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EP0464070A1 - Moulding material for the manufacture of films for laminated glass panes - Google Patents

Moulding material for the manufacture of films for laminated glass panes

Info

Publication number
EP0464070A1
EP0464070A1 EP90904810A EP90904810A EP0464070A1 EP 0464070 A1 EP0464070 A1 EP 0464070A1 EP 90904810 A EP90904810 A EP 90904810A EP 90904810 A EP90904810 A EP 90904810A EP 0464070 A1 EP0464070 A1 EP 0464070A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
silane
group
composition according
molding composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90904810A
Other languages
German (de)
French (fr)
Inventor
Jürgen EGENOLF
Hans-Joachim KÖTZSCH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels Troisdorf AG
Original Assignee
Huels Troisdorf AG
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 Huels Troisdorf AG filed Critical Huels Troisdorf AG
Publication of EP0464070A1 publication Critical patent/EP0464070A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • 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
    • B32B17/10688—Adjustment of the adherence to the glass layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the invention relates to a molding composition for the production of foils or the like for composite security panes based on plasticized, partially acetalized polyvinyl alcohol, in particular partially butyralized polyvinyl alcohol (polyvinyl butyral, PVB) with silane compounds as adhesion-regulating additives and their use as an intermediate layer (adhesive film) in Compound safety washers.
  • plasticized, partially acetalized polyvinyl alcohol in particular partially butyralized polyvinyl alcohol (polyvinyl butyral, PVB) with silane compounds as adhesion-regulating additives and their use as an intermediate layer (adhesive film) in Compound safety washers.
  • Plasticized (plasticized) PVB films with a moisture content of 0.2 to 0.8% by weight have proven particularly useful for the production of composite safety panes.
  • the polyvinyl butyral resin is characterized by a proportion of 10 to 28% by weight, preferably 15 to 23% by weight, of vinyl alcohol units.
  • the plasticizer content of the plasticized polyvinyl butyral resin is 20 to 60 parts by weight, preferably 33 to 44 parts by weight, based on 100 parts by weight of polyvinyl butyral resin.
  • Laminated safety glasses are widely used in the automotive and construction sectors.
  • the requirements placed on the laminated glass panes are very diverse.
  • the chemical properties of the plasticized physikali ⁇ rule Pol_ ⁇ vinylbutyralform- are ultimately body crucial to the quality and safety of laminated glass, which as an intermediate layer connecting two or more panes of glass together.
  • This intermediate layer has the task of providing the composite pane with good shock resistance and binding the glass splinters which arise in the event of an impact through good adhesion.
  • the intermediate layer also has to ensure a high level of transparency, light, moisture and aging resistance (adhesion resistance).
  • the plasticized polyvinyl butyral foils used as an intermediate layer for laminated safety glass generally have too high a glass adhesion for vehicle construction. To ensure that the windshield is retained in its entirety in the event of impacts and at the same time the impact can be absorbed by energy absorption, the adhesion must be optimized.
  • the disadvantages of these alkaline compounds are a chemical change in the plasticized polyvinyl butyral resin, which is reflected in discoloration due to damage to the polyvinyl butyral / plasticizer system and in clouding of the resulting laminated safety glass due to unsatisfactory moisture resistance. Discoloration and clouding impair the transparency of the laminated safety glass.
  • the alkalinity as a further consequence changes molecular sizes such as the molecular weight and distribution of the polymer and the resistance to aging. If the film is moistened at the edges, the adhesion is reduced and the film comes off the glass.
  • silanes as adhesion-influencing agents in plasticized polyvinyl butyral films has therefore already been considered (JP-A-81296/69, DE-C3- 24 10 153, DE-Al-26 50 120).
  • all of the silanes previously proposed have poor reproducibility of the adhesion properties.
  • the condensation and crosslinking products made from hydrolysed silanes during the large-scale production of films - recognizable with the naked eye as nodules in the film - imply that the quality of the laminated safety glass meets the requirements and that it is reproducible Adhesion adjustment of the film to the glass, so that their application has so far failed in practice.
  • the object of the present invention is to provide a molding composition for the production of films or the like for composite security panes on the basis of plasticizer-containing, partially acetalized polyvinyl alcohol with silane compounds as adhesion-regulating additives, which does not have the disadvantages mentioned.
  • the invention solves this problem in that an organosilane of the general formula is used as the silane compound
  • R - "- and R each independently of one another are an optionally branched alkyl group having 1 to 4 carbon atoms or a group of the formula -0- (R - 0-_ " m R 3 ;
  • R is in each case an optionally branched alkyl group with 1 to 4 carbon atoms or hydrogen, where the groups R J can be the same or different;
  • R is in each case an optionally branched alkylene group having 2 to 4 carbon atoms, where the groups R 4 can be the same or different;
  • R J is an optionally branched alkylene group with 1 to 6 carbon atoms and in each case independently of one another one of the numbers from 0 to 16.
  • the organosilanes proposed according to the invention surprisingly combine the advantages of alkali or alkaline earth compounds - reproducible adhesion regulation - with those of the known silicon compounds - high transparency, avoidance of edge clouding and discoloration - without their specific Show disadvantages. This is all the more surprising since, for more than twenty years, the search for suitable substances has been unsuccessful.
  • An organosilane of the formula (I) is preferably used in which
  • R 4 is a straight-chain alkylene group with 2 to 4 carbon atoms, the groups R 4 being the same;
  • R 3 is a straight chain alkyl group having 1 to 4 carbon atoms;
  • R 5 is a straight-chain alkylene group with 2 to 6 carbon atoms.
  • the groups R 1 and R 2 preferably correspond to the corresponding FFoorramel -0- (R 4 -0 ⁇ / ⁇ n R 3 and are identical to one another.
  • R 4 is furthermore preferably an alkylene group with 2 carbon atoms (ethylene group) and R 3 is in each case a methyl group.
  • M is preferably 3 in each case.
  • Organosilanes suitable according to the invention are, for example, 3- (ethyltriethylene glycol) -propylsilane-tris-methyltriethylene glycol esters of the structure CH3- (OC 2 H 4 ) 3-0- (CH2) 3-Si - [(0C 2 H 4 ) 3-O- CH3] 3 ;
  • the silane is particularly preferred
  • Organosilanes of this structure are known from DE-C2-26 52 719 as additives to hydraulic fluids. With regard to their manufacture, reference is made to this document and to DE-OS 39 08 792 (earlier application P 39 08 792.1 from Huls AG from March 17, 1989, designation: "Process for the preparation of unsymmetrical, terminally unsaturated glycol ethers” ) and DE-OS 39 08 791 (earlier application P 39 08 791.3 from Hüls AG dated March 17, 1989, title: “Process for the preparation of organosilicon compounds”).
  • One or more of the organosilanes according to the invention are preferably incorporated homogeneously into the plasticizer-containing polymer.
  • the silanes according to the invention have the desired adhesion-regulating effect even in very small amounts of 0.003 to 0.8% by weight, based on the plasticized polyvinyl butyral.
  • silicon- and organofunctional silanes are preferably dissolved (optionally dispersed) in the plasticizer and processed with the polymer in a known manner on a calender or in an extruder to give preferably 0.3 to 1.5 mm thick films ( EP-A1-0 185 863, GB-PS-12 71 188).
