EP0888395A1 - Polymeres contenant des groupes 2,3-dihydrofuranne - Google Patents

Polymeres contenant des groupes 2,3-dihydrofuranne

Info

Publication number
EP0888395A1
EP0888395A1 EP97915357A EP97915357A EP0888395A1 EP 0888395 A1 EP0888395 A1 EP 0888395A1 EP 97915357 A EP97915357 A EP 97915357A EP 97915357 A EP97915357 A EP 97915357A EP 0888395 A1 EP0888395 A1 EP 0888395A1
Authority
EP
European Patent Office
Prior art keywords
dihydrofuran
polymer
groups
derivatives
reactive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97915357A
Other languages
German (de)
English (en)
Inventor
Wolfgang Reich
Reinhold Schwalm
Erich Beck
Lukas HÄUSSLING
Oskar Nuyken
Roman-Benedikt Raether
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0888395A1 publication Critical patent/EP0888395A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification

Definitions

  • the invention relates to a polymer which can be crosslinked by high-energy radiation and which comprises 0.05 to 50% by weight, based on the polymer, of 2,3-dihydrofuran groups or derivatives of 2,3-dihydrofuran groups, calculated in each case as 2.3 Dihydrofuran, contains and a process for the production of coatings and moldings by radiation curing.
  • Radiation curing of compounds that can be polymerized by free radicals or cationic polymerization is generally known. Radiation hardening of acrylate compounds has gained special technical importance. With acrylate compounds, however, there is basically the problem that the photopolymerization is inhibited by oxygen.
  • cationically polymerizable compounds can be an alternative to the free-radically polymerizable compounds. What is required, however, is a curing rate that is comparable to the free-radically polymerizable compounds, in particular the acrylate compounds, and the application properties of the coatings or moldings obtained that are as good as possible.
  • EP-A-123 912 describes dihydropyrans as cationically polymerizable, cyclic vinyl ethers for radiation curing.
  • the rate of curing i.e. the reactivity in radiation curing, however, is still completely inadequate.
  • Dihydrofurans and their thermal, cationic polymerization are known as such, e.g. from Polymer Bulletin 28, 117-122 (1992).
  • the object of the present invention was therefore a process for the production of coatings or moldings by radiation curing, oxygen inhibition not or hardly occurring, the reactivity of the compounds used as far as possible is high and the application properties of the coatings and moldings obtained are satisfactory.
  • the 2,3-dihydrofuran groups contained in the polymer can be polymerized cationically by high-energy radiation (without oxygen inhibition), so that a molecular weight build-up or crosslinking of the polymer (briefly curing) takes place.
  • the polymer according to the invention contains 0.05 to 50% by weight, preferably 0.05 to 20 and particularly preferably 0.05 to 10% by weight, based on the total weight of the polymer, of 2,3-dihydrofuran groups or Derivatives thereof, each dihydrofuran group and each derivative of a dihydrofuran group being calculated as 2,3-dihydrofuran.
  • R 1 to R 4 independently of one another represent an H atom or a hydrocarbon radical having 1 to 15 C atoms and one of the radicals R 1 to R 4 is omitted and the bond to the polymer occurs for this purpose.
  • the radicals R 1 to R 4 are preferably an H atom or a C 1 -C 4 alkyl radical. They are particularly preferably an H atom.
  • the bond to the polymer is preferably carried out on the carbon atom of the R 2 substituent, so that R 2 in the above formula ent ⁇ falls.
  • the polymer according to the invention can be obtained by reacting polymers with functional groups (briefly called functional polymers) with 2,3-dihydrofuran derivatives which contain at least one, preferably one or two, particularly preferably one group reactive with the functional groups (briefly reactive 2, 3 -Dihydrofuran derivatives called).
  • the functional polymers can contain, for example, acid, in particular carboxylic acid, acid anhydride, in particular carboxylic acid anhydride, epoxy, halogen, in particular carboxylic acid halide, hydroxyl, primary or secondary amino or isocyanate groups which are reactive with the reactive dihydrofuran derivatives are.
  • the functional polymers are obtainable in particular by free-radical polymerization of free-radically polymerizable, ethylenically unsaturated compounds (monomers).
  • the functional polymer and thus also the polymer according to the invention is largely composed of so-called main monomers a).
  • Main monomers a) are selected from Ci-C 20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers from 1 to 10 C Atoms containing alcohols, aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers.
  • Examples include (Meth) acrylic acid alkyl esters with a C ⁇ -C ⁇ o alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
  • Suitable vinyl aromatic compounds are vinyl toluene a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers examples include Vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred.
  • Butadiene, isoprene and chloroprene may be mentioned as hydrocarbons with 2 to 8 carbon atoms and two olefinic double bonds.
