WO2014090895A1 - Molded bodies made of polyvinyl (iso)acetals - Google Patents

Molded bodies made of polyvinyl (iso)acetals 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
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German (de)
French (fr)
Inventor
Markus Meise
Michael Frank
Marco Greb
Jan-Sebastian Weber
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Kuraray Europe Gmbh
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Publication of WO2014090895A1 publication Critical patent/WO2014090895A1/en

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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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  • Manufacturing & Machinery (AREA)
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Abstract

The invention relates to molded bodies made of plasticizer-free polyvinyl (iso)acetal.

Description

Formkörper aus Polyvinyl(iso)acetalenMoldings of polyvinyl (iso) acetals Technisches GebietTechnical area
Die Erfindung betrifft durch thermoplastische Verarbeitung hergestellte Formkörper von Polyvinyl(iso)acetalen, sowie deren Herstellung und Anwendung.The invention relates to moldings produced by thermoplastic processing of polyvinyl (iso) acetals, and to their production and use.
Stand der TechnikState of the art
Gemische aus Polyvinylacetalen und Weichmachern sind seit langem zur Herstellung von Folien bzw. Filmen durch thermoplastische Verarbeitung bekannt. Insbesondere Filme die im Wesentlichen aus Polyvinylbutyralen (PVB) bestehen sind weit verbreitet und werden als Zwischenfilme für Verbundsicherheitsgläser für Gebäudeverglasungen oder im Automobilbereich eingesetzt. Die physikalischen und mechanischen Eigenschaften derartiger Folien werden durch den Zusatz von Additiven, insbesondere von bis zu 30 Gew.-% Weichmacher eingestellt. Blends of polyvinyl acetals and plasticizers have long been known for producing films by thermoplastic processing. In particular, 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.
So sind aus DE 2 846 837 A1 weichmacherhaltige Folien aus Polyvinylbutyral bekannt, die als Weichmacher beispielsweise einen Montansäureester enthalten. Ferner ist die prinzipielle Herstellung und Zusammensetzung von Folien auf Basis von Polyvinylacetalen mit unterschiedlichen Weichmachen z. B. in EP 185 863 B1, EP 1 118 258 B1 WO 02/102591 A1, EP 1 118 258 B1, EP 387 148 B1 oder EP 0877655 B1 beschrieben.Thus, 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. In 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.
Die bekannten PVB-Folien auf Basis von n-Butyraldehyd weisen aufgrund der Weichstellung eine relativ große Feuchteaufnahme, was in Verbundverglasungen zu unerwünschten Trübungen führen kann, auf. Dazu kann die hohe Feuchteaufnahme zu einem niedrigen Durchgangswiederstand führen, was für elektronische Anwendungen unerwünscht ist.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. In addition, the high moisture absorption can lead to a low passage resistance, which is undesirable for electronic applications.
Analog zu Polyvinyl(n)butyral ist auch Polyvinyl(iso)butyral bekannt, besitzt aber keine kommerzielle Bedeutung. Die Herstellung von Polyvinyl(iso)butyral ist aus DE 899864 bekannt und erfolgt durch ein zweistufiges Verfahren über alkalische Verseifung von Polyvinylestern und anschließender saurer Acetalisierung mit iso-Butyraldehyd.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.
Weichmacherhaltige Polyvinyl(iso)acetale sind aus US 2008/0286542 zur Herstellung von Zwischenschichtfilmen für dekorative Glaselemente bekannt. Die hier beschriebenen Polyvinyl(iso)acetale weisen für Verbundsicherheitsverglasungen einen zu niedrigen Acetalisierungsgrad von 8-30 Gew.-% auf und werden zwischen zwei Schichten von weichmacherhaltigem Polyvinyl(n)acetal einlaminiert.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.
Die Herstellung von thermoplastischen Formteilen aus Polyvinyl(n)acetalen z.B. durch Extrusion für Folien oder Schmelzspinnen für Fasern ist mit Schwierigkeiten verbunden, da die relative Schmelzviskosität von Polyvinyl(n)acetalen hoch ist. Um die thermoplastische Verarbeitung solcher Polymere gangbar zu machen, müssen Weichmacher zugesetzt werden. Der Nachteil hierbei ist, dass der Zusatz von Weichmachern die mechanischen Eigenschaften, die thermische Stabilität und die mechanische Belastbarkeit der erhaltenen Formkörper, signifikant reduziert. Eine Reduzierung der mechanischen Belastbarkeit hat insbesondere den Nachteil, dass sich dünne Schichtstärken bei z.B. Folien nicht realisieren lassen. Des Weiteren können die in den Formkörper enthaltenden Weichmacher oder deren, durch z.B. UV-Strahlung entstandenen Abbauprodukte migrieren.The production of 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. In order to make the thermoplastic processing of such polymers feasible, 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. Furthermore, the plasticizer contained in the molded article or its plasticizer, e.g. Migrate degradation products formed by UV radiation.
Aufgabetask
Der Erfindung liegt als Aufgabe zugrunde, Formkörper durch thermoplastische Verarbeitung von Polyvinylacetalen bereitzustellen, die trotz der Abwesenheit von Weichmachern, mit einer im Vergleich zu den bekannten weichmacherfreien Formkörpern reduzierten Schmelzviskosität unter gleichzeitiger Erhöhung der mechanischen Festigkeiten hergestellt werden können. It is an object of the present invention to provide moldings by thermoplastic processing of polyvinyl acetals which, despite the absence of plasticizers, can be produced with a reduced melt viscosity compared with the known plasticizer-free moldings, while at the same time increasing the mechanical strengths.