  • Suitable plasticizers are the esters of polyhydric acids, polyhydric alcohols or oligoether glycols known from the prior art, such as e.g. Di (2-ethylhexyl) adipate, dihexyl adipate, dibutyl sebacate, dioctyl phthalate, esters of di-, tri- and tetraethylene glycols with linear or branched aliphatic carboxylic acids and mixtures of these plasticizers.
  • Plasticizer mixtures with phosphoric acid esters are used in polyvinyl butyrals with higher vinyl alcohol units.
  • the plasticizers according to the present invention are mainly esters of aliphatic diols with long-chain aliphatic carboxylic acids, in particular esters of triethylene glycol with 6 to 10 carbon atoms-containing aliphatic car- bonic acids such as 2-ethylbutyric acid and heptanoic acid.
  • Plasticized polyvinyl butyral preferably contains 24 to 32% by weight of plasticizer.
  • the silane can also be used in a suitable solvent which does not impair the film properties but improves the wetting of the silane on the film by suitable methods (spraying, dipping, printing) ) are applied to the film surface.
  • suitable solvent which does not impair the film properties but improves the wetting of the silane on the film by suitable methods (spraying, dipping, printing) ) are applied to the film surface.
  • Aromatics, esters, chlorinated hydrocarbons and comparable non-polar solvents are suitable as solvents.
  • the silane diluted in a solvent can be applied to the surface of the glass plates which face the plasticized polyvinyl butyral during the production of the composite safety disks.
  • the silane concentrations are between 0.003 and 0.8% by weight, preferably and in many cases sufficiently 0.003 to 0.3% by weight, very preferably between 0.01 and 0.1% by weight on the plasticized polyvinyl butyral.
  • the polyvinyl acetals are produced by acetalization of hydrolyzed polyvinyl esters.
  • aldehydes for example formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and the like.
  • butyraldehyde can be used.
  • the carboxyl group of the polyvinyl ester belongs to an aliphatic acid with 1 to 8 carbon atoms, preferably it is an acetate group.
  • the polyvinyl acetal contains 0 to 20% by weight, preferably 0.5 to 3.0% by weight, of acetyl groups.
  • a partially butyralized polyvinyl alcohol (PVB) is preferably used.
  • thermoplastic deformable polyvinyl butyral resin can be used as the polyvinyl butyral resin.
  • a resin is preferably used which contains 15 to 23% by weight of vinyl alcohol units.
  • the water content of the films should be set to 0.2 to 0.8% by weight.
  • a film according to the invention is placed between glass plates of the same thickness or different thickness and pressed at 60 to 100 ° C. to form a preliminary bond.
  • the final composite is e.g. in an autoclave at 120 to 160 ° C and 8 to 16 bar within a pressing time of 10 to 30 min.
  • the dielectric strength is tested based on ANSI 26.1-1983, 5.26 Test 26.
  • a laminated glass pane of 30 x 30 cm tempered at 23 ° C. is placed horizontally in a frame.
  • a 2.26 kg steel ball is freely dropped onto the center of the laminated glass pane from above.
  • the drop heights are varied and the drop height is determined at which 8 of the 10 samples are not penetrated by the steel ball.
  • the distance of the ball from the glass surface is given as the ball drop height. The greater this drop height, the higher the dielectric strength of the laminated safety glass.
  • the yellowness index (AYI, means difference from measured value of the laminated safety glass and glass without foil) according to ASTM-D-1925 (light type C, 2 ° observer) is determined.
  • the entered b-value corresponds to the YI of ASTM-D-1925.
  • the edge clouding which affects the adhesion resistance and transparency was determined according to ANSI 26.1-1977, no. 5.3, Test 3 evaluated, it being measured in what width the clouding edge strip has penetrated into the interior of the laminated safety glass.
  • Example 1 72% by weight of polyvinyl butyral resin, which has a vinyl alcohol unit content of 20.5% by weight, and 28% by weight of triethylene glycol di-n-heptanoic acid ester as plasticizer, in which 0.7% by weight % Tinuvin P (light stabilizer, Ciba Geigy) and 0.14 to 0.21% by weight of 3- (methyltriethylene glycol) -propylsilane-tris-methyltriethylene glycol ester, based in each case on the plasticizer content, are dissolved in accordance with EP-A1-0 185 863 extruded into a 0.76 mm thick film and, after the air conditioning had been brought to an average moisture level of 0.45% by weight, processed with 2.2 mm thick float glass panes to form laminated safety glasses.
  • plasticizer in which 0.7% by weight % Tinuvin P (light stabilizer, Ciba Geigy) and 0.14 to 0.21% by weight of 3- (methyltriethylene glycol) -propylsilane
  • a laminated glass pane was produced as in Example 1, except that 2- (methyltriethylene glycol) -ethylsilanetris-methyltriethylene glycol ester with a proportion of 0.14 to 0.21% by weight, based on the proportion of plasticizer, was used as the silane .
  • Example 3 A laminated glass pane was produced as in Example 1, but with 4- (methyltriethylene glycol) -butylsilanetris-methyltriethylene glycol ester as the silane in a proportion of 0.14 to
  • Example 2 The procedure was as in Example 1, but instead of the silane according to the invention, 4.6% by weight, based on the plasticizer part - a 10 wt .-% aqueous potassium acetate solution was used.
  • Comparative Example 5 The procedure was as in Example 1, but instead of the silane according to the invention, an isobutyl-tri-methoxisilane according to DE-C-24 10 153 in amounts of 1 to 1.8% by weight, based on the plasticizer content, was used.
  • the laminated glasses corresponding to tests 1 to 5 were then subjected to a ball drop test in accordance with ANSI 26.1-1983 (Table 1).
  • Additive concentration ball drop height (m) d.Additive wt .-% beginning d. Mid-d. Year
  • the adhesion-reducing effect of the silanes which is expressed in the height of the ball drop, and the optical purity of the film (freedom from nodules) are only reproducible in accordance with the requirements of the silane according to the invention.
  • the reproducibility of the breakdown strength (> 4m) according to the requirements for the silane according to the invention is demonstrated on laminated glass panes, the foils of which were produced in different periods (beginning and middle of the year).
  • Additive concentration ball drop height (m) d.Additive wt .-% beginning d. Mid-d. Year

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La matière de moulage décrite est à base d'alcool polyvynilique plastifié, partiellement acétalisé, notamment du butyral polyvinylique (PVB), avec des composés de silane comme additif régulant l'adhérence. L'invention concerne également la mise en oeuvre de cette matière de moulage pour fabriquer des films extrudés utilisés comme nappe intermédiaire dans des vitres en verre feuilleté. Il est proposé que le composé de silicium soit un organosilane de formule (I), où R1 et R2 sont indépendamment un groupe alkyl éventuellement ramifié, avec 1 à 4 atomes de carbone, ou bien un groupe de formule (II); chaque R3 est un groupe alkyl éventuellement ramifié, avec 1 à 4 atomes de carbone, ou bien un hydrogène, et les groupes R3 peuvent être identiques ou différents; chaque R4 est un groupe alkylène éventuellement ramifié, avec 2 à 4 atomes de carbone, et les groupes R4 peuvent être identiques ou différents; R5 est un groupe alkylène éventuellement ramifié, avec 1 à 6 atomes de carbone; et chaque m peut être n'importe quel nombre de 0 à 16.The molding material described is based on plasticized, partially acetalized polyvinyl alcohol, in particular polyvinyl butyral (PVB), with silane compounds as an adhesion regulating additive. The invention also relates to the use of this molding material to manufacture extruded films used as an intermediate sheet in laminated glass panes. It is proposed that the silicon compound is an organosilane of formula (I), where R1 and R2 are independently an optionally branched alkyl group, with 1 to 4 carbon atoms, or a group of formula (II); each R3 is an optionally branched alkyl group, with 1 to 4 carbon atoms, or alternatively a hydrogen, and the R3 groups may be the same or different; each R4 is an optionally branched alkylene group, with 2 to 4 carbon atoms, and the R4 groups may be the same or different; R5 is an optionally branched alkylene group with 1 to 6 carbon atoms; and each m can be any number from 0 to 16.

