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EP1622946A1 - Polyvinylacetals reticules - Google Patents

Polyvinylacetals reticules

Info

Publication number
EP1622946A1
EP1622946A1 EP03785800A EP03785800A EP1622946A1 EP 1622946 A1 EP1622946 A1 EP 1622946A1 EP 03785800 A EP03785800 A EP 03785800A EP 03785800 A EP03785800 A EP 03785800A EP 1622946 A1 EP1622946 A1 EP 1622946A1
Authority
EP
European Patent Office
Prior art keywords
formula
carbon atoms
weight
compound
structural units
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Withdrawn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
EP03785800A
Other languages
German (de)
English (en)
Inventor
Bernd Papenfuhs
Martin Steuer
Matthias Gutweiler
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.)
Kuraray Europe GmbH
Original Assignee
Kuraray Specialities Europe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10319201A external-priority patent/DE10319201A1/de
Application filed by Kuraray Specialities Europe GmbH filed Critical Kuraray Specialities Europe GmbH
Publication of EP1622946A1 publication Critical patent/EP1622946A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F8/28—Condensation with aldehydes or ketones

Definitions

  • the present invention relates to crosslinked polyvinyl acetals, processes for their preparation and their use, in particular for laminated safety glasses.
  • the modification of polyvinyl alcohol by means of acetalization, especially with n-butyraldehyde, is a reaction which has been known and used for a long time.
  • Films of the polyvinyl acetals obtainable in this way, in particular polyvinyl butyrals, are used as intermediate layers in laminated safety glasses, in particular in automobile windows (front and side windows), because of their high light resistance and their very good adhesive properties.
  • laminated glasses offer a high degree of safety, since in the event of an impact, the elastic polyvinyl acetal film absorbs the mechanical energy and the glass fragments which may arise remain stuck to the film.
  • laminated safety glasses based on conventional polyvinyl acetal types often have inadequate mechanical properties, especially at higher temperatures above 150 ° C.
  • This problem can also only be solved with difficulty with the use of polyvinyl acetals with higher molecular weights, since at this point there is a lack of processing problems (eg blistering, too high or too low viscosity of the polyvinyl acetals at the processing temperature) Constancy of properties during processing) usually reaches the limits of what is practically feasible.
  • the European patent application EP 0 211 818 AI proposes to use polyvinyl butyrals which have been crosslinked using aldehydes having at least two aldehyde groups via intermolecular diacetal linkages before or during the acetalization reaction of the polyvinyl alcohol with the butyraldehyde.
  • this type of crosslinking leads to highly crosslinked, very high molecular weight and therefore partially insoluble polyvinyl butyrals, which are only of limited use, if at all, for the production of high-quality laminated safety glasses.
  • the polyvinyl butyrals crosslinked by di- or polyaldehydes are not sufficiently stable under the conditions of the thermoplastic processing of the polymer (e.g. extrusion), which is why, depending on the temperatures, residence times, shear rates, etc., a more or less pronounced cleavage the crosslinking sites (molecular weight reduction) takes place.
  • This lack of thermal stability in particular makes it difficult to produce reproducible product qualities, since the polymer reacts extremely sensitively to process fluctuations, and furthermore leads to a deterioration in the mechanical properties of the polyvinyl acetals, especially at higher temperatures.
  • polyvinyl acetals with improved mechanical properties, in particular at higher temperatures, preferably greater than 150 ° C.
  • the polyvinyl acetals according to the invention should be suitable in particular for the production of films and in particular for the production of high-quality laminated safety glasses, and for this reason preferably an improved constancy of the material properties, especially the mechanical properties during processing into films and composite safety glasses.
  • the present invention was also based on the object of specifying a process for producing the polyvinyl acetals according to the invention which can be carried out in a simple manner, on an industrial scale and at low cost.