Darstellung der ErfindungPresentation of the invention
Die Erfinder haben überraschenderweise festgestellt, dass Formkörper aus Polyvinyl(iso)acetalen durch thermoplastische Formgebung einfacher zugänglich sind als aus den analogen Polyvinyl(n)acetalen (d.h. niedrigere Schmelzviskositäten aufweisen) aber eine höhere Glasübergangstemperaturen und höhere mechanische Festigkeiten als diese aufweisen.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.
So besitzen iso-Polyvinylacetale eine höhere Fließfähigkeit und eine höhere mechanische Belastbarkeit als ihre Analoga aus n-Butyraldehyd. Dadurch lassen sich bei einer geforderten mechanischen Belastbarkeit des Materials die Molekulargewichte absenken. Dadurch wird eine weiter erniedrigte Viskosität erzeugt und die Herstellung der Formkörper zu (Fasern, Folien, etc.) kann energetisch günstiger und in kürzerer Zeit ablaufen. Bei der Verwendung der Formkörper ergeben sich die gleichen Vorteile, da z.B. das Verkleben von z.B. Glas, Holz, Fasermatten etc. bei niedrigerer Temperatur und geringerer Taktzeit erfolgen kann, als bei herkömmlichen n-Polyvinylacetal-Formkörpern.For example, iso-polyvinyl acetals have a higher flowability and a higher mechanical strength than their analogs from n-butyraldehyde. As a result, the molecular weights can be lowered with a required mechanical load-bearing capacity of the material. As a result, 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. When using the molded articles, 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.
Ohne an die Richtigkeit dieser Theorie gebunden zu sein, wird vermutet, dass dies auf eine sterische Verzweigung der Polymere in der Acetalseitenkette zurückgeführt werden kann.Without being bound by the correctness of this theory, it is believed that this may be due to steric branching of the polymers in the acetal side chain.
Gegenstand der vorliegenden Erfindung sind daher Formkörper aus weichmacherfreiem Polyvinyl(iso)acetal, insbesondere erhältlich aus thermoplastischer Formgebung. The present invention therefore relates to moldings of unplasticized polyvinyl (iso) acetal, in particular obtainable from thermoplastic molding.
Im Vergleich zu herkömmlichen weichmacherhaltigen und -freien Formkörpern aus Polyvinyl(n)acetal weisen erfindungsgemäße Formkörper signifikant höhere mechanische Eigenschaften / Stabilitäten auf.Compared to conventional plasticized and non-free moldings of polyvinyl (n) acetal, moldings according to the invention have significantly higher mechanical properties / stabilities.
Die erfindungsgemäßen Formkörper sind weichmacherfrei, d.h. sie enthalten keinen Weichmacher, insbesondere keinen der für Polyvinyl(n)butyral als Weichmacher eingesetzten Verbindungen wie Wasser, Triethylenglycoloctanoat (3G8) oder Dihexyladipat (DHA). Im Rahmen der vorliegenden Erfindung umfasst der Begriff „weichmacherfrei“ geringe Zusätze oder Restmengen von Additiven, die aber 1 Gew.-%, bezogen auf das Polyvinyl(iso)acetal nicht überschreiten 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). In the context of the present invention, the term "plasticizer-free" comprises small additions or residual amounts of additives, but these do not exceed 1% by weight, based on the polyvinyl (iso) acetal
Unter dem Begriff „thermoplastische Verarbeitung“ werden alle Prozesse verstanden, bei denen das Polymer durch thermische Einwirkung verformt wird, dazu zählen z.B. das Spritzgießen, Pressen, Extrudieren, Granulieren, Kompaktieren, Sintern oder Schmelzspinnen.By the term "thermoplastic processing" is meant all processes in which the polymer is deformed by thermal action, including e.g. injection molding, pressing, extruding, granulating, compacting, sintering or melt spinning.
Verwendetes Poly(iso)acetalUsed poly (iso) acetal
Die erfindungsgemäßen Formkörper bestehen in den o.g. Grenzen Polyvinyl(iso)acetalen, die durch Acetalisierung eines ganz oder teilweise verseiften Polyvinylalkohols mit verzweigten Aldehydverbindungen erhalten werden.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.
Bevorzugt resultieren die Polyvinyl(iso)acetalgruppen des Poylvinyl(iso)acetals aus der Umsetzung von mindestens einem Polyvinylalkohol mit mindestens einem verzweigten Aldehyd mit 4-10 Kohlenstoffatomen, d.h. die die Acetalgruppe des Polyvinyl(iso)acetal resultiert aus einer oder mehreren aliphatischen Carbonylverbindungen mit 4 bis 10 Kohlenstoffatomen mit mindestens einer Verzweigung an der alpha- oder beta-Position zur Carbonylgruppe.Preferably, 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.
Bevorzugt wird aliphatische Carbonylverbindung mit 4 bis 10 Kohlenstoffatomen mit mindestens einer Verzweigung an der alpha- oder beta-Position zur Carbonylgruppe mindestens eine Verbindung der Gruppe iso-Butyraldehyd, iso-Valeraldehyd, (alpha)-Isovaleraldehyd [2-Methylbutanal], (beta)-Isovaleraldeyhd [3-Methylbutanal] und Pivalinaldehyd [2,2-dimethylpropanal] eingesetzt. Preferred is aliphatic carbonyl compound having 4 to 10 carbon atoms with at least one branching at the alpha or beta position to the carbonyl group at least one compound of the group iso-butyraldehyde, iso-valeraldehyde, (alpha) -Isovaleraldehyd [2-methylbutanal], (beta) Isovaleraldeyhd [3-methylbutanal] and pivalaldehyde [2,2-dimethylpropanal] used.
Es ist auch möglich, Polyvinyl(iso)acetale mit einem Anteil an unverzweigten Aldehyd einzusetzen. It is also possible to use polyvinyl (iso) acetals with a proportion of unbranched aldehyde.