Description

BesehreibungDescription
Formmasse zur Herstellung von Folien für Verbundsicherheits¬ scheibenMolding compound for the production of films for composite safety disks
Technisches GebietTechnical field
Die Erfindung betrifft eine Formmasse zur Herstellung von Fo¬ lien o. dgl. für Verbundsicherheitsscheiben auf der Basis von weichgemachtem, teilacetalisiertem Polyvinylalkohol- insbeson- dere teilbutyralisiertem Polyvinylalkohol (Polyvinylbutyral, PVB) mit Silanverbindungen als haftungsregulierenden Zusätzen sowie deren Verwendung als Zwischenschicht (Klebefolie) in Ver¬ bundsicherheitsscheiben.The invention relates to a molding composition for the production of foils or the like for composite security panes based on plasticized, partially acetalized polyvinyl alcohol, in particular partially butyralized polyvinyl alcohol (polyvinyl butyral, PVB) with silane compounds as adhesion-regulating additives and their use as an intermediate layer (adhesive film) in Compound safety washers.
Für die Herstellung von Verbundsicherheitsscheiben haben sich insbesondere plastifizierte (weichgemachte) PVB-Folien bewährt, die einen Feuchtigkeitsgehalt von 0,2 bis 0,8 Gew.-% haben. Das Polyvinylbutyralharz ist durch einen Anteil von 10 bis 28 Gew.- %, vorzugsweise 15 bis 23 Gew.-%, Vinylalkoholeinheiten gekenn- zeichnet. Der Weichmachergehalt des plastifzierten Polyvinylbu- tyralharzes beträgt 20 bis 60 Gew.-Teile- vorzugsweise 33 bis 44 Gew.-Teile, bezogen auf 100 Gew.-Teile Polyvinylbutyralharz.Plasticized (plasticized) PVB films with a moisture content of 0.2 to 0.8% by weight have proven particularly useful for the production of composite safety panes. The polyvinyl butyral resin is characterized by a proportion of 10 to 28% by weight, preferably 15 to 23% by weight, of vinyl alcohol units. The plasticizer content of the plasticized polyvinyl butyral resin is 20 to 60 parts by weight, preferably 33 to 44 parts by weight, based on 100 parts by weight of polyvinyl butyral resin.
Verbundsicherheitsgläser sind im Fahrzeug- und Baubereich weit verbreitet. Die an die Verbundglasscheiben gestellten Anforde¬ rungen sind sehr vielfältig. Für die Qualität und Sicherheit der Verbundglasscheiben sind letztlich die chemisch-physikali¬ schen Eigenschaften des plastifizierten Pol_~vinylbutyralform- körpers entscheidend, der als Zwischenschicht zwei oder mehr Glasscheiben miteinander verbindet. Diese Zwischenschicht hat die Aufgabe, der Verbundscheibe eine gute Stoßfestigkeit zu verleihen und die bei einem Aufprall entstehenden Glassplitter durch gute Haftung zu binden.Laminated safety glasses are widely used in the automotive and construction sectors. The requirements placed on the laminated glass panes are very diverse. The chemical properties of the plasticized physikali¬ rule Pol_ ~ vinylbutyralform- are ultimately body crucial to the quality and safety of laminated glass, which as an intermediate layer connecting two or more panes of glass together. This intermediate layer has the task of providing the composite pane with good shock resistance and binding the glass splinters which arise in the event of an impact through good adhesion.
Neben diesen mechanischen Eigenschaften hat die Zwischenschicht auch eine hohe Transparenz, Licht-, Feuchtigkeits- und Alte¬ rungsbeständigkeit (Haftungsbeständigkeit) zu gewährleisten. Die als Zwischenschicht für Verbundsicherheitsglas benutzten plastifizierten Polyvinylbutyralfolien haben im allgemeinen für den Fahrzeugbau eine zu hohe Glashaftung. Damit die Windschutz¬ scheibe bei Stößen in ihrer Gesamtheit erhalten bleibt und gleichzeitig der Stoß durch Energieabsorption abgefangen werden kann, ist die Haftung zu optimieren.In addition to these mechanical properties, the intermediate layer also has to ensure a high level of transparency, light, moisture and aging resistance (adhesion resistance). The plasticized polyvinyl butyral foils used as an intermediate layer for laminated safety glass generally have too high a glass adhesion for vehicle construction. To ensure that the windshield is retained in its entirety in the event of impacts and at the same time the impact can be absorbed by energy absorption, the adhesion must be optimized.
Stand der TechnikState of the art
Es ist bekannt, daß die Glashaftung der Folien durch Zusatz verschiedener Alkali- oder Erdalkaliverbindungen, beispielswei¬ se in Form von Hydroxiden, Salzen, Komplexen, reduziert wird (DE-B-15 96 902, DE-B-15 96 894, US-A-3,249,488, US-A- 3,249,489, US-A-3,262,835, ÜS-A-3,262,836) .It is known that the glass adhesion of the films is reduced by adding various alkali or alkaline earth compounds, for example in the form of hydroxides, salts, complexes (DE-B-15 96 902, DE-B-15 96 894, US Pat. A-3,249,488, US-A-3,249,489, US-A-3,262,835, US-A-3,262,836).
Die Nachteile dieser alkalisch reagierenden Verbindungen liegen in einer chemischen Veränderung des plastifizierten Polyvinyl- butyralharzes, was sich in Verfärbungen infolge einer Schädi¬ gung des Polyvinylbutyral/Weichmacher-Systems und in Trübungen des resultierenden Verbundsicherheitsglases infolge unbefriedi- gender Feuchtigkeitsbeständigkeit äußert. Verfärbungen und Trü¬ bungen beeinträchtigen die Transparenz des Verbundsicherheits¬ glases. Darüber hinaus ändern sich durch die Alkalität als wei¬ tere Folge molekulare Größen wie Molmasse und -Verteilung des Polymeren sowie die Alterungsbeständigkeit. Bei einer Randauf- feuchtung der Folie wird die Haftung reduziert, und es treten Ablösungen der Folie vom Glas ein.The disadvantages of these alkaline compounds are a chemical change in the plasticized polyvinyl butyral resin, which is reflected in discoloration due to damage to the polyvinyl butyral / plasticizer system and in clouding of the resulting laminated safety glass due to unsatisfactory moisture resistance. Discoloration and clouding impair the transparency of the laminated safety glass. In addition, the alkalinity as a further consequence changes molecular sizes such as the molecular weight and distribution of the polymer and the resistance to aging. If the film is moistened at the edges, the adhesion is reduced and the film comes off the glass.