  • a further object of the present invention was to be seen in showing particularly suitable fields of application of the polyvinyl acetals according to the invention.
  • R 1 is hydrogen or methyl, b.) 0 to 99.0% by weight of structural units of the formula (2)
  • R 2 represents hydrogen or an alkyl radical having 1 to 6 carbon atoms, c.) 0 to 70.0% by weight of structural units of the formula (3)
  • R 3 , R 4 , R 5 and R 6 each independently of one another, have a radical
  • R 7 is a bond, an alkylene group with 1 to 10
  • Carbon atoms or an optionally substituted arylene group having 6 to 12 carbon atoms and R 8 is hydrogen, COOH, a
  • a polymer (A2) is crosslinked which, based on its total weight, a.) 1.0 to 99.9% by weight of structural units of the formula (1) b. ) 0 to 99.0% by weight of structural units of the formula (2) c.) 0 to 70.0% by weight of structural units of the formula (3), where
  • R 10 and R 11 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 12 carbon atoms, (ii) adding at least one compound of the formula (4b),
  • R 7 is a bond, an alkylene group with 1 to 10
  • Carbon atoms or an optionally substituted arylene group having 6 to 12 carbon atoms and R 8 is hydrogen, COOH, a Is alkyl group with 1 to 10 carbon atoms or an optionally substituted aryl group with 6 to 12 carbon atoms, (iii) adds a polyaldehyde of formula (5), and
  • crosslinked polyvinyl acetals according to the invention have a number of further advantages. These include a .:
  • the polyvinyl acetals according to the invention are distinguished by an improved constancy of their material properties, in particular of their mechanical properties, such as, for example, their storage module. This advantage can be observed in particular at higher temperatures, in particular above 150 ° C. A change in the crosslinking density as in EP 0 211 818 A1 cannot be observed in the context of the present invention; on the contrary, the polyvinyl acetals according to the invention have a significantly improved constancy of their crosslinking density even at higher temperatures, in particular above 150 ° C.
  • the crosslinked polyvinyl acetals according to the invention can be produced very quickly and gently, so that, owing to the high molecular weights of the polyvinyl acetals at the beginning, very short extrusion distances or extruder residence times can be selected.
  • the polyvinyl acetals according to the invention are particularly suitable for laminated safety glasses, which can be produced in a simple manner, on an industrial scale and inexpensively, in particular by an extrusion process.
  • the main advantage is that the use of the polyvinyl acetals according to the invention largely avoids both the formation of bubbles and fluctuations in properties during processing and thus makes laminated safety glasses with improved optical and mechanical properties accessible with high reproducibility.
  • the present invention relates to polyvinyl acetals which can be obtained starting from a polymer (AI) which, based on its total weight, a) has from 1.0 to 99.9% by weight of structural units of the formula (1) b.) 0 to 99.0% by weight of structural units of the formula (2)
  • the structural unit of the formula (3) does not include the structural units of the formula (1), (2) and / or (4a).
  • the radical R 1 each independently represents hydrogen or methyl, preferably hydrogen.
  • the radical R 2 denotes hydrogen or an alkyl radical with 1 to 6 carbon atoms, preferably an alkyl radical with 1 to 6 carbon atoms, advantageously a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl -, tert-butyl, n-pentyl or an n-hexyl group, advantageously a methyl or an ethyl group, in particular a methyl group.
  • the radicals R 3 , R 4 , R 5 and R 6 are each, independently of one another, radicals with a molecular weight in the range from 1 to 500 g / mol, advantageously hydrogen, an optionally branched, aliphatic or cycloaliphatic radical with 1 to 16 carbon atoms, which, if appropriate may contain one or more carboxylic acid amide and / or sulfonic acid groups.
  • the radical R 7 is a bond, an alkylene group with 1 to 10 carbon atoms or an optionally substituted arylene group with 6 to 12 carbon atoms, advantageously hydrogen or a methylene, ethylene, n-propylene, iso-propylene, n-butylene , sec-butylene, tert-butylene, n-pentylene or an n-hexylene group, which may optionally have one or more COOH groups as a substituent.