Solche Co-Polyvinyl(iso)acetale sind durch gleichzeitige Umsetzung von Polvinylalkoholen mit
a) einer oder mehreren aliphatischen Carbonylverbindungen mit 4 bis 10 Kohlenstoffatomen mit mindestens einer Verzweigung an der alpha- oder beta-Position zur Carbonylgruppe und
b) einer oder mehreren weiteren unverzweigten aliphatischen Carbonylverbindungen mit 2 bis 10 Kohlenstoffatomen.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.
Geeignete unverzweigte aliphatischen Carbonylverbindungen sind z.B. n-Butyraldehyd oder Acetaldehyd.Suitable unbranched aliphatic carbonyl compounds are e.g. n-butyraldehyde or acetaldehyde.
Jedoch sollte der Anteil an verzweigten Aldehydverbindungen bei mehr als 50 Gew.-%, insbesondere mehr als 80 Gew.-% der Summe aus verzweigten und unverzweigten Aldehydverbindungen liegen. However, 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.
Der Polyvinylalkoholgehalt der Polyvinyl(iso)acetale bzw. Co-Polyvinyl(iso)acetale kann durch die Menge des bei der Acetalisierung eingesetzten Aldehyd(e)s bzw. der Menge an Katalysator, wie z.B. Mineralsäuren eingestellt werden. Bevorzugt enthalten die erfindungsgemäßen Formkörper Polyvinyl(iso)acetal bzw. Co-Polyvinyl(iso)acetale mit einem Anteil an Polyvinylalkoholgruppen von 10 – 50 Gew.-% und bevorzugt 12 – 35 Gew.-%. 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.
Der Polyvinylacetatgehalt der erfindungsgemäß verwendeten Polyvinyl(iso)acetale bzw. Co-Polyvinyl(iso)acetale kann durch Verwendung eines zu einem entsprechenden Anteil hydrolisierten Polyvinylalkohols eingestellt werden. Durch den Polyvinylacetatgehalt wird die Polarität des Polyvinyl(iso)acetals beeinflusst. Bevorzugt enthalten die erfindungsgemäßen Formkörper Polyvinyl(iso)acetal bzw. Co-Polyvinyl(iso)acetale mit einem Anteil an Polyvinylacetatgruppen von 0,1 bis 15 Gew.-%, bevorzugt 5 bis 15 Gew.-% oder 0,1 bis 5 Gew.-%.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 .-%.
Der Einsatz von vernetzten Polyvinyl(iso)acetalen insbesondere vernetztem Polyvinyl(iso)butyral ist ebenso möglich. Geeignete Methoden zur Vernetzung sind z.B. in EP 1527107 B1 und WO 2004/063231 A1 (thermische Selbstvernetzung von carboxylgruppenhaltigen Polyvinylacetalen), EP 1606325 A1 (mit Polyaldehyden vernetzte Polyvinylacetale) und WO 03/020776 A1 (mit Glyoxylsäure vernetzte Polyvinylacetale) beschrieben. The use of 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).
Zur Herstellung von Polyvinyl(iso)acetal wird Polyvinylalkohol in Wasser gelöst und mit einer Carbonylverbindung wie iso-Butyraldehyd unter Zusatz eines Säurekatalysators acetalysiert. Das ausgefallene Polyvinylacetal wird abgetrennt, neutral gewaschen, ggf. in einem alkalisch eingestellten wässrigen Medium suspendiert, danach erneut neutral gewaschen und getrocknet. For the preparation of 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. The precipitated polyvinyl acetal is separated, washed neutral, optionally suspended in an alkaline aqueous medium, then washed neutral again and dried.
Als Polyvinylalkohol können im Rahmen der vorliegenden Erfindung neben Copolymeren aus Vinylalkohol und Vinylacetat auch Terpolymere aus hydrolysierten Vinylacetat/Ethylen-Copolymeren eingesetzt werden. Diese Verbindungen sind in der Regel zu mehr als 98% hydrolysiert und enthalten 1 bis 10 Gew. auf Ethylen basierende Einheiten (z.B. Typ „Exceval“ der Kuraray Europe GmbH). For the purposes of the present invention, as the 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).
Als Polyvinylalkohol können im Rahmen der vorliegenden Erfindung weiterhin auch hydrolysierte Copolymere aus Vinylacetat und mindestens einem weiteren ethylenisch ungesättigten Monomer eingesetzt werden.In the context of the present invention, the polyvinyl alcohol used can also be hydrolyzed copolymers of vinyl acetate and at least one further ethylenically unsaturated monomer.
Aufgrund der Verzweigungen in der Acetalseitenkette besitzen die erfindungsgemäßen Formkörper andere Glasübergangstemperaturen als herkömmliche, auf geradkettigen Aldehyden basierende Systeme.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-Polyvinylacetal-Formkörper wie z.B. Laminatfolien für Verbundsicherheitsgläser werden typischerweise unter bestimmten Verarbeitungsbedingungen (Schmelzedruck, Schmelzetemperatur und Werkzeugtemperatur) erhalten. Hierzu werden den Polyvinylacetalen Weichmacher zugesetzt. Diese Weichmacher erfüllen die Aufgabe das Polyvinylacetalpolymer zu plastifizieren, um es a) für den thermischen Prozess niedrig schmelzend zu machen, d.h. die Schmelzviskosität abzusenken und b) die Verfilmungseigenschaften der erhaltenen Produkte einzustellen. 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). For this purpose, 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.
Als nachteilig hat sich hier erwiesen, dass Formkörper, erhalten aus derartig plastifizierter Materialien, nicht mehr formstabil sind. Dies bedeutet, dass z.B. Fasern in der Herstellung und Verwendung reißen bzw. nach dem Spinnen verkleben können und z.B. Filme Mindestschichtstärken aufweisen müssen. So können Filme hergestellt aus weichmacherhaltigen Polyvinyl(n)acetalen bei Schichtstärken kleiner 300 µm nicht mehr effektiv abgezogen werden können. Darüber hinaus neigen sie zum Reißen und zeigen zu niedrige mechanische Belastbarkeiten. A disadvantage has been found here that molded articles obtained from such 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 μm. In addition, they tend to crack and show too low mechanical loads.
