WO2014090895A1 - Corps moulés en polyvinyl(iso)acétals - Google Patents

Corps moulés en polyvinyl(iso)acétals Download PDF

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Publication number
WO2014090895A1
WO2014090895A1 PCT/EP2013/076274 EP2013076274W WO2014090895A1 WO 2014090895 A1 WO2014090895 A1 WO 2014090895A1 EP 2013076274 W EP2013076274 W EP 2013076274W WO 2014090895 A1 WO2014090895 A1 WO 2014090895A1
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WO
WIPO (PCT)
Prior art keywords
polyvinyl
iso
acetal
acetals
weight
Prior art date
Application number
PCT/EP2013/076274
Other languages
German (de)
English (en)
Inventor
Markus Meise
Michael Frank
Marco Greb
Jan-Sebastian Weber
Original Assignee
Kuraray 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
Application filed by Kuraray Europe Gmbh filed Critical Kuraray Europe Gmbh
Publication of WO2014090895A1 publication Critical patent/WO2014090895A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/546—Polyvinyl acetate

Definitions

  • the invention relates to moldings produced by thermoplastic processing of polyvinyl (iso) acetals, and to their production and use.
  • Blends of polyvinyl acetals and plasticizers have long been known for producing films by thermoplastic processing.
  • films consisting essentially of polyvinyl butyrals (PVB) are widely used and are used as intermediates for laminated safety glass for building glazing or in the automotive field.
  • the physical and mechanical properties of such films are adjusted by the addition of additives, in particular of up to 30 wt .-% plasticizer.
  • DE 2 846 837 A1 discloses plasticized films of polyvinyl butyral which contain, for example, a montanic acid ester as plasticizer. Furthermore, the principle production and composition of films based on polyvinyl acetals with different softening z.
  • EP 185 863 B1 EP 1 118 258 B1, WO 02/102591 A1, EP 1 118 258 B1, EP 387 148 B1 or EP 0877655 B1.
  • the known PVB films based on n-butyraldehyde have a relatively large moisture absorption due to the softening, which can lead to undesirable turbidity in composite glazings on.
  • the high moisture absorption can lead to a low passage resistance, which is undesirable for electronic applications.
  • Polyvinyl (iso) butyral is also known analogously to polyvinyl (n) butyral, but has no commercial significance.
  • the preparation of polyvinyl (iso) butyral is known from DE 899864 and is carried out by a two-stage process via alkaline saponification of polyvinyl esters and subsequent acidic acetalization with isobutyraldehyde.
  • Plasticizer-containing polyvinyl (iso) acetals are known from US 2008/0286542 for the production of interlayer films for decorative glass elements.
  • the polyvinyl (iso) acetals described here have too low a degree of acetalization of 8-30% by weight for laminated safety glazings and are laminated between two layers of plasticized polyvinyl (n) acetal.
  • thermoplastic molded parts from polyvinyl (n) acetals e.g. by extrusion for films or melt spinning for fibers is difficult because the relative melt viscosity of polyvinyl (n) acetals is high.
  • plasticizers must be added.
  • the disadvantage here is that the addition of plasticizers significantly reduces the mechanical properties, the thermal stability and the mechanical strength of the resulting moldings.
  • a reduction of the mechanical load-bearing capacity has in particular the disadvantage that thin layer thicknesses occur at e.g. Do not let slides realize.
  • the plasticizer contained in the molded article or its plasticizer e.g. Migrate degradation products formed by UV radiation.
  • the inventors have surprisingly found that molded articles of polyvinyl (iso) acetals are more readily accessible by thermoplastic molding than from the analogous polyvinyl (n) acetals (i.e., having lower melt viscosities) but having higher glass transition temperatures and higher mechanical strengths than these.
  • iso-polyvinyl acetals have a higher flowability and a higher mechanical strength than their analogs from n-butyraldehyde.
  • the molecular weights can be lowered with a required mechanical load-bearing capacity of the material.