  • the radical R 8 denotes hydrogen, a carboxyl group or an alkyl group with 1 to 10 carbon atoms or an optionally substituted aryl group with 6 to 12 carbon atoms, advantageously hydrogen or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, sec-butyl, tert-butyl, n-pentyl or an n-hexyl group, which may optionally have one or more COOH groups as a substituent.
  • Particularly preferred R 8 radicals include hydrogen, a methyl group and -CH 2 COOH.
  • Particularly preferred structural units of the formula (3) are derived from straight-chain or branched olefms having 2 to 18 carbon atoms, (meth) acrylamides and / or ethylene sulfonic acid.
  • olefins especially those with a terminal CC double bond, which preferably have 2 to 6 carbon atoms, especially ethylene. proven to be particularly cheap.
  • structural units (3) which are derived from acrylamidopropenylsulfonic acid (AMPS) also lead to very particularly advantageous results according to the invention.
  • Particularly preferred structural units of the formula (4) can be obtained by acetalizing structural units of the formula (1) with glyoxylic acid.
  • the present invention relates to polyvinyl acetals which can be obtained from a polymer (A2) which, based on its total weight, a.) 1.0 to 99.9% by weight of structural units of the formula (1) b. ) 0 to 99.0% by weight of structural units of the formula (2) c.) 0 to 70.0% by weight of structural units of the formula (3).
  • the structural unit of the formula (3) does not include the structural units of the formula (1) and / or (2).
  • radicals R 1 to R 6 are defined as already described above.
  • composition of the polymers (AI) and / or (A2) the following preferably applies:
  • the total number of structural units of the formula (2) is preferably in the range from 0.1 to 40 mol%, advantageously in the range from 0.5 to 25.0 mol%, in particular in the range from 1.0 to 15.0 mol -%, each based on the total number of structural units of the formula (1) and (2).
  • polymers (AI) and / or (A2) are used, which are based on the total number Structural units of the formula (1) and (2) contain 1.0 to 2.0 mol% of structural units of the formula (2).
  • polymers (AI) and / or (A2) are used which, based on the total number of structural units of the formula (1) and (2), 3.0 to 7.0 mol structural units of the formula ( 2) included.
  • polymers (AI) and / or (A2) are used which, based on the total number of structural units of the formula (1) and (2), 10.0 to 15.0 mol% of structural units of the formula (2) included.
  • the polymers (AI) and / or (A2) based in each case on their total weight, contain> 50.0% by weight, advantageously> 60.0% by weight, advantageously> 70 , 0 wt .-%, in particular> 80.0 wt .-% of structural units of the formula (1) and / or (2).
  • Particularly advantageous results can be achieved with polymers (AI) and / or (A2) which, based in each case on their total weight, are> 85.0% by weight, expediently> 90.0% by weight, advantageously> 95, 0% by weight, in particular> 99.0% by weight, of structural units of the formula (1) and / or (2).
  • the polymers (AI) and / or (A2) can have a syndiotactic, isotactic and / or atactic chain structure. Furthermore, it can exist both as a random and as a block copolymer.
  • the viscosity of the polymers (AI) and / or (A2) is of minor importance according to the invention; in principle, both low-molecular and high-molecular polymers (AI) and / or (A2) can be used. Nevertheless, it has proven to be particularly advantageous in the context of the present invention that the polymers (AI) and / or (A2) have a viscosity in the range from 1 to 70 mPas, preferably in the range from 2 to 40 mPas, in particular in the Range from 3 to 30 mPas (measured as a 4% by weight aqueous solution according to Höppler at 20 ° C, DIN 53015).
  • polymers (AI) or (A2) are not subject to any particular restrictions with regard to their molecular weight, but for the purposes of the present invention, polymers (AI) and / or (A2) with a weight average molecular weight of at least 20,000 g / mol have become very special proven.
  • the weight average molecular weight is preferably determined by means of gel permeation chromatography, expediently using a polyethylene oxide calibration.
  • the polymers (AI) and / or (A2) to be used according to the invention can be prepared in a manner known per se in a multi-stage process.
  • a first step the corresponding vinyl ester is radically polymerized in a suitable solvent, usually water or an alcohol, such as methanol, ethanol, propanol and / or butanol, using a suitable radical initiator. If the polymerization is carried out in the presence of free-radically copolymerizable monomers, the corresponding vinyl ester copolymers are obtained.