Erfindungsgemäße Formkörper können verschieden Formen bzw. Geometrien aufweisen. In der Regel werden erfindungsgemäß darunter Filme, Folien, Granulate, Pellets, Stränge und Fasern wie Faservliese, Filament-Fasern, Kurzschnittfasern, etc. verstanden.Inventive moldings can have different shapes or geometries. In general, according to the invention, these mean films, films, granules, pellets, strands and fibers, such as non-woven fabrics, filament fibers, short-cut fibers, etc.
Unter Folien / Filmen werden erfindungsgemäß flächige Formkörper verstanden, die durch Blasfolienextrusion, Extrusion unter Verwendung einer Breitschlitzdüse oder das Pressen von PVB unter Verwendung eines Temperatur/Druckprofils verstanden. Erfindungsgemäße Formkörper in Form von Folien können Dicken von 10 bis 300 µm aufweisen.According to the invention, 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.
Unter Fasern werden erfindungsgemäß Formkörper verstanden, die durch Schmelzspinnen, Trockenspinnen, Naßspinnen oder Elektrospinnen hergestellt wurden.According to the invention, fibers are understood as meaning shaped bodies which have been produced by melt spinning, dry spinning, wet spinning or electrospinning.
Als Granulate werden kleine, feste Partikel verstanden, die durch physikalische und/oder mechanische Umwandlung thermoplastischer Pulver bzw. Granulate erhalten werden können. Die Umwandlung eines Gemisches zu Granulaten kann beispielsweise durch Austrocknung von Lösungen und anschließender Vermahlung, durch Sprühtrocknung von Lösungen, Dispersionen oder Emulsionen erfolgen. Die Granulierung kann ebenfalls durch Beschichtung, Dragierung, über Aufbaugranulation im Wirbelbettverfahren oder über Pelletierung mit entsprechenden Verfahren erfolgen. Ein geeignetes Verfahren ist auch das Vermischen bzw. Verkneten unter Wärmezufuhr und anschließende Granulierung bzw. Vermahlung zu Granulaten bzw. mikronisierten Pulvern.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.
Bevorzugt erfolgt die Herstellung der Granulate über thermoplastische Extrusion der Polyvinyl(iso)acetale mit angeschlossener Granulierung. Während der Extrusion wird das pulverförmige Polyvinylacetal aufgeschmolzen und anschließend über Düsen geformt und in Luft oder Wasser abgekühlt.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.
Die Form der Granulate kann irregulär oder regelmäßig sein. Typische Formen sind sogenannte Strang- oder Linsengranulate, wie sie in der für die thermoplastische Verarbeitung von Kunststoffen bekannt sind. 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.
Unter dem Begriff Granulate werden erfindungsgemäß auch Compounds, Mikrogranulate, kompaktierte Pulver oder Granulate als Masterbatch verstanden. According to the invention, the term granules also means compounds, microgranules, compacted powders or granules as a masterbatch.
Zusätzlich können die erfindungsgemäßen Formkörper dem Fachmann bekannte Zusätze enthalten wie Restmengen an Weichmacher, Wasser, UV-Absorber, Antioxidantien, Haftungsregulatoren, optische Aufheller, Stabilisatoren, Farbmittel, Verarbeitungshilfs-mittel, organische oder anorganische Nanopartikel sowie partikuläre Füllstoffe, wie Aluminumoxid, pyrogene Kieselsäure, plättchenförmige Partikel wie Schichtsilikate und/oder oberflächen­aktive Stoffe sowie weitere funktionale Materialien wie IR-absorbierende und / oder IR-reflektierende Stoffe, wärme- oder elektrisch-leitfähige Materialien (wie z.B. Metallpartikel, dotierte Metalloxide, Graphit, Ruß oder Carbon-Nanotubes). Die Menge dieser Additive überschreitet nicht 1 Gew.-%, bezogen auf das Polyvinyl(iso)acetal.In addition, 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). The amount of these additives does not exceed 1% by weight, based on the polyvinyl (iso) acetal.
Verwendung der Formkörper/Gewerbliche AnwendbarkeitUse of the molded articles / industrial applicability
Erfindungsgemäße Formkörper im Wesentlichen bestehend aus Polyvinyl(iso)butyralen können in einer Vielzahl von Anwendungen Verwendung finden. Folgende Anwendungen sollen beispielhaft sein, ohne die Anwendung auf diese Anwendung zu beschränken. So lassen sich erfindungsgemäße Formkörper in Form dünner Folien als Klebeschicht bzw. Laminatschicht zur Verklebung von Substraten wie Glas, Metallen, Keramiken, Holz, Fasergeweben und/oder Kombinationen daraus verwenden. Eine erhöhte mechanische Stabilität bei zugleich möglichst geringen Schichtstärken ist hierbei z.B. aus Gewichtsersparnisgründen ein signifikanter Vorteil.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. Thus, 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.
Erfindungsgemäße Formkörper können beispielsweise als Fasern oder sog. Non-woven (Faservliese) Verwendung finden in der textilen Verarbeitung zur Verklebung von Fasern oder als adhesive Faservliese, die in analoger Weise zur Verwendung der erfindungsgemäßer Formkörper als Folien zur Laminierung bzw. Verklebung 3-dimensional geformter Geometrien.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.