  • Particularly preferred main monomers are -CC 20 alkyl (meth) acrylates.
  • the functional polymer preferably consists of at least 30, in particular at least 50 and particularly preferably at least 70% by weight of the main monomers.
  • the functional polymer contains monomers b) with the above-mentioned functional groups, which react with the reactive 2,3-dihydrofuran derivatives.
  • monomers b) e.g. called: (meth) acrylic acid, maleic acid, itaconic acid, maleic anhydride, glycidyl (meth) acrylate, isocyanatoalkyl (meth) acrylates, aminoalkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
  • the proportion of monomer b) generally corresponds to the desired content of 2,3-dihydrofuran groups of the formula I, i.e. the amount of functional groups in the polymer is preferably equimolar to the reactive groups of the reactive 2,3-dihydrofuran derivatives.
  • the functional polymer may also contain further monomers c), e.g. crosslinking monomers such as divinylbenzene.
  • the radical polymerization to produce the functional polymer can e.g. in solution, e.g. an organic solvent (solution polymerization) in aqueous dispersion (emulsion polymerization, suspension polymerization) or in bulk, i.e. be carried out essentially in the absence of water or organic solvents (bulk polymerization).
  • solution polymerization e.g. an organic solvent
  • emulsion polymerization emulsion polymerization, suspension polymerization
  • bulk i.e. be carried out essentially in the absence of water or organic solvents
  • the emulsion polymerization may, for example, batchwise, with or without the use of seed latices, by initially introducing all or individual ⁇ ner components of the reaction mixture, or, preferably, with partial initial and subsequent metering of the constituents or individual constituents of the reaction mixture, or by the metering process without initial be performed.
  • the monomers can be polymerized in the emulsion polymerization as usual in the presence of a water-soluble initiator and an emulsifier at preferably 30 to 95 ° C.
  • Suitable initiators are, for example, sodium, potassium and ammonium persulfate, tert. -Butyl hydroperoxides, water-soluble azo compounds or redox initiators such as H 2 0 2 / ascorbic acid. 5
  • Other suitable emulsifiers are reaction products of alkylene oxides, in particular ethylene or propylene oxide, with fatty alcohols, fatty acids or phenol, or alkylphenols.
  • the copolymer is first prepared by solution polymerization in an organic solvent and then with the addition of salt formers, e.g. from copolymers containing ammonia to carboxylic acid groups, dispersed in water without the use of an emulsifier or dispersant.
  • the organic solvent can be distilled off.
  • the preparation of aqueous secondary dispersions is known to the person skilled in the art and e.g. described in DE-A37 20 860.
  • Regulators can be used in the polymerization to adjust the molecular weight. Suitable are e.g. -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerol, ethyl thioglycolate, methyl thioglycolate and tert. -Dodecyl mercaptan.
  • the solids content of the polymer dispersions obtained is preferably 40 to 80% by weight, particularly preferably 45 to 75
  • High polymer solids can e.g. according to the methods described in German patent application P 4 307 683.1 or EP 37 923.
  • a particularly preferred polymerization method is solution polymerization.
  • the solution polymerization can be carried out continuously, discontinuously as a batch process or, preferably, semi-continuously in the feed process. In the latter case, some of the monomers are initially charged, heated to the polymerization temperature and the rest of the monomers are fed in continuously.
  • Alcohols such as i-butanol, i-propanol, aromatics such as toluene or xylene, ethers such as dioxane or tetrahydrofuran, ketones such as acetone, cyclohexanone or esters such as ethyl acetate or n-butyl acetate can be used.
  • Preferred initiators are dibenzoyl peroxide, tert. Butyl perpivalate, tert. -Butylper-2-ethylhexanoate, tert. -Amyl-2-ethyl-hexyl peroxide, di-tert. -butyl peroxide, tert.
  • part of the polymerization batch is generally initially charged and heated to the polymerization temperature, after which the remainder is fed in continuously.
  • the functional polymer is obtained in the form of an aqueous dispersion of the polymer, a solution in an organic solvent or essentially free of water and solvents.
  • the polymer is particularly preferably used essentially free of water and solvents.
  • the polymer is preferably produced by solution polymerization with subsequent removal of the solvent or water or by bulk polymerization.
  • the functional polymer preferably has a number average molecular weight M n of from 500 to 50,000, particularly preferably from 500 to 20,000 and very particularly preferably from 1000 to 10,000.
  • the functional polymer preferably has a uniformity calculated as the quotient M w (weight-average molecular weight) / M n of ⁇ 4.
  • M w and M n are determined by gel permeation chromatography.
  • the functional polymer is preferably reacted with the reactive 2,3-dihydrofuran derivatives.