  • the vinyl ester (co) polymer is then saponified in a second step, usually by transesterification with methanol, it being possible to set the degree of saponification in a manner known per se, for example by varying the catalyst concentration, the reaction temperature and / or the reaction time.
  • a second step usually by transesterification with methanol, it being possible to set the degree of saponification in a manner known per se, for example by varying the catalyst concentration, the reaction temperature and / or the reaction time.
  • the current specialist literature in particular to Ulimann's Encyclopedia of Industrial Chemistry, Fifth Edition on CD-Rom Wiley-VCH, 1997, Keyword: Poly (Vinyl Acetals) and the literature references specified therein.
  • the polymers (Al) can then be obtained by reaction and acetalization with a compound of the formula (4b)
  • R 7 is a bond, an alkylene group with 1 to 10
  • Carbon atoms or an optionally substituted arylene group having 6 to 12 carbon atoms and R 8 is hydrogen, COOH, a
  • the reaction of the polyvinyl alcohol with the compound (4b) is preferably carried out in at least one inert solvent, the term “inert solvent” meaning those solvents which, under the respective reaction conditions, do not interfere with or even prevent the desired reaction from proceeding
  • inert solvent meaning those solvents which, under the respective reaction conditions, do not interfere with or even prevent the desired reaction from proceeding
  • a particularly useful solvent is water.
  • the reaction is conveniently carried out in the presence of acidic catalysts.
  • Suitable acids include both organic acids, such as acetic acid, and mineral acids, such as hydrochloric acid, sulfuric acid and / or nitric acid, the use of hydrochloric acid, sulfuric acid and / or nitric acid having proven particularly useful in industry.
  • the reaction is preferably carried out in such a way that the polyvinyl alcohol is initially introduced in aqueous solution, the compound (4b) is introduced into this solution and then the acidic catalyst is added dropwise.
  • the crosslinked polyvinyl acetals are obtained by, in any order, (i) reacting the polymer (AI) with at least one polyaldehyde of the formula (5)
  • R 9 (CHO) n (5) and (ii) at least partially esterified groups of the formula (1) and the formula (4a) with one another.
  • R 9 denotes a bond or a radical having 1 to 40 carbon atoms, preferably an aliphatic, cycloaliphatic and / or aromatic group with expediently 1 to 20, preferably 1 to 12, in particular 2 to 10, carbon atoms.
  • n is an integer greater than or equal to 2, preferably in the range from 2 to 10, advantageously in the range from 2 to 6, in particular 2 or 3. According to a very particularly preferred embodiment of the present invention, n is 2.
  • Compounds of the formula (5) which are very particularly suitable according to the invention include glyoxyl, propanedial, n-butanedial, glutardialdehyde, n-hexanedial, n-heptanedial, n-octanedial, n-nonadial, n-decanedial, n-undecanedial, n-dodecanedial, 4 , 4'-ethylenedioxydibenzaldehyde and 2-hydroxyhexanedial, in particular glutardialdehyde and n-nonandial.
  • the amount of polyaldehyde (5) can in principle be chosen arbitrarily in the context of the present invention, but it has proven particularly useful for the purposes of the present invention, based on the total weight of polymer (Al), 0.001 to 1.0% by weight. %, advantageously 0.005 to 2.0% by weight, in particular 0.01 to 1.0% by weight, of polyaldehyde (5).
  • Steps (i) and (ii) can be carried out in any order, that is, it is possible to first carry out step (i) and then step (ii) or first step (ii) and then step (i) or both at the same time Steps. However, for the purposes of the present invention, it has proven to be particularly advantageous to carry out step (i) first and then step (ii).
  • At least one compound of the formula (6) is further added at any time
  • the radicals R 10 and R 11 are each independently hydrogen, an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 12 carbon atoms. These alkyl and aryl radicals can be substituted with one or more hydroxyl, sulfonic acid groups and / or halogen atoms, such as fluorine, chlorine, bromine, iodine.