Messmethodenmeasurement methods Polyvinylalkohol- und Polyvinylacetat­gehaltPolyvinyl alcohol and polyvinyl acetate content
Die Bestimmung des Polyvinylalkohol- und Polyvinylacetat­gehaltes der Polyvinylacetale erfolgt gemäß ASTM D 1396-92. Der Acetalysierungsgrad (= Butyralgehalt) kann als der zu Hundert fehlende Teil aus der gemäß ASTM D 1396-92 bestimmten Summe aus Polyvinylalkohol- und Polyvinylacetatgehalt berechnet werden. Die Umrechnung von Gew.-% in mol-% erfolgt gemäß dem Fachmann bekannten Formeln.The determination of the polyvinyl alcohol and polyvinyl acetate content of the polyvinyl acetals carried out according to ASTM D 1396-92. The degree of acetalation (= butyral content) can be calculated as the one hundredth missing part from the sum of polyvinyl alcohol and polyvinyl acetate content determined 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.
GlasübergangstemperaturGlass transition temperature
Die Bestimmung der Glasübergangstemperatur der Polyvinylacetale erfolgt mittels Dynamischer Differenzkalorimetrie (DSC) gemäß DIN 53765 unter Verwendung einer Heizrate von 10K/min im Temperaturintervall -50 °C – 150°C. Es wird eine erste Heizrampe, gefolgt von einer Kühlrampe, gefolgt von einer zweiten Heizrampe gefahren. Die Lage der Glasübergangstemperatur wird an der der zweiten Heizrampe zugehörigen Messkurve nach DIN 51007 ermittelt. Der DIN-Mittelpunkt (Tg DIN) ist definiert als Schnittpunkt einer Horizontalen auf halber Stufenhöhe mit der Messkurve. Die Stufenhöhe ist durch den vertikalen Abstand der beiden Schnittpunkte der Mitteltangente mit den Basislinien der Messkurve vor und nach Glasumwandlung definiert.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.
Messung der Zugeigenschaften von Formkörpern/FolienMeasurement of the tensile properties of moldings / films
Die Werte für die Reißfestigkeiten der Folie wurden mittels Zugprüfmaschine (Fa.TIRA) gemäß ISO 527 bei einer Geschwindigkeit von 200 mm/min bestimmt.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.
Messung der Schichtdicke von Folien Measurement of the layer thickness of films
Die Schichtdicken der Folien wurden als Mittelwert von 10 Einzelmessungen mittels Schichtdickenmessgerät (Erichsen Minitest 600 FN2, Induktionsmessung auf Metalplatte) an der Folie ermittelt.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.
BeispieleExamples Allgemeine Synthesevorschrift für Polyvinyl(n)acetal mit Polyvinylacetatgehalt von 0,9 Gew.-% General Synthesis Procedure for Polyvinyl Acetal with Polyvinyl Acetate Content of 0.9% by Weight
100 Gewichtsteile des Polyvinylalkohols Mowiol 28-99 (Handelsprodukt von Kuraray Europe GmbH) wurden in 975 Gewichtsteilen Wasser unter Erwärmen auf 90 °C gelöst. Es wurden bei einer Temperatur von 40 °C 57,5 Gewichtsteile n-Butyraldehyd und bei einer Temperatur von 12 °C unter Rühren 75 Gewichtsteile 20 %ige Salzsäure zugegeben. Die Mischung wurde nach Ausfallen des Polyvinylbutyrals (PVB) auf 73°C erwärmt und bei dieser Temperatur für 2 Stunden gerührt. Das PVB wurde nach Abkühlen auf Raumtemperatur abgetrennt, mit Wasser neutral gewaschen und getrocknet. Es wurde ein Polyvinyl(n)acetal mit einem Polyvinylalkoholgehalt von 20,2 Gew.-% und einem Polyvinylacetatgehalt von 0,9 Gew.-% erhalten.100 parts by weight of the polyvinyl alcohol Mowiol 28-99 (commercial product of Kuraray Europe GmbH) were dissolved in 975 parts by weight of water with heating to 90 ° C. There were added at a temperature of 40 ° C 57.5 parts by weight of n-butyraldehyde and at a temperature of 12 ° C with stirring 75 parts by weight of 20% hydrochloric acid. The mixture was heated to 73 ° C after precipitation of the polyvinyl butyral (PVB) and stirred at this temperature for 2 hours. The PVB was separated after cooling to room temperature, washed neutral with water and dried. A polyvinyl (n) acetal having a polyvinyl alcohol content of 20.2% by weight and a polyvinyl acetate content of 0.9% by weight was obtained.
Allgemeine Synthesevorschrift für Polyvinyl(iso)acetal Polyvinylacetatgehalt von 1,0 Gew.-% General Synthesis Procedure for Polyvinyl (iso) acetal Polyvinyl acetate content of 1.0% by weight
100 Gewichtsteile des Polyvinylalkohols Mowiol 28-99 (Handelsprodukt von Kuraray Europe GmbH) wurden in 975 Gewichtsteilen Wasser unter Erwärmen auf 90 °C gelöst. Es wurden bei einer Temperatur von 40 °C 57,6 Gewichtsteile iso-Butyraldehyd und bei einer Temperatur von 12 °C unter Rühren 75 Gewichtsteile 20 %ige Salzsäure zugegeben. Die Mischung wurde nach Ausfallen des Polyvinylbutyrals (PVB) auf 73°C erwärmt und bei dieser Temperatur für 2 Stunden gerührt. Das PVB wurde nach Abkühlen auf Raumtemperatur abgetrennt, mit Wasser neutral gewaschen und getrocknet. Es wurde ein Polyvinyl(iso)acetal mit einem Polyvinylalkoholgehalt von 20,3 Gew.-% und einem Polyvinylacetatgehalt von 1,0 Gew.-% erhalten.100 parts by weight of the polyvinyl alcohol Mowiol 28-99 (commercial product of Kuraray Europe GmbH) were dissolved in 975 parts by weight of water with heating to 90 ° C. There were added at a temperature of 40 ° C 57.6 parts by weight of isobutyraldehyde and at a temperature of 12 ° C with stirring 75 parts by weight of 20% hydrochloric acid. The mixture was heated to 73 ° C after precipitation of the polyvinyl butyral (PVB) and stirred at this temperature for 2 hours. The PVB was separated after cooling to room temperature, washed neutral with water and dried. There was obtained a polyvinyl (iso) acetal having a polyvinyl alcohol content of 20.3% by weight and a polyvinyl acetate content of 1.0% by weight.