Es wurde daher auch schon die Verwendung von Silanen als die Haftung beeinflussende Mittel bei plastifizierten Polyvinyl- butyralfolien in Betracht gezogen (JP-A-81296/69, DE-C3- 24 10 153, DE-Al-26 50 120). Sämtliche bisher vorgeschlagenen Silane weisen aber eine mangelhafte Reproduzierbarkeit der Haf¬ tungseigenschaften auf. Die aus hydrolisierten Silanen während der großtechnischen Folienherstellung entstandenen Kondensa- tions- und Vernetzungsprodukte - mit bloßem Auge als Knötchen in der Folie erkennbar - schließen eine anforderungsgerechte Qualität der Verbundsicherheitsgläser und eine reproduzierbare Haftungseinstellung der Folie zum Glas aus, so daß deren Anwen¬ dung in der Praxis bislang scheiterte.The use of silanes as adhesion-influencing agents in plasticized polyvinyl butyral films has therefore already been considered (JP-A-81296/69, DE-C3- 24 10 153, DE-Al-26 50 120). However, all of the silanes previously proposed have poor reproducibility of the adhesion properties. The condensation and crosslinking products made from hydrolysed silanes during the large-scale production of films - recognizable with the naked eye as nodules in the film - imply that the quality of the laminated safety glass meets the requirements and that it is reproducible Adhesion adjustment of the film to the glass, so that their application has so far failed in practice.
Aufgabe der Erfindung Aufgabe der vorliegenden Erfindung ist es, eine Formmasse zur Herstellung von Folien o. dgl. für Verbundsicherheitsscheiben auf der Basis von weichmacherhaltigem, teilacetalisiertem Poly¬ vinylalkohol mit Silanverbindungen als haftungsregulierenden Zusätzen zur Verfügung zu stellen, die die genannten Nachteile nicht aufweist.OBJECT OF THE INVENTION The object of the present invention is to provide a molding composition for the production of films or the like for composite security panes on the basis of plasticizer-containing, partially acetalized polyvinyl alcohol with silane compounds as adhesion-regulating additives, which does not have the disadvantages mentioned.
Darstellung der ErfindungPresentation of the invention
Die Erfindung löst diese Aufgabe dadurch, daß als Silanverbin- dung ein Organosilan der allgemeinen FormelThe invention solves this problem in that an organosilane of the general formula is used as the silane compound
I) R3-(0-R4-rmO-R5-SiR1R2[-0-(R'-O ^R3]I) R 3 - (0-R 4 -r m OR 5 -SiR 1 R 2 [-0- (R'-O ^ R 3 ]
eingesetzt wird, wobeiis used, whereby
R-"- und R jeweils unabhängig voneinander eine ggf. ver- zweigte Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder eine Gruppe der Formel -0-(R--0-_"mR3 sind;R - "- and R each independently of one another are an optionally branched alkyl group having 1 to 4 carbon atoms or a group of the formula -0- (R - 0-_ " m R 3 ;
R jeweils eine ggf. verzweigte Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder Wasserstoff ist, wo- bei die Gruppen RJ gleich oder verschieden sein können;R is in each case an optionally branched alkyl group with 1 to 4 carbon atoms or hydrogen, where the groups R J can be the same or different;
R jeweils eine ggf. verzweigte Alkylengruppe mit 2 bis 4 Kohlenstoffatomen ist, wobei die Gruppen R4 gleich oder verschieden sein können;R is in each case an optionally branched alkylene group having 2 to 4 carbon atoms, where the groups R 4 can be the same or different;
RJ eine ggf. verzweigte Alkylengruppe mit 1 bis 6 Kohlenstoffatomen und jeweils unabhängig voneinander eine der Zahlen von 0 bis 16 ist.R J is an optionally branched alkylene group with 1 to 6 carbon atoms and in each case independently of one another one of the numbers from 0 to 16.
Die erfindungsgemäß vorgeschlagenen Organosilane verbinden überraschend die Vorteile von Alkali- bzw. Erdalkaliverbindun¬ gen - reproduzierbare Haftungsregulierung - mit denen der be¬ kannten Siliciumverbindungen - hohe Transparenz, Vermeidung ei¬ ner Randeintrübung und Verfärbung - ohne deren spezifische Nachteile aufzuweisen. Dieses ist um so überraschender, da seit mehr als zwanzig Jahren mit großem Aufwand vergeblich nach ent¬ sprechenden Substanzen gesucht wird.The organosilanes proposed according to the invention surprisingly combine the advantages of alkali or alkaline earth compounds - reproducible adhesion regulation - with those of the known silicon compounds - high transparency, avoidance of edge clouding and discoloration - without their specific Show disadvantages. This is all the more surprising since, for more than twenty years, the search for suitable substances has been unsuccessful.
Bevorzugt ist ein Organosilan der Formel (I) eingesetzt, bei demAn organosilane of the formula (I) is preferably used in which
R4 eine geradkettige Alkylengruppe mit 2 bis 4 Kohlenstoff¬ atomen ist, wobei die Gruppen R4 gleich sind; R3 eine geradkettige Alkylgruppe mit 1 bis 4 Kohlenstoffato- men ist;R 4 is a straight-chain alkylene group with 2 to 4 carbon atoms, the groups R 4 being the same; R 3 is a straight chain alkyl group having 1 to 4 carbon atoms;
R5 eine geradkettige Alkylengruppe mit 2 bis 6 Kohlenstoff¬ atomen.R 5 is a straight-chain alkylene group with 2 to 6 carbon atoms.
Bevorzugt entsprechen die Gruppen R1 und R2 jjeewweeiillss ddeerr FFoorramel -0-(R4-0</^nR3 und sind unter- einander gleich.The groups R 1 and R 2 preferably correspond to the corresponding FFoorramel -0- (R 4 -0 < / ^ n R 3 and are identical to one another.
Bevorzugt ist weiterhin R4 eine Alkylengruppe mit 2 Kohlen¬ stoffatomen (Ethylengruppe) und R3 jeweils eine Methylgruppe. Bevorzugt ist m jeweils 3.R 4 is furthermore preferably an alkylene group with 2 carbon atoms (ethylene group) and R 3 is in each case a methyl group. M is preferably 3 in each case.