  • the preferred compounds of formula (6) include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-ethoxybutyraldehyde, paraldehyde, 1,3,5-trioxane, capronaldehyde, 2-ethylhexanal, pelargonaldehyde, 3.5, 5- trimethylhexanal, 2-formylbenzenesulfonic acid, acetone, ethyl methyl ketone, butyl ethyl ketone and / or ethyl hexyl ketone.
  • the ratio of components (5) and (6) is preferably chosen as follows
  • reaction of the polymer (AI) with the compound (5) and / or (6) is preferably carried out in at least one inert solvent, the term “inert solvent” standing for those solvents which, under the respective reaction conditions, do not mean the desired reaction Water is a particularly useful solvent in this context.
  • the reaction is also conveniently carried out in the presence of acidic catalysts.
  • Suitable acids include both organic acids, such as acetic acid, and mineral acids, such as hydrochloric acid, sulfuric acid and / or nitric acid, the use of hydrochloric acid, sulfuric acid and / or nitric acid having proven particularly useful in industry.
  • the reaction is preferably carried out in such a way that the polymer (AI) is initially introduced in an aqueous solution, the compound (5) and / or (6) is introduced into this solution and the acidic catalyst is then added dropwise.
  • crosslinked polyvinyl acetals are obtained by
  • esterification (ii) and / or (iv) can be carried out in a manner known per se, although it has proven to be particularly advantageous in the context of the present invention to crosslink, if appropriate in the presence of at least one plasticizer, at melt temperatures in the range from 80 to 280 ° C, preferably in the range from 120 to 280 ° C, in particular in the range from 140 to 260 ° C, thermally.
  • the thermal crosslinking of the polyvinyl acetal can be carried out using all heatable units known to the person skilled in the art, such as Ovens, kneaders, extruders, presses or autoclaves. However, the thermal crosslinking is preferably carried out in extruders or in kneading units, since these ensure good homogenization with the plasticizer (s) which is / are contained in a preferred embodiment.
  • the crosslinking is recognizable by the higher molecular weight of the crosslinked polyvinyl acetal compared to the uncrosslinked polyvinyl acetal.
  • the degree of networking - depending on the application - can be chosen freely. Nevertheless, in the context of the present invention it has proven to be particularly expedient that at least 10 mol%, preferably at least 20 mol%, expediently at least 30 mol%, in particular at least 40 mol%, of all carboxyl groups originally contained in the polyvinyl acetal are esterified become.
  • the content of carboxyl groups, based on the total weight of the crosslinked polyvinyl acetal, is preferably less than or equal to 10.0% by weight and is preferably in the range from 0.00001 to 10.0% by weight, particularly preferably in the range from 0.001 to 10.0% by weight, advantageously in the range from 0.01 to 5.0% by weight and in particular in the range from 0.01 to 2.0% by weight.
  • the crosslinked polyvinyl acetals according to the invention contain plasticizers. All plasticizers known to the person skilled in the art can be used as plasticizers. The plasticizer is used in customary amounts known to the person skilled in the art.
  • plasticizers for polyvinyl acetals are the esters of aliphatic mono- and dicarboxylic acids with mono- or polyhydric alcohols or oligoalkylene glycol ethers, phosphoric acid esters and various phthalates, as are disclosed, for example, in US Pat. No. 5,137,954.
  • the diesters of di-, tri- and tetraethylene glycols with aliphatic monocarboxylic acids, adipic acid dialkyl esters and the dibenzoates of alkylene and polyalkylene glycols described in the unpublished DE-A-101 00 681 are preferably used.
  • crosslinked polyvinyl acetals Possible areas of use of the crosslinked polyvinyl acetals according to the invention are obvious to the person skilled in the art. They are particularly suitable for all applications which are drawn for crosslinked polyvinyl acetals, in particular for polyvinyl formals and / or polyvinyl butyrals. Particularly preferred fields of application include their use as films, in particular for laminated glasses, which can preferably be produced by direct extrusion with the aid of slot dies. Further details on the extrusion of polyvinyl acetals and on the production of polyvinyl acetal, in particular polyvinalbutyral, films are well known to the person skilled in the art from the specialist literature.