Allgemeine Synthesevorschrift für Polyvinyl(n)acetalPolyvinylacetatgehalt von 1,9 Gew.-% General procedure for polyvinyl (n) acetalPolyvinyl acetate content of 1.9% by weight
100 Gewichtsteile des Polyvinylalkohols Mowiol 10-98 (Handelsprodukt von Kuraray Europe GmbH) wurden in 900 Gewichtsteilen Wasser unter Erwärmen auf 90 °C gelöst. Es wurden bei einer Temperatur von 40 °C 56,3 Gewichtsteile n-Butyraldehyd und bei einer Temperatur von 10 °C unter Rühren 100 Gewichtsteile 20 %ige Salzsäure zugegeben. Die Mischung wurde nach Ausfallen des Polyvinylbutyrals (PVB) auf 40°C erwärmt und bei dieser Temperatur für 110 min. gerührt. Das PVB wurde nach Abkühlen auf Raumtemperatur abgetrennt, mit Wasser neutral gewaschen und getrocknet. Es wurde ein Polyvinyl(n)acetal mit einem Polyvinylalkoholgehalt von 21 Gew.-% und einem Polyvinylacetatgehalt von 1,9 Gew.-% erhalten.100 parts by weight of the polyvinyl alcohol Mowiol 10-98 (commercial product of Kuraray Europe GmbH) were dissolved in 900 parts by weight of water while heating to 90 ° C. There were added at a temperature of 40 ° C 56.3 parts by weight of n-butyraldehyde and at a temperature of 10 ° C with stirring 100 parts by weight of 20% hydrochloric acid. The mixture was heated to 40 ° C after precipitation of the polyvinyl butyral (PVB) and at this temperature for 110 min. touched. The PVB was separated after cooling to room temperature, washed neutral with water and dried. There was obtained a polyvinyl (n) acetal having a polyvinyl alcohol content of 21% by weight and a polyvinyl acetate content of 1.9% by weight.
Allgemeine Synthesevorschrift für Polyvinyl(iso)acetal Polyvinylacetatgehalt von 1,9 Gew.-% General Synthesis Procedure for Polyvinyl (iso) acetal Polyvinyl acetate content of 1.9% by weight
100 Gewichtsteile des Polyvinylalkohols Mowiol 10-98 (Handelsprodukt von Kuraray Europe GmbH) wurden in 900 Gewichtsteilen Wasser unter Erwärmen auf 90 °C gelöst. Es wurden bei einer Temperatur von 40 °C 61 Gewichtsteile iso-Butyraldehyd und bei einer Temperatur von 10 °C unter Rühren 100 Gewichtsteile 20 %ige Salzsäure zugegeben. Die Mischung wurde nach Ausfallen des Polyvinylbutyrals (PVB) auf 40°C erwärmt und bei dieser Temperatur für 110 min. gerührt. Das PVB wurde nach Abkühlen auf Raumtemperatur abgetrennt, mit Wasser neutral gewaschen und getrocknet. Es wurde ein Polyvinyl(n)acetal mit einem Polyvinylalkoholgehalt von 21 Gew.-% und einem Polyvinylacetatgehalt von 1,9 Gew.-% erhalten.100 parts by weight of the polyvinyl alcohol Mowiol 10-98 (commercial product of Kuraray Europe GmbH) were dissolved in 900 parts by weight of water while heating to 90 ° C. There were added at a temperature of 40 ° C 61 parts by weight of isobutyraldehyde and at a temperature of 10 ° C with stirring 100 parts by weight of 20% hydrochloric acid. The mixture was heated to 40 ° C after precipitation of the polyvinyl butyral (PVB) and at this temperature for 110 min. touched. The PVB was separated after cooling to room temperature, washed neutral with water and dried. There was obtained a polyvinyl (n) acetal having a polyvinyl alcohol content of 21% by weight and a polyvinyl acetate content of 1.9% by weight.
Allgemeine Herstellungsvorschrift für PressfolienGeneral manufacturing specification for press foils
Zur Herstellung der Pressfolien wird Polyvinylacetal Harz flächig zwischen zwei Triacetatfolien eingebracht. Zur Erreichung der gewünschten Schichtdicken werden zudem Abstandshalter zwischen den Triacetatfolien verlegt. Die Menge an eingebrachtem Polyvinylacetal Harz richtet sich nach der Größe der herzustellenden Pressfolie. Anschließend wird bei 160 °C und einem Druck von 20 bar für 20 min. die Pressfolie erzeugt. Diese ist homogen aufgeschlossen und zeigt keinerlei Schlieren oder Reste von nicht geschmolzenen Polyvinylacetalen.To produce the press foils, 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.
Allgemeine Herstellungsvorschrift für CastfolienGeneral manufacturing specification for cast films
Zur Herstellung der Castfolien wurde das Polyvinylacetal als Pulver über eine Extrusionsanlage mit Doppelschneckenextruder (Fa. Leistritz) bei Prozesstemperaturen von 220-240 °C aufgeschmolzen und bei 200 bar über eine Breitschlitzdüse (2 mm Düsenspalt, Düsentemperatur 230-240 °C) ausgetragen und auf eine Kühlwalzeneinheit ausgebracht. Die Einstellung der Dicke der Folie erfolgte durch die entsprechende Anpassung der Abzugsgeschwindigkeiten der Folienabzugseinheit For the production of Castfolien 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
Allgemeine Herstellungsvorschrift für LaminateGeneral manufacturing instructions for laminates
Zwischen zwei Glasscheiben (à 2 mm) wird die Polyvinylacetalfolie eingebracht bei 120 °C bzw. 140 °C, einem Druck von 10 bar für 10 min. verpresst.Between two sheets of glass (2 mm each), the polyvinyl acetal film is introduced at 120 ° C or 140 ° C, a pressure of 10 bar for 10 min. pressed.