  • a further reduced viscosity is generated and the production of the molded body (fibers, films, etc.) can be energetically favorable and proceed in a shorter time.
  • the same advantages result, since e.g. the gluing of e.g. Glass, wood, fiber mats, etc. can be done at a lower temperature and lower cycle time than conventional n-polyvinyl acetal moldings.
  • the present invention therefore relates to moldings of unplasticized polyvinyl (iso) acetal, in particular obtainable from thermoplastic molding.
  • moldings according to the invention have significantly higher mechanical properties / stabilities.
  • the moldings of the invention are plasticizer-free, i. they contain no plasticizer, in particular none of the compounds used for polyvinyl (n) butyral as plasticizer, such as water, triethylene glycol octanoate (3G8) or dihexyl adipate (DHA).
  • plasticizer-free comprises small additions or residual amounts of additives, but these do not exceed 1% by weight, based on the polyvinyl (iso) acetal
  • thermoplastic processing all processes in which the polymer is deformed by thermal action, including e.g. injection molding, pressing, extruding, granulating, compacting, sintering or melt spinning.
  • the moldings according to the invention consist in the o.g. Limits polyvinyl (iso) acetals, which are obtained by acetalization of a fully or partially saponified polyvinyl alcohol with branched aldehyde compounds.
  • the polyvinyl (iso) acetal groups of the polyvinyl (iso) acetal result from the reaction of at least one polyvinyl alcohol with at least one branched aldehyde of 4-10 carbon atoms, i. the acetal group of the polyvinyl (iso) acetal results from one or more aliphatic carbonyl compounds of 4 to 10 carbon atoms having at least one branch at the alpha or beta position to the carbonyl group.
  • Such co-polyvinyl (iso) acetals are by simultaneous reaction of Polvinylalkoholen with a) one or more aliphatic carbonyl compounds having 4 to 10 carbon atoms with at least one branch at the alpha or beta position to the carbonyl group and b) one or more further unbranched aliphatic carbonyl compounds having 2 to 10 carbon atoms.
  • Suitable unbranched aliphatic carbonyl compounds are e.g. n-butyraldehyde or acetaldehyde.
  • the proportion of branched aldehyde compounds should be more than 50% by weight, in particular more than 80% by weight, of the sum of branched and unbranched aldehyde compounds.
  • the polyvinyl alcohol content of the polyvinyl (iso) acetals or co-polyvinyl (iso) acetals can be determined by the amount of aldehyde (s) used in the acetalization or the amount of catalyst, such as, for example, Mineral acids are adjusted.
  • the moldings according to the invention preferably contain polyvinyl (iso) acetal or co-polyvinyl (iso) acetals having a proportion of polyvinyl alcohol groups of 10 to 50% by weight and preferably 12 to 35% by weight.
  • the polyvinyl acetate content of the polyvinyl (iso) acetals or co-polyvinyl (iso) acetals used according to the invention can be adjusted by using a polyvinyl alcohol hydrolyzed to a corresponding proportion.
  • the polyvinyl acetate content influences the polarity of the polyvinyl (iso) acetal.
  • the moldings according to the invention preferably contain polyvinyl (iso) acetal or co-polyvinyl (iso) acetals with a proportion of polyvinyl acetate groups of 0.1 to 15% by weight, preferably 5 to 15% by weight or 0.1 to 5% by weight .-%.
  • crosslinked polyvinyl (iso) acetals in particular crosslinked polyvinyl (iso) butyral is also possible.
  • Suitable methods of crosslinking are e.g. in EP 1527107 B1 and WO 2004/063231 A1 (thermal self-crosslinking of carboxyl-containing polyvinyl acetals), EP 1606325 A1 (polyvinyl acetals crosslinked with polyaldehydes) and WO 03/020776 A1 (polyvinyl acetals crosslinked with glyoxylic acid).
  • polyvinyl (iso) acetal polyvinyl alcohol is dissolved in water and acetalysed with a carbonyl compound such as iso-butyraldehyde with the addition of an acid catalyst.
  • a carbonyl compound such as iso-butyraldehyde
  • the precipitated polyvinyl acetal is separated, washed neutral, optionally suspended in an alkaline aqueous medium, then washed neutral again and dried.