Erfindungsgemäß geeignete Organosilane sind beispielsweise 3-( ethyltriethylenglykoxi)-propylsilan-tris-methyltriethylen- glykolester der Struktur CH3-(OC2H4)3-0-(CH2)3-Si-[(0C2H4)3-O-CH3]3;Organosilanes suitable according to the invention are, for example, 3- (ethyltriethylene glycol) -propylsilane-tris-methyltriethylene glycol esters of the structure CH3- (OC 2 H 4 ) 3-0- (CH2) 3-Si - [(0C 2 H 4 ) 3-O- CH3] 3 ;
3-(Methyltriethylenglykoxi)-2-methylpropylsilan-tris-methyltri- ethylenglykolester der Struktur CH3-(OC2H4) (0C2H4)3-O-CH3]3; 3- (methyltriethylene glycol) -2-methylpropylsilane-tris-methyltriethylene glycol ester of the structure CH3- (OC 2 H 4 ) (0C 2 H 4 ) 3-O-CH3] 3;
3-(Ethyltriethylenglykoxi)-propylsilan-tris-ethyltriethylengly- kolester der Struktur3- (Ethyltriethylenglykoxi) -propylsilan-tris-ethyltriethylenglykolester of the structure
CH3-CH2-(0C2H4)3-O-(CH2)3-Si-[(OC2H4)3-0-CH2-CH3]3;CH 3 -CH 2 - (0C 2 H 4 ) 3-O- (CH 2 ) 3-Si - [(OC 2 H 4 ) 3 -0-CH 2 -CH 3 ] 3;
3-(Ethyltriethylenglykoxi)-2-methylpropylsilan-tris-ethyltri- ethylenglykolester der Struktur CH3-CH2-( (0C2H4)3-0-CH2-CH3]3; 3- (Ethyltriethylenglykoxi) -2-methylpropylsilan-tris-ethyltriethylene glycol ester of the structure CH 3 -CH 2 - ((0C 2 H 4 ) 3 -0-CH 2 -CH 3 ] 3;
3-(Butyltriethylenglykoxi)-propylsilan-tris-butyltriethylengly- kolester der Struktur3- (butyltriethylene glycol) propyl silane tris butyl triethylene glycol ester of the structure
CH3-(CH2)3-(0C2H4)3-O-(CH2)3-Si-[(0C2H4)3-O-(CH2)3-CH3]3;CH 3 - (CH 2 ) 3- (0C 2 H 4 ) 3-O- (CH 2 ) 3-Si - [(0C 2 H 4 ) 3-O- (CH 2 ) 3-CH3] 3 ;
2-(Methyltriethylenglykoxi)-ethylsilan-tris-methyltriethylen- glykolester der Struktur CH3-(OC2H4)3-O-(CH2)2-Si-[(OC2H4)3-O-CH3]3;2- (methyltriethylene glycol) -ethylsilane-tris-methyltriethylene glycol ester of the structure CH3- (OC 2 H 4 ) 3-O- (CH 2 ) 2 -Si - [(OC 2 H 4 ) 3-O-CH3] 3;
4-(Methyltriethylenglykoxi)-butylsilan-tris-methyltriethylen- glykolester der Struktur CH3-(OC2H4)3-0-(CH2)4-Si[(OC2H4)3-0-α_3]3;4- (methyltriethylene glycol) -butylsilane-tris-methyltriethylene glycol ester of the structure CH 3 - (OC 2 H 4 ) 3-0- (CH 2 ) 4 -Si [(OC 2 H 4 ) 3-0-α_3] 3 ;
3-(Methyltetraethylenglykoxi)-propylsilan-tris-methyltetraethy- lenglykolester der Struktur CH3-(OC2H4)4-0-(CH2)3-Si-[(0C2H4)4-O-CH3]3;3- (Methyltetraethyleneglykoxi) propylsilane-tris-methyltetraethylene glycol ester of the structure CH 3 - (OC 2 H 4 ) 4 -0- (CH 2 ) 3 -Si - [(0C 2 H 4 ) 4 -O-CH 3 ] 3 ;
3-(Methylpentaethylenglykoxi)-propylsilan-tris-methylpentaethy- lenglykolester der Struktur CH3-(0C2H4)5-0-(CH2)3-Si-[(0C2H4)5-O-CH3]3;3- (Methylpentaethyleneglykoxi) propylsilane-tris-methylpentaethylene glycol ester of the structure CH 3 - (0C 2 H 4 ) 5 -0- (CH 2 ) 3-Si - [(0C 2 H 4 ) 5 -O-CH 3 ] 3;
Si-Methyl-(methyltriethylenglykoxi)-methyl-bis-methyltriethy- lenglykolesterSi-methyl- (methyltriethylene glycol) -methyl-bis-methyltriethylene glycol ester
CH3(0C2H4)30CH2Si(CH3)[ (0C2H4)3OCH3]2;CH3 (0C 2 H 4 ) 3 0CH 2 Si (CH3) [(0C 2 H 4 ) 3OCH3] 2 ;
Si-Si-Dimethyl-(methyltriethylenglykoxi)-methyl-methyltriethy- lenglykolester CH3(0C2H4)3OCH2Si(CH3)2(OC2H4)3OCH3.Si-Si-dimethyl- (methyltriethylene glycol) -methyl-methyltriethylene glycol ester CH3 (0C 2 H 4 ) 3 OCH 2 Si (CH3) 2 (OC 2 H 4 ) 3OCH3.
Besonders bevorzugt wird das SilanThe silane is particularly preferred
3-(Methyltriethylenglykoxi)-propylsilan-tris-methyltriethylen- glykolester der Struktur3- (methyltriethylene glycol) -propylsilane-tris-methyltriethylene glycol ester of the structure
CH3-(OC2H4)3-0-(CH2)3 - Si-[(OC2H4)3-OCH3]3 CH 3 - (OC 2 H 4 ) 3 -0- (CH 2 ) 3 - Si - [(OC 2 H 4 ) 3 -OCH 3 ] 3
verwendet. Organosilane dieser Struktur sind aus der DE-C2-26 52 719 als Zusätze zu Hydraulikflüssigkeiten bekannt. Bezüglich ihrer Her¬ stellung wird auf diese Schrift sowie auf die DE-OS 39 08 792 (ältere Anmeldung P 39 08 792.1 der Fa. Hüls AG vom 17.03.1989, Bezeichnung: "Verfahren zur Herstellung unsymmetrischer, end¬ ständig einfach ungesättigter Glykolether") und DE-OS 39 08 791 (ältere Anmeldung P 39 08 791.3 der Fa. Hüls AG vom 17.03.1989, Bezeichnung: "Verfahren zur Herstellung von siliciumorganischen Verbindungen") verwiesen.used. Organosilanes of this structure are known from DE-C2-26 52 719 as additives to hydraulic fluids. With regard to their manufacture, reference is made to this document and to DE-OS 39 08 792 (earlier application P 39 08 792.1 from Huls AG from March 17, 1989, designation: "Process for the preparation of unsymmetrical, terminally unsaturated glycol ethers" ) and DE-OS 39 08 791 (earlier application P 39 08 791.3 from Hüls AG dated March 17, 1989, title: "Process for the preparation of organosilicon compounds").
Bevorzugt werden ein oder mehrere der erfindungsgemäßen Organo¬ silane homogen in das weichmacherhaltige Polymerisat eingear¬ beitet.One or more of the organosilanes according to the invention are preferably incorporated homogeneously into the plasticizer-containing polymer.
Überraschend hat sich herausgestellt, daß die erfindungsgemäßen Silane schon in sehr geringen Mengen von 0,003 bis 0,8 Gew.-%, bezogen auf das weichgemachte Polyvinylbutyral, die gewünschte haftungsregulierende Wirkung entfalten.Surprisingly, it has been found that the silanes according to the invention have the desired adhesion-regulating effect even in very small amounts of 0.003 to 0.8% by weight, based on the plasticized polyvinyl butyral.
Diese silicium- und organofunktionellen Silane werden vorzugs¬ weise im Weichmacher gelöst (ggf. dispergiert) und mit dem Po¬ lymerisat auf bekannte Weise auf einem Kalander oder in einem Extruder zu vorzugsweise 0,3 bis 1,5 mm dicken Folien verarbei¬ tet (EP-A1-0 185 863, GB-PS-12 71 188).These silicon- and organofunctional silanes are preferably dissolved (optionally dispersed) in the plasticizer and processed with the polymer in a known manner on a calender or in an extruder to give preferably 0.3 to 1.5 mm thick films ( EP-A1-0 185 863, GB-PS-12 71 188).