Wie aus Tabelle 1 ersichtlich, besitzen iso-Polyvinylacetale eine höhere Fließfähigkeit und eine höhere mechanische Belastbarkeit als ihre Analoga aus n-Butyraldehyd. As can be seen from Table 1, iso-polyvinyl acetals have higher flowability and higher mechanical strength than their analogs of n-butyraldehyde.
Bei der Verwendung der Formkörper ergeben sich die gleichen Vorteile, da z.B. das Verkleben von z.B. Glas, Holz, Fasermatten etc. bei niedrigerer Temperatur und geringerer Taktzeit erfolgen kann als bei herkömmlichen n-Polyvinylacetal-Formkörpern (vgl. Tabelle 2).When using the molded articles, the same advantages result, since e.g. the gluing of e.g. Glass, wood, fiber mats, etc. at lower temperature and lower cycle time can be done than conventional n-polyvinyl acetal molded bodies (see Table 2).
Tabelle 1Table 1
NrNo DPDP Aldehydaldehyde PP CC PVOH [%]PVOH [%] PVAc [%]PVAc [%] Sp [N/mm2]Sp [N / mm2] Tg [°C]Tg [° C] MFR 100MFR 100 SD [µm]SD [μm]
11 10001000 isoButisobut xx 20,920.9 1,71.7 66,666.6 7878 0,960.96 99,599.5
22 17001700 isoButisobut xx 20,320.3 11 69,769.7 8282 0,060.06 101101
33 10001000 isoButisobut xx 20,920.9 1,71.7 67,167.1 7878 0,960.96 151151
44 17001700 isoButisobut xx 20,320.3 11 69,769.7 8282 0,060.06 152152
V1V1 10001000 n-butn-but xx 2121 1,91.9 43,143.1 7070 0,740.74 100100
V2V2 17001700 n-but n-but xx 20,220.2 0,90.9 51,451.4 7373 0,040.04 100100
B3B3 10001000 n-butn-but xx 2121 1,91.9 58,858.8 7070 0,740.74 149149
V4V4 17001700 n-butn-but xx 20,220.2 0,90.9 60,360.3 7373 0,040.04 152152
Tabelle 1: Erhaltene Messwerte der Polyvinylacetalformkörper als Folien. Table 1: Measured values of the polyvinyl acetal moldings obtained as films.
Tabelle 2Table 2
NrNo Aldehydaldehyde PP CC Presstemperatur [°C]Pressing temperature [° C] Pressdruck [bar]Pressing pressure [bar] Beurteilungevaluation
11 iso-butiso-but xx 120120 1010 11
22 iso-butiso-but xx 140140 1010 33
33 iso-butiso-but xx 120120 1010 11
44 iso-butiso-but xx 140140 1010 33
V1V1 n-butn-but xx 120120 1010 33
V2V2 n-butn-but xx 140140 1010 44
V3V3 n-butn-but xx 120120 1010 33
V4V4 n-butn-but xx 140140 1010 44
Tabelle 2: Erhaltene Messwerte der Glas-Poylvinylacetal-Glas-Verbunde Table 2: Received measurements of the glass-polyvinyl acetal-glass composites
Es bedeuten DP: Polymerisationsgrad; IsoBut : isoButyraldehyd; nBut: n-Butyraldehyd; P: Pressfolie; C: Castfolie; SP: Max. Spannung [N/mm²]; SD: Schichtdicke [µm]DP means: degree of polymerization; IsoBut: isobutyraldehyde; nBut: n-butyraldehyde; P: pressed film; C: cast film; SP: Max. Tension [N / mm²]; SD: layer thickness [μm]
Beurteilung der Laminierung: 1= vollständig, 2 = sehr wenige Fehler, 3 = wenige Fehler, 4 = zahlreiche Fehler, 5 = sehr viele Fehler, 6 = keine LaminierungAssessment of lamination: 1 = complete, 2 = very few errors, 3 = few errors, 4 = many errors, 5 = very many errors, 6 = no lamination

Claims (8)

  1. Formkörper aus weichmacherfreiem Polyvinyl(iso)acetal.Moldings of unplasticized polyvinyl (iso) acetal.
  2. Formkörper nach Anspruch 1 dadurch gekennzeichnet das die Formkörper durch thermoplastische Formgebung aus weichmacherfreiem Polyvinyl(iso)acetal erhalten werden.Shaped body according to claim 1, characterized in that the shaped bodies are obtained by thermoplastic shaping of unplasticized polyvinyl (iso) acetal.
  3. Formkörper nach einem der Ansprüche 1 oder 2 dadurch gekennzeichnet dass die Acetalgruppe des Polyvinyl(iso)acetal aus einer oder mehreren aliphatischen Carbonylverbindungen mit 4 bis 10 Kohlenstoffatomen mit mindestens einer Verzweigung an der alpha- oder beta-Position zur Carbonylgruppe resultiert.Shaped body according to one of claims 1 or 2, characterized in that the acetal group of the polyvinyl (iso) acetal of one or more aliphatic carbonyl compounds having 4 to 10 carbon atoms with at least one branching at the alpha or beta position to the carbonyl group results.