  • the reactive 2,3-dihydrofuran derivatives are in particular those which, for example, contain a hydroxyl, carboxyl or halogen group.
  • the reactive 2, 3-dihydrofuran derivatives can contain one dihydrofuran ring or also several dihydrofuran rings, which are connected directly or via organic bridge members.
  • each dihydrofuran ring, calculated as dihydrofuran is included in the calculation of the proportion by weight of the dihydrofuran groups (see above).
  • Particularly preferred reactive dihydrofuran derivatives are those of the formula
  • R 1 to R 4 independently of one another represent an H atom or a hydrocarbon radical having 1 to 15 C atoms, but one of the radicals R 1 to R 4 is omitted and the group R 5 -X takes its place.
  • R 5 stands for a single bond or an organic group with 1 to 20 C atoms
  • X stands for a hydroxyl group OH or a carboxyl group COOH or a halogen, for example chlorine or bromine.
  • R 2 is preferably omitted in the above formula I and is replaced by the group R 5 -X.
  • the radicals R 1 to R 4 are preferably H atoms.
  • R 5 is in particular a single compound (R 5 is therefore omitted in formula I) or a Ci-Cirj, preferably Ci-C 4 alkylene group.
  • reactive 2,3-dihydrofuran derivatives include 3-hydroxymethyl-2,3-dihydrofuran or 3-carboxymethyl-2, 3-dihydrofuran or its salt, e.g. Na salt, or 3-bromo (or 3-chloro) methyl-2,3-dihydrofuran.
  • reaction takes place e.g. with functional polymers which contain carboxylic acid, carboxylic anhydride or carboxylic acid chloride groups, isocyanate, epoxy or halogen groups.
  • reaction takes place, for example, with functional polymers which contain hydroxyl groups, epoxy or isocyanate groups.
  • the functional polymers are reacted with the reactive dihydrofuran derivatives preferably in an organic solvent, for example tetrahydrofuran, toluene, etc.
  • the reaction involves conventional organic reactions, e.g. esterification (in the case of hydroxyl groups on the one hand and carboxylic acid or carboxylic anhydride or carboxylic acid chloride groups as the reaction partner), or reaction of carboxylic acid groups with epoxide groups, to form urethane (in the case of isocyanate groups and hydroxyl groups as the reaction partner).
  • esterification in the case of hydroxyl groups on the one hand and carboxylic acid or carboxylic anhydride or carboxylic acid chloride groups as the reaction partner
  • reaction of carboxylic acid groups with epoxide groups to form urethane (in the case of isocyanate groups and hydroxyl groups as the reaction partner).
  • reaction types which are well known to the person skilled in the art, can be catalyzed acidic or basic and, if appropriate, accelerated by increasing the temperature.
  • the polymers according to the invention can be cationically polymerized or crosslinked, briefly cured, on account of the content of 2,3-dihydrofuran groups.
  • the cationic curing can be initiated thermally or, preferably, photochemically.
  • the polymers according to the invention are preferably suitable as or in radiation-curable compositions, for example for the production of coatings or moldings.
  • the radiation-curable compositions can also contain further radiation-curable, cationically or free-radically polymerizable compounds.
  • the radiation-curable compositions according to the invention contain 1 to 100% by weight, preferably 10 to 100, particularly preferably 40 to 100% by weight and very particularly preferably 70 to 100% by weight, based on the cationically and optionally radically polymerizable Compounds, the polymers of the invention.
  • further cationically polymerizable compounds include, in particular, linear or cyclic vinyl ethers, for example vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, vinyl octadecyl ether, vinyl cyclohexyl ether, and ⁇ -methyl-vinyl alkyl ether, in particular also 2,3-dihydrofuran and 2,3- Dihydrofuran derivatives such as those listed above in German patent application P 19539294.9 are also considered.
  • linear or cyclic vinyl ethers for example vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether, vinyl octadecyl ether, vinyl cyclohexyl ether, and ⁇ -methyl-vinyl alkyl ether, in particular also 2,3-dihydrofuran and 2,3- Dihydrofuran derivatives such as those listed above in German patent application P
  • epoxides for example cyclopentene oxide, cyclohexene oxide, epoxidized polybutadiene, epoxidized soybean oil, Degacure K 126 or glycidyl ether, for example butanediol diclycidyl ether, hexanediokiglycidyl ether, for example biphenol-A diglycidyl ether, pentaerytylthritol big acid.
  • epoxides for example cyclopentene oxide, cyclohexene oxide, epoxidized polybutadiene, epoxidized soybean oil, Degacure K 126 or glycidyl ether, for example butanediol diclycidyl ether, hexanediokiglycidyl ether, for example biphenol-A diglycidyl ether, pentaerytylthritol big acid.
  • Cationically polymerizable monomers such as unsaturated aldehydes and ketones, dienes such as butanediene, vinyl aromatics such as styrene, N-substituted vinylamines such as vinyl carbazole, cyclic ethers such as tetrahydrofuran can also be used.