Als Weichmacher eignen sich die nach dem Stand der Technik be¬ kannten Ester von mehrwertigen Säuren, mehrwertigen Alkoholen oder Oligoetherglykolen, wie z.B. Di(2-ethylhexyl)adipat, Dihe- xyladipat, Dibutylsebacat, Dioctylphthalat, Ester von Di-, Tri- und Tetraethylenglykolen mit linearen oder verzweigten alipha- tischen Carbonsäuren und Mischungen dieser Weichmacher. Weich¬ machermischungen mit Phosphorsäureester werden bei Polyvinylbu- tyralen mit höheren Vinylalkoholeinheiten eingesetzt.Suitable plasticizers are the esters of polyhydric acids, polyhydric alcohols or oligoether glycols known from the prior art, such as e.g. Di (2-ethylhexyl) adipate, dihexyl adipate, dibutyl sebacate, dioctyl phthalate, esters of di-, tri- and tetraethylene glycols with linear or branched aliphatic carboxylic acids and mixtures of these plasticizers. Plasticizer mixtures with phosphoric acid esters are used in polyvinyl butyrals with higher vinyl alcohol units.
Als Weichmacher nach der vorliegenden Erfindung werden vor al¬ lem Ester von aliphatischen Diolen mit langkettigen aliphati- schen Carbonsäuren verwendet, insbesondere Ester von Triethy- lenglykol mit 6 bis 10 C-Atome enthaltenden aliphatischen Car- bonsäuren, wie 2-Ethylbuttersäure und Heptansäure. Plastifi- ziertes Polyvinylbutyral enthält vorzugsweise 24 bis 32 Gew.-% Weichmacher.The plasticizers according to the present invention are mainly esters of aliphatic diols with long-chain aliphatic carboxylic acids, in particular esters of triethylene glycol with 6 to 10 carbon atoms-containing aliphatic car- bonic acids such as 2-ethylbutyric acid and heptanoic acid. Plasticized polyvinyl butyral preferably contains 24 to 32% by weight of plasticizer.
Neben der Einarbeitung des Silans in das plastifizierte Polyvi¬ nylbutyral kann das Silan aber auch in einem geeigneten Lö¬ sungsmittel, das die Folieneigenschaften nicht beeinträchtigt, aber das Benetzen des Silans auf der Folie verbessert, nach ge¬ eigneten Methoden (Sprühen, Tauchen, Drucken) auf der Folien- Oberfläche aufgebracht werden. Als Lösungsmittel eignen sich Aromaten, Ester, Chlorkohlenwasserstoffe und vergleichbar unpo¬ lare Lösungsmittel.In addition to the incorporation of the silane into the plasticized polyvinyl butyral, the silane can also be used in a suitable solvent which does not impair the film properties but improves the wetting of the silane on the film by suitable methods (spraying, dipping, printing) ) are applied to the film surface. Aromatics, esters, chlorinated hydrocarbons and comparable non-polar solvents are suitable as solvents.
Ebenso läßt sich das in einem Lösungsmittel verdünnte Silan auf die Oberfläche der Glasplatten auftragen, welche dem plastifi¬ zierten Polyvinylbutyral bei der Herstellung der Verbundsicher¬ heitsscheiben zugewandt sind.Likewise, the silane diluted in a solvent can be applied to the surface of the glass plates which face the plasticized polyvinyl butyral during the production of the composite safety disks.
Im allgemeinen liegen die Silan-Konzentrationen zwischen 0,003 und 0,8 Gew.-%, bevorzugt und in vielen Fällen ausreichend 0,003 bis 0,3 Gew.-%, sehr bevorzugt zwischen 0,01 und 0,1 Gew.-%, bezogen auf das plastifizierte Polyvinylbutyral.In general, the silane concentrations are between 0.003 and 0.8% by weight, preferably and in many cases sufficiently 0.003 to 0.3% by weight, very preferably between 0.01 and 0.1% by weight on the plasticized polyvinyl butyral.
Die Polyvinylacetale werden durch Acetalisierung von hydroli- sierten Polyvinylestern hergestellt. Als Aldehyde können bei¬ spielsweise Formaldehyd, Acetaldehyd, Propionaldehyd, Butyral- dehyd, Valeraldehyd u. dgl., bevorzugt Butyraldehyd, verwendet werden. Die Carboxylgruppe des Polyvinylesters gehört zu einer aliphatischen Säure mit 1 bis 8 C-Atomen, bevorzugt ist es eine Acetatgruppe. Das Polyvinylacetal enthält 0 bis 20 Gew.-%, be¬ vorzugt 0,5 bis 3,0 Gew.-%, Acetylgruppen.The polyvinyl acetals are produced by acetalization of hydrolyzed polyvinyl esters. As aldehydes, for example formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and the like. Like., Preferably butyraldehyde, can be used. The carboxyl group of the polyvinyl ester belongs to an aliphatic acid with 1 to 8 carbon atoms, preferably it is an acetate group. The polyvinyl acetal contains 0 to 20% by weight, preferably 0.5 to 3.0% by weight, of acetyl groups.
Bevorzugt wird ein teilbutyralisierter Polyvinylalkohol (PVB) eingesetzt.A partially butyralized polyvinyl alcohol (PVB) is preferably used.
Als Polyvinylbutyralharz kann grundsätzlich jedes thermopla¬ stisch verformbare Polyvinylbutyralharz verwendet werden. Vor- zugsweise wird ein Harz benutzt, das 15 bis 23 Gew.-% Vinylal- koholeinheiten enthält.In principle, any thermoplastic deformable polyvinyl butyral resin can be used as the polyvinyl butyral resin. In front- a resin is preferably used which contains 15 to 23% by weight of vinyl alcohol units.
Der Wassergehalt der Folien ist auf 0,2 bis 0,8 Gew.-% einzu- stellen.The water content of the films should be set to 0.2 to 0.8% by weight.
Bei einem bevorzugten Verfahren zur Herstellung des Verbundsi¬ cherheitsglases wird eine erfindungsgemäße Folie zwischen gleich starke oder in der Dicke unterschiedliche Glasplatten gebracht und bei 60 bis 100 °C zu einem Vorverbund verpreßt. Der Endverbund erfolgt z.B. in einem Autoklaven bei 120 bis 160 °C und 8 bis 16 bar innerhalb einer Preßzeit von 10 bis 30 min.In a preferred method for producing the laminated safety glass, a film according to the invention is placed between glass plates of the same thickness or different thickness and pressed at 60 to 100 ° C. to form a preliminary bond. The final composite is e.g. in an autoclave at 120 to 160 ° C and 8 to 16 bar within a pressing time of 10 to 30 min.