  • polyvinyl alcohol in addition to copolymers of vinyl alcohol and vinyl acetate, it is also possible to use terpolymers of hydrolyzed vinyl acetate / ethylene copolymers. These compounds are usually hydrolyzed to greater than 98% and contain from 1 to 10 wt. Ethylene-based units (e.g., "Exceval" type from Kuraray Europe GmbH).
  • the polyvinyl alcohol used can also be hydrolyzed copolymers of vinyl acetate and at least one further ethylenically unsaturated monomer.
  • the molded articles of the present invention Due to branching in the acetal side chain, the molded articles of the present invention have glass transition temperatures other than conventional straight chain aldehyde-based systems.
  • n-polyvinyl acetal molded articles such as e.g. Laminated sheets for laminated safety glass are typically obtained under certain processing conditions (melt pressure, melt temperature and mold temperature).
  • plasticizers are added to the polyvinyl acetals. These plasticizers serve the purpose of plasticizing the polyvinyl acetal polymer to make it a) low melting for the thermal process, i. lower the melt viscosity; and b) adjust the filming properties of the resulting products.
  • plasticized materials are no longer dimensionally stable. This means that, for example, fibers can break during manufacture and use or stick together after spinning and, for example, films must have minimum layer thicknesses. Thus, films made from plasticized polyvinyl (n) acetals can no longer be effectively removed at layer thicknesses of less than 300 ⁇ m. In addition, they tend to crack and show too low mechanical loads.
  • Inventive moldings can have different shapes or geometries.
  • these mean films, films, granules, pellets, strands and fibers, such as non-woven fabrics, filament fibers, short-cut fibers, etc.
  • films / films are understood to mean sheet-like shaped bodies which are understood by blown film extrusion, extrusion using a slot die or the pressing of PVB using a temperature / pressure profile.
  • Inventive moldings in the form of films can have thicknesses of 10 to 300 .mu.m.
  • fibers are understood as meaning shaped bodies which have been produced by melt spinning, dry spinning, wet spinning or electrospinning.
  • Granules are small, solid particles which can be obtained by physical and / or mechanical conversion of thermoplastic powders or granules.
  • the conversion of a mixture into granules can be carried out, for example, by drying solutions and subsequent grinding, by spray-drying solutions, dispersions or emulsions.
  • the granulation can also be carried out by coating, coating, by built-up granulation in the fluidized bed process or by pelleting with appropriate methods.
  • a suitable method is also the mixing or kneading under heat and subsequent granulation or grinding to granules or micronized powders.
  • the granules are preferably produced by thermoplastic extrusion of the polyvinyl (iso) acetals with attached granulation. During extrusion, the powdered polyvinyl acetal is melted and then formed via nozzles and cooled in air or water.
  • the shape of the granules can be irregular or regular. Typical forms are so-called strand or lens granules, as are known in the thermoplastic processing of plastics.
  • granules also means compounds, microgranules, compacted powders or granules as a masterbatch.
  • the shaped bodies according to the invention may contain additives known to the person skilled in the art, such as residual amounts of plasticizer, water, UV absorbers, antioxidants, adhesion regulators, optical brighteners, stabilizers, colorants, processing aids, organic or inorganic nanoparticles and particulate fillers, such as aluminum oxide, fumed silica, platelet-shaped particles such as sheet silicates and / or surface-active substances and other functional materials such as IR-absorbing and / or IR-reflecting substances, heat-conductive or electrically-conductive materials (such as metal particles, doped metal oxides, graphite, carbon black or carbon nanotubes).