  • free-radically polymerizable compounds or both free-radically and cationically polymerizable compounds can also be used.
  • free-radically polymerizable compounds or both free-radically and cationically polymerizable compounds can also be used.
  • Trimethylolpropane triacrylate dipropylene glycol diacrylate, tripropylene glycol diacrylate, hexanediol diacrylate or polyester, polyether, epoxy or urethane acrylates.
  • (meth) acrylate compounds with 2 to 6, particularly preferably 2 to 4 (meth) acrylic groups.
  • the molecular weight of the acrylate compounds is preferably below 5000, particularly preferably below 3000 g / mol.
  • Unsaturated polyesters are also suitable as radical-polymerizable compounds.
  • the radiation-curable compositions preferably contain a photoinitiator for photopolymerization.
  • the total amount of the photoinitiator is preferably 0.1 to 10, particularly preferably 0.5 to 5% by weight, based on the total amount of the compounds which can be cationically and optionally radically polymerized.
  • Photoinitiators for cationic photopolymerization when irradiated with UV light, provide acids, called its aryldiazonium, aryliodonium or arylsulfonium salts, disulfones, diazodisulfones, imidotriflates or benzointosylates of the following structures:
  • Exemplary p-Methoxybenzoldiazoniumhexafluoro ⁇ be further phosphate, Benzoldiazoniumtetrafluoroborat, Toluoldiazoniumtetra- fluoroarsenat, diphenyliodonium hexafluoroarsenate, hexafluorophosphate Triphenylsulfo-, Benzolsulfoniumhexafluorophosphat, toluenesulfonic olsulfoniumhexafluorophosphat or Degacure KI85 (bis [4-diphenyl sulfonio-phenyl] sulfide-bis-hexafluorophosphate), isoquinolinium salts , Phenylpyridiniumsalze or Picoliniumsalze, such as M-ethoxy-isochinoliniumhexafluorophosphat, N-ethoxy-4-phenylpyri diniumhexafluoro
  • the radiation-curable compositions also contain compounds which can be polymerized by free radicals, photoinitiators for free-radical photopolymerization are also preferably used, depending on the content of these compounds.
  • photoinitiators exclusively for free-radical polymerization, in particular if the proportion of free-radically polymerizable compounds is greater than 50 mol%, based on the total amount of the polymerizable compounds.
  • Suitable photoinitiators for radical polymerization are, for example, benzophenone and derivatives thereof, such as, for example, alkylbenzophenones, halogen-methylated benzophenones, Michler's ketone and benzoin and benzoin ethers such as ethylbenzoin ether.
  • Benzyl ketals such as benzil dimethyl ketal, acetone phenone derivatives such as hydroxy-2-methyl-l-phenylpropan-l-one and hydroxycyclohexyl phenyl ketone.
  • Anthraquinone and its derivatives such as methylanthra quinone and especially acylphosphine oxides such as Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and bisacylphosphine oxides.
  • acylphosphine oxides such as Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and bisacylphosphine oxides.
  • the radiation-curable compositions are used to produce coatings on the substrates to be coated, e.g. applied from wood, paper, plastic or metal or brought into the intended shape for the production of moldings.
  • the radiation-curable compositions can contain the additives customary for the respective intended use.
  • this can e.g. Leveling agents, enhancers, pigments or fillers.
  • UV curing is preferably carried out with UV light. Suitable for this are e.g. UV lamp with a wavelength range of 240 to 400 nm and a power of 50 to 240 W / cm.
  • the radiation-curable compositions are particularly preferably suitable for the production of coatings on wood, plastic, paper, metal, where they are crosslinked by electron beams or, after the addition of photoinitiators, by UV radiation, i.e. are cured and give coatings that meet the requirements for protective coatings or decorative coatings.
  • the radiation-curable compositions have a high reactivity, i.e. high curing speed in radiation curing.
  • the coatings or moldings obtained have good performance properties.
  • the mixture is stirred for 12 hours at room temperature, then 1 ml of a 1 molar sodium methylate solution in tetrahydrofuran (a little methanol to improve the solubility) is added and the mixture is stirred for a further 30 minutes.
  • the polymer is precipitated in 500 ml of n-hexane.
  • the crosslinking product is washed with methanol and dried in vacuo at 60 ° C. for 48 hours.
  • the product obtained is insoluble and could only be characterized by IR spectroscopy.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Polymère réticulable par rayonnement riche en énergie, contenant 0,1 à 50 % en poids, par rapport au polymère, de groupes 2,3-dihydrofuranne ou de dérivés de groupes 2,3-dihydrofuranne, calculés chaque fois en tant que 2,3-dihydrofuranne.
EP97915357A 1996-03-22 1997-03-10 Polymeres contenant des groupes 2,3-dihydrofuranne Withdrawn EP0888395A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19611349A DE19611349A1 (de) 1996-03-22 1996-03-22 Polymerisate mit 2,3-Dihydrofurangruppen
DE19611349 1996-03-22
PCT/EP1997/001206 WO1997035907A1 (fr) 1996-03-22 1997-03-10 Polymeres contenant des groupes 2,3-dihydrofuranne