  • a particularly preferred area of application of the polyvinyl acetals according to the invention in the context of the present invention is flat structures, in particular films, preferably with a thickness in the range from 0.5 ⁇ m to 1 mm.
  • the films according to the invention can contain further, conventional additives, such as, for example, oxidation stabilizers, UN stabilizers, dyes, fillers, pigments and / or non-stick agents.
  • the polyvinyl acetals according to the invention are also particularly suitable for the coating of substrates, in particular of wood, metal, plastic, glass, textiles, paper, leather and ceramic and mineral substrates.
  • the present invention therefore also relates to coatings comprising the polyvinyl acetals according to the invention.
  • the coatings can furthermore polymer resins, plasticizers, pigments, fillers, stabilizers, adhesion improvers, rheological aids, pH-influencing additives and / or additives which catalyze chemical reactions both between the polyvinyl acetal according to the invention and other polymer resins and also between the other polymer resins, contain.
  • the coating according to the invention can be carried out in a manner known per se both as a powder, which is then preferably melted and crosslinked at elevated temperature, and also, preferably from an organic solution, by means of coating processes known to the person skilled in the art.
  • the polyvinyl acetal to be crosslinked according to the invention is preferably dissolved in the solvent or solvent mixture and then onto the substrate to be coated, if appropriate together with further binders and optionally other constituents, such as, for example, plasticizers, pigments, fillers, stabilizers, adhesion improvers, theological auxiliaries applied.
  • the crosslinking according to the invention is preferably carried out after evaporation of the solvent, advantageously at a temperature in the range from 20 to 200 ° C.
  • the crosslinking reaction is advantageously supported by pH-lowering additives, such as organic and / or inorganic acids.
  • the polyvinyl acetals according to the invention are also particularly suitable for producing ion-conductive intermediate layers for electrochromic systems.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de production de polyvinylacétals réticulés, selon lequel un polymère (A1) contenant un alcool polyvinylique à base de groupes carboxyle est réticulé, par les mesures suivantes, quel que soit l'ordre d'exécution : (i) le polymère (A1) est mis à réagir avec au moins un polyaldéhyde de formule (5), R9(CHO)n et (ii) au moins en partie des groupes de formule (1) et de formule (4a) sont estérifiés mutuellement. L'invention concerne en outre un procédé de production de polyvinylacétals réticulés, selon lequel un polymère (A2) contenant un alcool polyvinylique est réticulé, par les mesures suivantes : (i) le polymère (A2) est mis à réagir avec au moins un composé de formule (6), (ii) au moins un composé de formule (4b) est ajouté, (iii) un polyaldéhyde de formule (5) est ajouté et (iv) des groupes de formule (1) et des unités structurales dérivées du composé de formule (4b) sont estérifiés mutuellement, au moins en partie. A cet effet, les restes R7, R8, R9, R10 et R11, ainsi que l'indice n sont définis comme dans la description. L'invention concerne par ailleurs les polyvinylacétals réticulés obtenus selon ledit procédé, ainsi que des domaines d'application particulièrement utiles de ces polymères.
EP03785800A 2003-01-09 2003-12-12 Polyvinylacetals reticules Withdrawn EP1622946A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10300321 2003-01-09
DE10319201A DE10319201A1 (de) 2003-01-09 2003-04-29 Vernetzte Polyvinylacetale
PCT/EP2003/014109 WO2004063231A1 (fr) 2003-01-09 2003-12-12 Polyvinylacetals reticules

Publications (1)

Publication Number Publication Date
EP1622946A1 true EP1622946A1 (fr) 2006-02-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP03785800A Withdrawn EP1622946A1 (fr) 2003-01-09 2003-12-12 Polyvinylacetals reticules

Country Status (7)

Country Link
US (1) US7511096B2 (fr)
EP (1) EP1622946A1 (fr)
JP (1) JP2006513284A (fr)
AU (1) AU2003294838A1 (fr)
BR (1) BR0317977A (fr)
MX (1) MXPA05007218A (fr)
WO (1) WO2004063231A1 (fr)

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AU2003294838A1 (en) 2004-08-10
US20060052533A1 (en) 2006-03-09
US7511096B2 (en) 2009-03-31
BR0317977A (pt) 2005-12-06
MXPA05007218A (es) 2005-11-23
JP2006513284A (ja) 2006-04-20

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