lösung insbesondere als zusatz zum stärkeklebstoff |
| US08/894,369 US6176917B1 (en) | 1995-02-24 | 1996-02-23 | Boron-containing aqueous solution particularly for addition to amyloid glue |
| AU48828/96A AU4882896A (en) | 1995-02-24 | 1996-02-23 | Boron-containing aqueous solution particularly for addition to amyloid glue |
| NO973885A NO973885D0 (no) | 1995-02-24 | 1997-08-22 | Borholdig vandig opplösning, særlig for tilsetning til amyloid lim |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9502391A FR2731008B1 (fr) | 1995-02-24 | 1995-02-24 | Solution aqueuse boree, notamment pour l'adjuvantation de colle amylacee |
| FR95/02391 | 1995-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996026252A1 true WO1996026252A1 (fr) | 1996-08-29 |
Family
ID=9476629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1996/000292 Ceased WO1996026252A1 (fr) | 1995-02-24 | 1996-02-23 | Solution aqueuse boree notamment pour l'adjuvantation de colle amylacee |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6176917B1 (fr) |
| EP (1) | EP0811044B2 (fr) |
| AT (1) | ATE196492T1 (fr) |
| AU (1) | AU4882896A (fr) |
| CA (1) | CA2212559A1 (fr) |
| DE (1) | DE69610412T3 (fr) |
| ES (1) | ES2153094T5 (fr) |
| FR (1) | FR2731008B1 (fr) |
| NO (1) | NO973885D0 (fr) |
| WO (1) | WO1996026252A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2816954A1 (fr) * | 2000-11-22 | 2002-05-24 | Innov Chimie Internat | Solution aqueuse boree, realiser a partir d'un compose d'acide borique et de carbonate de sodium |
| WO2008131499A1 (fr) * | 2007-04-26 | 2008-11-06 | Realco Sa | Procédé de traitement de la cercosporiose du bananier et composition de traitement |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2731008B1 (fr) * | 1995-02-24 | 1999-05-07 | Dev Activites Chimiques Distri | Solution aqueuse boree, notamment pour l'adjuvantation de colle amylacee |
| US6605158B1 (en) | 2001-10-12 | 2003-08-12 | Bobolink, Inc. | Radioactive decontamination and translocation method |
| US7163579B2 (en) * | 2004-04-14 | 2007-01-16 | H.B. Fuller Licensing & Financing Inc. | Method of making water resistant corrugated boards |
| FR2890957B1 (fr) * | 2005-08-11 | 2007-12-07 | Chimiquement Votre Soc Respons | Preparation boree utilisable, notamment en apport de bore actif pour la fertilisation dans le domaine agricole ou en substitution du borax pour colle amylacee |
| US7851434B2 (en) * | 2006-03-15 | 2010-12-14 | The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Amyloid and amyloid-like structures |
| FR2968648B1 (fr) * | 2010-12-13 | 2013-07-05 | Goemar Lab Sa | Solutions comprenant un complexe de bore, procede de preparation desdites solutions, leurs utilisations |
| WO2025179090A1 (fr) * | 2024-02-23 | 2025-08-28 | U.S. Borax Inc. | Solution aqueuse de bore |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3228781A (en) * | 1962-04-30 | 1966-01-11 | Viscomatic Corp | Continuous cooking and blending of starch adhesive for the corrugating industry |
| DE2401554A1 (de) * | 1974-01-14 | 1975-07-24 | Basf Ag | Mittel zur verbesserung der kaltklebekraft von holzleimen |
| BE842649A (fr) * | 1975-06-06 | 1976-12-06 | Solutions de polyborates stables, fortement concentrees, et procede pour leur preparation | |
| US4332609A (en) * | 1981-03-05 | 1982-06-01 | Standard Oil Company (Indiana) | Fertilizing plants with polyborates |