  4. Formkörper nach Anspruch 3, dadurch gekennzeichnet, dass als aliphatische Carbonylverbindung mit 4 bis 10 Kohlenstoffatomen mit mindestens einer Verzweigung an der alpha- oder beta-Position zur Carbonylgruppe mindestens eine Verbindung der Gruppe iso-Butyraldehyd, iso-Valeraldehyd, (alpha)-Isovaleraldehyd [2-Methylbutanal], (beta)-Isovaleraldeyhd [3-Methylbutanal] und Pivalinaldehyd [2,2-dimethylpropanal] eingesetzt wird. Shaped body according to claim 3, characterized in that as aliphatic carbonyl compound having 4 to 10 carbon atoms with at least one branching at the alpha or beta position to the carbonyl group at least one compound of the group iso-butyraldehyde, iso-valeraldehyde, (alpha) -Isovaleraldehyd [ 2-methylbutanal], (beta) -Isovaleraldeyhd [3-methylbutanal] and pivalaldehyde [2,2-dimethylpropanal] is used.
  5. Formkörper nach einem der Ansprüche 1 bis 5 dadurch gekennzeichnet dass das Polyvinyl(iso)acetale einen Restalkoholgehalt von 10-50 Gew.-% aufweisen.Shaped body according to one of claims 1 to 5 characterized in that the polyvinyl (iso) acetals has a residual alcohol content of 10-50 % By weight.
  6. Formkörper nach einem der Ansprüche 1 bis 5 dadurch gekennzeichnet dass das Polyvinyl(iso)acetale einen Restacetatgehalt von 0,1-15 Gew.-% aufweisen.Shaped body according to one of claims 1 to 5 characterized in that the polyvinyl (iso) acetals have a residual acetate content of 0.1-15 wt .-%.
  7. Formkörper nach einem der Ansprüche 1 bis 6 dadurch gekennzeichnet dass die thermoplastische Formgebung durch Spritzgießen, Pressen, Extrudieren, Granulieren, Kompaktieren, Sintern oder Schmelzspinnen des Polyvinyl(iso)acetals erfolgt.Shaped body according to one of claims 1 to 6 characterized in that the thermoplastic molding is carried out by injection molding, pressing, extruding, granulating, compacting, sintering or melt spinning of the polyvinyl (iso) acetal.
  8. Verwendung der Formkörper nach einem der Ansprüche 1 bis 7 zur Herstellung von Folien, zur Verklebung von Substraten, als Fasern oder als Non-woven oder als Granulat.Use of the moldings according to one of claims 1 to 7 for the production of films, for the bonding of substrates, as fibers or as nonwovens or as granules.
PCT/EP2013/076274 2012-12-15 2013-12-11 Molded bodies made of polyvinyl (iso)acetals WO2014090895A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016094213A1 (en) * 2014-12-08 2016-06-16 Solutia Inc. HIGH Tg MONOLITHIC POLY(VINYL ACETAL) SHEET
EP3272792A1 (en) * 2016-07-19 2018-01-24 Kuraray Europe GmbH Thin films comprising plasticizer-free polyvinyl-co-acetal
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 (en) * 1951-04-24 1953-12-17 Hoechst Ag Process for the preparation of polyvinyl butyraldehyde and isobutyraldehyde acetals
JP2007177211A (en) * 2005-11-30 2007-07-12 Kuraray Co Ltd Polyvinyl acetal powder and powder coating
EP2410027A1 (en) * 2010-07-21 2012-01-25 Kuraray Europe GmbH Use of polyvinyl isoacetals in printing ink formulas
WO2012026393A1 (en) * 2010-08-23 2012-03-01 株式会社クラレ Solar-cell sealant and laminated-glass interlayer
WO2012043455A1 (en) * 2010-09-28 2012-04-05 株式会社クラレ Polyvinyl acetal resin for thermoforming

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE899864C (en) * 1951-04-24 1953-12-17 Hoechst Ag Process for the preparation of polyvinyl butyraldehyde and isobutyraldehyde acetals
JP2007177211A (en) * 2005-11-30 2007-07-12 Kuraray Co Ltd Polyvinyl acetal powder and powder coating
EP2410027A1 (en) * 2010-07-21 2012-01-25 Kuraray Europe GmbH Use of polyvinyl isoacetals in printing ink formulas
WO2012026393A1 (en) * 2010-08-23 2012-03-01 株式会社クラレ Solar-cell sealant and laminated-glass interlayer
EP2610225A1 (en) * 2010-08-23 2013-07-03 Kuraray Co., Ltd. Solar-cell sealant and laminated-glass interlayer
WO2012043455A1 (en) * 2010-09-28 2012-04-05 株式会社クラレ Polyvinyl acetal resin for thermoforming
EP2623525A1 (en) * 2010-09-28 2013-08-07 Kuraray Co., Ltd. Polyvinyl acetal resin for thermoforming

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016094213A1 (en) * 2014-12-08 2016-06-16 Solutia Inc. HIGH Tg MONOLITHIC POLY(VINYL ACETAL) SHEET
CN107001758A (en) * 2014-12-08 2017-08-01 首诺公司 High Tg poly- (vinyl acetal) sheet material of entirety
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 (en) * 2016-07-19 2018-01-24 Kuraray Europe GmbH Thin films comprising plasticizer-free polyvinyl-co-acetal
WO2018015149A1 (en) * 2016-07-19 2018-01-25 Kuraray Europe Gmbh Thin films comprising plasticizer-free polyvinyl-co-acetal
CN109312089A (en) * 2016-07-19 2019-02-05 可乐丽欧洲有限责任公司 The film of not plasticizer-containing comprising polyvinyl alcohol cocondensation aldehyde
KR20190031484A (en) * 2016-07-19 2019-03-26 쿠라라이 유럽 게엠베하 A thin film comprising a plasticizer-free polyvinyl-co-acetal
KR102180063B1 (en) 2016-07-19 2020-11-17 쿠라라이 유럽 게엠베하 Thin film containing plasticizer-free polyvinyl-co-acetal

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