Publications (1)

Publication Number Publication Date
EP0888395A1 true EP0888395A1 (fr) 1999-01-07

Family

ID=7789104

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97915357A Withdrawn EP0888395A1 (fr) 1996-03-22 1997-03-10 Polymeres contenant des groupes 2,3-dihydrofuranne

Country Status (5)

Country Link
US (1) US6143233A (fr)
EP (1) EP0888395A1 (fr)
JP (1) JP2000508004A (fr)
DE (1) DE19611349A1 (fr)
WO (1) WO1997035907A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59610655D1 (de) * 1995-10-23 2003-09-18 Basf Ag Strahlungshärtung von Dihydrofuranderivaten
FR2829970B1 (fr) * 2001-09-27 2004-05-14 Michelin Soc Tech Bande de roulement pour pneumatique
EP1918309A1 (fr) * 2006-10-30 2008-05-07 Sika Technology AG Composition durcissable radicalairement comprenant un monomère polymérisable et un générateur de radicaux

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3881935A (en) * 1971-01-07 1975-05-06 Powers Chemco Inc Photosensitive polymer composition
US4060685A (en) * 1972-11-08 1977-11-29 Fuji Photo Film Co., Ltd. Furanacroyl esters
US4079038A (en) * 1976-03-05 1978-03-14 Alza Corporation Poly(carbonates)
EP0076158B1 (fr) * 1981-09-30 1989-10-25 National Research Development Corporation Compositions comprenant des particules encapsulées
CA1225789A (fr) * 1983-02-15 1987-08-18 Zoilo C. Tan Polymeres et resits sensibles aux faiseaux electroniques et aux rayons x
US4645781A (en) * 1983-03-29 1987-02-24 Union Carbide Corporation Blends of cyclic vinyl ether containing compounds and expoxides
US4816496A (en) * 1984-06-26 1989-03-28 Kabushiki Kaisha Toshiba Photocurable composition
US5102771A (en) * 1990-11-26 1992-04-07 Minnesota Mining And Manufacturing Company Photosensitive materials
JPH05339373A (ja) * 1992-06-11 1993-12-21 Hitachi Chem Co Ltd 耐熱性感光材料
DE19539294A1 (de) * 1995-10-23 1997-04-24 Basf Ag Strahlungshärtung von Dihydrofuranderivaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9735907A1 *

Also Published As

Publication number Publication date
WO1997035907A1 (fr) 1997-10-02
US6143233A (en) 2000-11-07
DE19611349A1 (de) 1997-09-25
JP2000508004A (ja) 2000-06-27

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