| EP0326247A2 (fr) * | 1988-01-11 | 1989-08-02 | Cerestar Holding Bv | Procédé pour apporter l'acide borique ou le borate à une zone de mélange ou de réaction |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2408332A (en) * | 1945-03-06 | 1946-09-24 | Arnold Hoffman & Co Inc | Water-soluble resinous condensates |
| BE483932A (fr) * | 1947-07-14 | |||
| US2994615A (en) * | 1957-10-09 | 1961-08-01 | Staley Mfg Co A E | Liquid laundry starch |
| US3066037A (en) * | 1962-07-02 | 1962-11-27 | Anheuser Busch | Starch product and method of making same |
| US4033914A (en) * | 1976-02-23 | 1977-07-05 | Anheuser-Busch, Incorporated | Water resistant corrugating adhesive containing aminohydroxy compound |
| SE419346B (sv) * | 1978-02-24 | 1981-07-27 | Opus Chemical Ab | Forfarande for stabilisering av bakteriologiska prover |
| US5026735A (en) * | 1988-06-08 | 1991-06-25 | Minnesota Mining And Manufacturing Company | Treatment of hazardous materials with aqueous air foam of polyhydroxy polymer |
| FR2731008B1 (fr) * | 1995-02-24 | 1999-05-07 | Dev Activites Chimiques Distri | Solution aqueuse boree, notamment pour l'adjuvantation de colle amylacee |
-
1995
- 1995-02-24 FR FR9502391A patent/FR2731008B1/fr not_active Expired - Lifetime
-
1996
- 1996-02-23 DE DE69610412T patent/DE69610412T3/de not_active Expired - Lifetime
- 1996-02-23 CA CA002212559A patent/CA2212559A1/fr not_active Abandoned
- 1996-02-23 ES ES96904902T patent/ES2153094T5/es not_active Expired - Lifetime
- 1996-02-23 US US08/894,369 patent/US6176917B1/en not_active Expired - Fee Related
- 1996-02-23 WO PCT/FR1996/000292 patent/WO1996026252A1/fr not_active Ceased
- 1996-02-23 AU AU48828/96A patent/AU4882896A/en not_active Abandoned
- 1996-02-23 AT AT96904902T patent/ATE196492T1/de not_active IP Right Cessation
- 1996-02-23 EP EP96904902A patent/EP0811044B2/fr not_active Expired - Lifetime
-
1997
- 1997-08-22 NO NO973885A patent/NO973885D0/no unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3228781A (en) * | 1962-04-30 | 1966-01-11 | Viscomatic Corp | Continuous cooking and blending of starch adhesive for the corrugating industry |
| DE2401554A1 (de) * | 1974-01-14 | 1975-07-24 | Basf Ag | Mittel zur verbesserung der kaltklebekraft von holzleimen |
| BE842649A (fr) * | 1975-06-06 | 1976-12-06 | Solutions de polyborates stables, fortement concentrees, et procede pour leur preparation | |
| US4332609A (en) * | 1981-03-05 | 1982-06-01 | Standard Oil Company (Indiana) | Fertilizing plants with polyborates |
| EP0326247A2 (fr) * | 1988-01-11 | 1989-08-02 | Cerestar Holding Bv | Procédé pour apporter l'acide borique ou le borate à une zone de mélange ou de réaction |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2816954A1 (fr) * | 2000-11-22 | 2002-05-24 | Innov Chimie Internat | Solution aqueuse boree, realiser a partir d'un compose d'acide borique et de carbonate de sodium |
| WO2008131499A1 (fr) * | 2007-04-26 | 2008-11-06 | Realco Sa | Procédé de traitement de la cercosporiose du bananier et composition de traitement |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2153094T5 (es) | 2007-11-01 |
| CA2212559A1 (fr) | 1996-08-29 |
| FR2731008A1 (fr) | 1996-08-30 |
| FR2731008B1 (fr) | 1999-05-07 |
| DE69610412T2 (de) | 2001-05-10 |
| DE69610412T3 (de) | 2007-10-31 |
| ES2153094T3 (es) | 2001-02-16 |
| US6176917B1 (en) | 2001-01-23 |
| EP0811044A1 (fr) | 1997-12-10 |
| NO973885D0 (no) | 1997-08-22 |
| EP0811044B2 (fr) | 2007-03-21 |
| AU4882896A (en) | 1996-09-11 |
| EP0811044B1 (fr) | 2000-09-20 |
| DE69610412D1 (de) | 2000-10-26 |
| ATE196492T1 (de) | 2000-10-15 |
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