  • additives known to the person skilled in the art, such as residual amounts of plasticizer, water, UV absorbers, antioxidants, adhesion regulators, optical brighteners, stabilizers, colorants, processing aids, organic or inorganic nanoparticles and particulate fillers, such as aluminum oxide, fumed silica, platelet-shaped particles such as sheet silicates and /
  • Inventive moldings consisting essentially of polyvinyl (iso) butyrals can be used in a large number of applications.
  • the following applications are intended to be exemplary without limiting the application to this application.
  • moldings according to the invention in the form of thin films can be used as the adhesive layer or laminate layer for bonding substrates such as glass, metals, ceramics, wood, fiber fabrics and / or combinations thereof.
  • An increased mechanical stability at the same time as low layer thicknesses is hereby e.g. for weight saving reasons, a significant advantage.
  • Moldings according to the invention can be used, for example, as fibers or so-called nonwovens in textile processing for bonding fibers or as adhesive fiber webs which are shaped in an analogous manner to the use of the moldings according to the invention as films for lamination or bonding geometries.
  • the determination of the polyvinyl alcohol and polyvinyl acetate content of the polyvinyl acetals carried out according to ASTM D 1396-92.
  • the conversion of% by weight into mol% is carried out according to formulas known to the person skilled in the art.
  • the determination of the glass transition temperature of the polyvinyl acetals by means of differential scanning calorimetry (DSC) according to DIN 53765 using a heating rate of 10K / min in the temperature range -50 ° C - 150 ° C. A first heating ramp is followed, followed by a cooling ramp followed by a second heating ramp. The position of the glass transition temperature is determined on the measurement curve of the second heating ramp according to DIN 51007.
  • the DIN midpoint (Tg DIN) is defined as the intersection of a horizontal halfway up the grade with the trace.
  • the step height is defined by the vertical distance of the two points of intersection of the central tangent with the baseline of the trace before and after glass transition.
  • the values for the tear strengths of the film were determined by means of tensile testing machine (Fa.TIRA) according to ISO 527 at a speed of 200 mm / min.
  • the layer thicknesses of the films were determined as an average of 10 individual measurements by means of a layer thickness measuring device (Erichsen Minitest 600 FN2, induction measurement on metal plate) on the film.
  • polyvinyl acetal resin is placed flat between two triacetate sheets. To achieve the desired layer thicknesses spacers are also laid between the triacetate. The amount of polyvinyl acetal resin incorporated depends on the size of the press film to be produced. Subsequently, at 160 ° C and a pressure of 20 bar for 20 min. produces the press foil. This is homogeneously digested and shows no streaks or residues of unmelted polyvinyl acetals.
  • the polyvinyl acetal was melted as a powder on an extrusion line with twin screw extruder (Leistritz) at process temperatures of 220-240 ° C and discharged at 200 bar through a slot die (2 mm nozzle gap, nozzle temperature 230-240 ° C) and on a chill roll unit discharged.
  • the adjustment of the thickness of the film was made by the corresponding adjustment of the take-off speeds of the film take-off unit
  • the polyvinyl acetal film is introduced at 120 ° C or 140 ° C, a pressure of 10 bar for 10 min. pressed.
  • iso-polyvinyl acetals have higher flowability and higher mechanical strength than their analogs of n-butyraldehyde.
  • Table 1 Measured values of the polyvinyl acetal moldings obtained as films.
  • DP means: degree of polymerization
  • IsoBut isobutyraldehyde
  • nBut n-butyraldehyde
  • P pressed film
  • C cast film
  • SP Max. Tension [N / mm2]
  • SD layer thickness [ ⁇ m]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne des corps moulés en polyvinyl(iso)acétal dépourvu de plastifiant.
PCT/EP2013/076274 2012-12-15 2013-12-11 Corps moulés en polyvinyl(iso)acétals WO2014090895A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012112349.7 2012-12-15
DE102012112349 2012-12-15