Bei den in den nachfolgenden Ausführungsbeispielen beschriebe¬ nen Versuchen wurden zur Beurteilung der Durchschlagfestigkeit, der Folieneigenfarbe und Randeintrübung des Verbundsicherheits¬ glases folgende Prüfmethoden festgelegt:In the tests described in the following exemplary embodiments, the following test methods were determined to assess the dielectric strength, the film's inherent color and the clouding of the edges of the laminated safety glass:
Die Durchschlagfestigkeit wird in Anlehnung an ANSI 26.1-1983, 5.26 Test 26 geprüft. In einem Rahmen wird eine bei 23 °C tem¬ perierte Verbundglasscheibe von 30 x 30 cm horizontal einge¬ legt. Eine Stahlkugel von 2,26 kg wird von oben auf die Mitte der Verbundglasscheibe frei fallengelassen. Bei diesen Versu- chen werden die Fallhöhen variiert und die Fallhöhe ermittelt, bei der 8 der 10 Proben von der Stahlkugel nicht durchschlagen werden. Der Abstand der Kugel von der GlasOberfläche wird als Kugelfallhöhe angegeben. Je größer diese Fallhöhe ist, desto höher ist die Durchschlagfestigkeit des Verbundsicherheitsgla- ses.The dielectric strength is tested based on ANSI 26.1-1983, 5.26 Test 26. A laminated glass pane of 30 x 30 cm tempered at 23 ° C. is placed horizontally in a frame. A 2.26 kg steel ball is freely dropped onto the center of the laminated glass pane from above. In these experiments, the drop heights are varied and the drop height is determined at which 8 of the 10 samples are not penetrated by the steel ball. The distance of the ball from the glass surface is given as the ball drop height. The greater this drop height, the higher the dielectric strength of the laminated safety glass.
Mit dem Spektralmeßgerät Modell Labscan 5100 wird der Yellow- ness-Index (AYI, bedeutet Differenz aus Meßwert des Verbundsi¬ cherheitsglases und Glases ohne Folie) nach ASTM-D-1925 (Licht- art C, 2° Beobachter) bestimmt. Der eingegebene b-Wert korres¬ pondiert mit dem Yl der ASTM-D-1925. Die die Haftungsbeständigkeit und Transparenz beeinflussende Randeintrübung wurde nach ANSI 26.1-1977, Ziff. 5.3, Test 3 be¬ wertet, wobei gemessen wird, in welcher Breite der Trübungs- randstreifen in das Innere des Verbundsicherheitsglases einge- drungen ist.With the spectral measuring device model Labscan 5100 the yellowness index (AYI, means difference from measured value of the laminated safety glass and glass without foil) according to ASTM-D-1925 (light type C, 2 ° observer) is determined. The entered b-value corresponds to the YI of ASTM-D-1925. The edge clouding which affects the adhesion resistance and transparency was determined according to ANSI 26.1-1977, no. 5.3, Test 3 evaluated, it being measured in what width the clouding edge strip has penetrated into the interior of the laminated safety glass.
Wege zur Ausführung der ErfindungWays of Carrying Out the Invention
Beispiel 1 72 Gew.-% Polyvinylbutyralharz, das einen Gehalt an Vinylalko- holeinheiten von 20,5 Gew.-% besitzt, und 28 Gew.-% Triethylen- glykol-di-n-Heptansäureester als Weichmacher, in dem 0,7 Gew.-% Tinuvin P (Lichtstabilisator, Fa. Ciba Geigy) und 0,14 bis 0,21 Gew.-% 3-(Methyltriethylenglykoxi)-propylsilan-tris-methyltri- ethylenglykolester, bezogen jeweils auf den Weichmacheranteil, gelöst sind, werden gemäß der EP-A1-0 185 863 zu einer 0,76 mm dicken Folie extrudiert und, nach der Klimatisierung auf einen Feuchtigkeitsgrad von durchschnittlich 0,45 Gew.-% gebracht, mit 2,2 mm dicken Floatglasscheiben zu Verbundsicherheitsglä- sern verarbeitet.Example 1 72% by weight of polyvinyl butyral resin, which has a vinyl alcohol unit content of 20.5% by weight, and 28% by weight of triethylene glycol di-n-heptanoic acid ester as plasticizer, in which 0.7% by weight % Tinuvin P (light stabilizer, Ciba Geigy) and 0.14 to 0.21% by weight of 3- (methyltriethylene glycol) -propylsilane-tris-methyltriethylene glycol ester, based in each case on the plasticizer content, are dissolved in accordance with EP-A1-0 185 863 extruded into a 0.76 mm thick film and, after the air conditioning had been brought to an average moisture level of 0.45% by weight, processed with 2.2 mm thick float glass panes to form laminated safety glasses.
Beispiel 2Example 2
Es wurde eine Verbundglasscheibe wie in Beispiel 1 hergestellt, wobei jedoch als Silan 2-(Methyltriethylenglykoxi)-ethylsilan- tris-methyltriethylenglykolester mit einem Anteil von 0,14 bis 0,21 Gew.-%, bezogen auf den Weichmacheranteil, eingesetzt wur¬ de.A laminated glass pane was produced as in Example 1, except that 2- (methyltriethylene glycol) -ethylsilanetris-methyltriethylene glycol ester with a proportion of 0.14 to 0.21% by weight, based on the proportion of plasticizer, was used as the silane .
Beispiel 3 Es wurde eine Verbundglasscheibe wie in Beispiel 1 hergestellt, wobei jedoch als Silan 4-(Methyltriethylenglykoxi)-butylsilan- tris-methyltriethylenglykolester mit einem Anteil von 0,14 bisExample 3 A laminated glass pane was produced as in Example 1, but with 4- (methyltriethylene glycol) -butylsilanetris-methyltriethylene glycol ester as the silane in a proportion of 0.14 to
0,21 Gew.-%, bezogen auf den Weichmacheranteil, eingesetzt wur- de.0.21% by weight, based on the plasticizer content, was used.
Vergleichbeispiel 4Comparative Example 4
Es wurde wie in Beispiel 1 verfahren, wobei statt des erfin¬ dungsgemäßen Silans 4,6 Gew.-% - bezogen auf den Weichmacheran- teil - einer 10 gew.-%igen wäßrigen Kaliumacetatlösung einge¬ setzt wurde.The procedure was as in Example 1, but instead of the silane according to the invention, 4.6% by weight, based on the plasticizer part - a 10 wt .-% aqueous potassium acetate solution was used.
Vergleichsbeispiel 5 Es wurde wie in Beispiel 1 verfahren, wobei statt des erfin¬ dungsgemäßen Silans ein Isobutyl-tri-methoxisilan entsprechend der DE-C-24 10 153 in Mengen von 1 bis 1,8 Gew.-%, bezogen auf den Weichmacheranteil, eingesetzt wurde.Comparative Example 5 The procedure was as in Example 1, but instead of the silane according to the invention, an isobutyl-tri-methoxisilane according to DE-C-24 10 153 in amounts of 1 to 1.8% by weight, based on the plasticizer content, was used.
Die Verbundgläser entsprechend der Versuche 1 bis 5 wurden an¬ schließend einem Kugelfalltest nach ANSI 26.1 - 1983 unterzogen (Tabelle 1).The laminated glasses corresponding to tests 1 to 5 were then subjected to a ball drop test in accordance with ANSI 26.1-1983 (Table 1).