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WO2014090895A1 true WO2014090895A1 (fr) 2014-06-19

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016094213A1 (fr) * 2014-12-08 2016-06-16 Solutia Inc. Feuille monolithique de polyvinylacétal à tg élevée
EP3272792A1 (fr) * 2016-07-19 2018-01-24 Kuraray Europe GmbH Films minces comprenant du co-acétal polyvinyl exempt de plastifiant
US10000039B2 (en) 2014-12-08 2018-06-19 Solutia Inc. Multilayer interlayers having high Tg and high modulus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE899864C (de) * 1951-04-24 1953-12-17 Hoechst Ag Verfahren zur Herstellung von Polyvinylbutyraldehyd- und -isobutyraldehydacetalen
JP2007177211A (ja) * 2005-11-30 2007-07-12 Kuraray Co Ltd ポリビニルアセタール粉体および粉体塗料
EP2410027A1 (fr) * 2010-07-21 2012-01-25 Kuraray Europe GmbH Utilisation d'iso-acétal de polyvinyle dans des formules de couleurs d'impression
WO2012026393A1 (fr) * 2010-08-23 2012-03-01 株式会社クラレ Matériau d'étanchéité pour cellule solaire et couche intermédiaire pour verre feuilleté
WO2012043455A1 (fr) * 2010-09-28 2012-04-05 株式会社クラレ Résine d'acétal polyvinylique pour le thermoformage

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE899864C (de) * 1951-04-24 1953-12-17 Hoechst Ag Verfahren zur Herstellung von Polyvinylbutyraldehyd- und -isobutyraldehydacetalen
JP2007177211A (ja) * 2005-11-30 2007-07-12 Kuraray Co Ltd ポリビニルアセタール粉体および粉体塗料
EP2410027A1 (fr) * 2010-07-21 2012-01-25 Kuraray Europe GmbH Utilisation d'iso-acétal de polyvinyle dans des formules de couleurs d'impression
WO2012026393A1 (fr) * 2010-08-23 2012-03-01 株式会社クラレ Matériau d'étanchéité pour cellule solaire et couche intermédiaire pour verre feuilleté
EP2610225A1 (fr) * 2010-08-23 2013-07-03 Kuraray Co., Ltd. Matériau d'étanchéité pour cellule solaire et couche intermédiaire pour verre feuilleté
WO2012043455A1 (fr) * 2010-09-28 2012-04-05 株式会社クラレ Résine d'acétal polyvinylique pour le thermoformage
EP2623525A1 (fr) * 2010-09-28 2013-08-07 Kuraray Co., Ltd. Résine d'acétal polyvinylique pour le thermoformage

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016094213A1 (fr) * 2014-12-08 2016-06-16 Solutia Inc. Feuille monolithique de polyvinylacétal à tg élevée
CN107001758A (zh) * 2014-12-08 2017-08-01 首诺公司 高Tg的整体聚(乙烯醇缩醛)片材
US10000039B2 (en) 2014-12-08 2018-06-19 Solutia Inc. Multilayer interlayers having high Tg and high modulus
US10086590B2 (en) 2014-12-08 2018-10-02 Solutia Inc. High Tg monolithic poly(vinyl acetal) sheet
US10696018B2 (en) 2014-12-08 2020-06-30 Solutia Inc. Multilayer interlayers having high Tg and high modulus
US10889087B2 (en) 2014-12-08 2021-01-12 Solatia Inc. High Tg monolithic poly(vinyl acetal) sheet
EP3272792A1 (fr) * 2016-07-19 2018-01-24 Kuraray Europe GmbH Films minces comprenant du co-acétal polyvinyl exempt de plastifiant
WO2018015149A1 (fr) * 2016-07-19 2018-01-25 Kuraray Europe Gmbh Films minces comprenant du co-acétal polyvinylique exempts de plastifiant
CN109312089A (zh) * 2016-07-19 2019-02-05 可乐丽欧洲有限责任公司 包含聚乙烯醇共缩醛的不含增塑剂的薄膜
KR20190031484A (ko) * 2016-07-19 2019-03-26 쿠라라이 유럽 게엠베하 가소제-부재 폴리비닐-코-아세탈을 포함하는 박막
KR102180063B1 (ko) 2016-07-19 2020-11-17 쿠라라이 유럽 게엠베하 가소제-부재 폴리비닐-코-아세탈을 포함하는 박막

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