Tabelle 1Table 1
Zusatzstoff Konzentration Kugelfallhöhe (m) d.Zusatzstoffes Gew.-% Anfang d. Jahres Mitte d. JahresAdditive concentration ball drop height (m) d.Additive wt .-% beginning d. Mid-d. Year
Kaliumacetat 0,13 5,25 5,50Potassium acetate 0.13 5.25 5.50
Isobutyl-tri- methoxisilan (Beispiel 5) 0,3 2,00 2,50 0,4 3,50 2,75 0,5 4,25 3,25Isobutyltrimethoxisilane (Example 5) 0.3 2.00 2.50 0.4 3.50 2.75 0.5 4.25 3.25
MTG-SilanJ• 0,04 5,25 5,25 MTG-Silanj■ 0,05 5,50 5,50 MTG-Silan1 0,06 5,50 5,75MTG-SilanJ • 0.04 5.25 5.25 MTG-Silanj ■ 0.05 5.50 5.50 MTG-Silane 1 0.06 5.50 5.75
MTG-Silan2 0,04 5,50 5,25 MTG-Silan2 0,05 5,25 5,50 MTG-Silan2 0,06 5,50 5,50MTG silane 2 0.04 5.50 5.25 MTG silane 2 0.05 5.25 5.50 MTG silane 2 0.06 5.50 5.50
MTG-Silan3 0,04 5,25 5,25 MTG-Silan3 0,05 5,50 5,25 MTG-Silan3 0,06 5,25 5,25MTG silane 3 0.04 5.25 5.25 MTG silane 3 0.05 5.50 5.25 MTG silane 3 0.06 5.25 5.25
1) 3-(Methyltriethylenglykoxi)-propylsilan-tris-methyltri- ethylenglykolester1) 3- (Methyltriethylenglykoxi) -propylsilan-tris-methyltriethylene glycol ester
2) 2-(Methyltriethylenglykoxi)-ethylsilan-tris-methyltriethy- lenglykolester 3 ) 4- (Methyltriethylenglykoxi ) -butylsilan-tris-methyltriethy- lenglykolester2) 2- (methyltriethylene glycol) -ethylsilane-tris-methyltriethylene glycol ester 3) 4- (methyltriethylene glycol) -butylsilane-tris-methyltriethylene glycol ester
4 ) bezogen auf das Gesamtgewicht der Polymer-Weichmacher-Mi¬ schung4) based on the total weight of the polymer-plasticizer mixture
Die haftungsreduzierende Wirkung der Silane, die sich in der Kugelfallhöhe ausdrückt, und die optische Reinheit der Folie (Freiheit von Knötchen) sind nur beim erfindungsgemäßen Silan anforderungsgerecht und reproduzierbar gegeben. Die Reprodu¬ zierbarkeit der anforderungsgerechten Durchschlagfestigkeit (> 4m) beim erfindungsgemäßen Silan wird an Verbundglasscheiben demonstriert, deren Folien in verschiedenen Zeiträumen (Anfang und Mitte des Jahres) gefertigt wurden.The adhesion-reducing effect of the silanes, which is expressed in the height of the ball drop, and the optical purity of the film (freedom from nodules) are only reproducible in accordance with the requirements of the silane according to the invention. The reproducibility of the breakdown strength (> 4m) according to the requirements for the silane according to the invention is demonstrated on laminated glass panes, the foils of which were produced in different periods (beginning and middle of the year).
Die Ergebnisse der Prüfungen zum Yellowness-Index (ASTM-D-1925) und zur Randeintrübung (ANSI 26.1 - 1977) sind in der Tabelle 2 zusammengefaßt.The results of the tests on the Yellowness Index (ASTM-D-1925) and on the marginal clouding (ANSI 26.1 - 1977) are summarized in Table 2.
Tabelle 2Table 2
Zusatzstoff Konzentration Randeintrüb. Bemerk. zurAdditive concentration marginally cloudy. Notice to
Gew.-% £YI Δb ( ) Randeintrüb.% By weight YI Δb () marginally cloudy.
KaliumacetatPotassium acetate
(als Vergl.- 0,13 3,35 1,85 8 dauerhaft beispiel)(as comparison - 0.13 3.35 1.85 8 permanent example)
MTG-Silan 1 0,04 1,80 1,06 2 innerhalb 14 Tagen nicht mehr vorhandenMTG silane 1 0.04 1.80 1.06 2 no longer available within 14 days
MTG-Silan J- 0,05 1,90 1,11 2MTG-Silane J- 0.05 1.90 1.11 2
MTG-Silan 1 0,06 1,73 1,01 2MTG silane 1 0.06 1.73 1.01 2
MTG-Silan2 0,04 1,85 1,10 2 MTG-Silan2 0,05 1,80 1,05 2 MTG-Silan2 0,06 1,90 1,15 2MTG silane 2 0.04 1.85 1.10 2 MTG silane 2 0.05 1.80 1.05 2 MTG silane 2 0.06 1.90 1.15 2
MTG-Silan3 0,04 1,75 1,02 2MTG silane 3 0.04 1.75 1.02 2
MTG-Silan3 0,05 1,82 1,07 2 MTG-Silan3 0,06 1,88 1,13 2MTG silane 3 0.05 1.82 1.07 2 MTG silane 3 0.06 1.88 1.13 2
1) 3-(Methyltriethylenglykoxi)-propylsilan-tris-methyltri- ethylenglykolester 2) 2-(Methyltriethylenglykoxi)-ethylsilan-tris-methyltriethy- lenglykolester1) 3- (Methyltriethylenglykoxi) -propylsilan-tris-methyltriethylene glycol ester 2) 2- (methyltriethylene glycol) -ethylsilane-tris-methyltriethylene glycol ester
3) 4-( ethyltriethylenglykoxi)-butylsilan-tris-methyltriethy- lenglykolester3) 4- (ethyltriethylene glycol) -butylsilane-tris-methyltriethylene glycol ester
Beispiel 6Example 6
Entsprechend dem Beispiel 1 werden Folie und Verbundsicher¬ heitsglas hergestellt, es wird jedoch als Weichmacher Triethy- lenglykol-di-i-Heptansäureester anstelle von Triethylenglykol- di-n-Heptansäureester verwendet. Die Ergebnisse sind in Tabellen 3 und 4 aufgeführt.Film and laminated safety glass are produced in accordance with Example 1, but triethylene glycol di-i-heptanoic acid ester is used as plasticizer instead of triethylene glycol di-n-heptanoic acid ester. The results are shown in Tables 3 and 4.
Tabelle 3Table 3
Zusatzstoff Konzentration Kugelfallhöhe (m) d.Zusatzstoffes Gew.-% Anfang d. Jahres Mitte d. JahresAdditive concentration ball drop height (m) d.Additive wt .-% beginning d. Mid-d. Year
Kaliu acetat 0,12 5,25 5,50Potassium acetate 0.12 5.25 5.50
MTG-Silan1 0,04 5,25 5,25 MTG-Silan1 0,05 5,25 5,50 MTG-Silan1 0,06 5,75 5,50MTG silane 1 0.04 5.25 5.25 MTG silane 1 0.05 5.25 5.50 MTG silane 1 0.06 5.75 5.50
MTG-Silan2 0,04 5,50 5,50 MTG-Silan2 0,05 5,50 5,25 MTG-Silan2 0,06 5,25 5,50MTG silane 2 0.04 5.50 5.50 MTG silane 2 0.05 5.50 5.25 MTG silane 2 0.06 5.25 5.50
MTG-Silan3 0,04 5,25 5,50 MTG-Silan3 0,05 5,50 5,50 MTG-Silan3 0,06 5,25 5,25MTG silane 3 0.04 5.25 5.50 MTG silane 3 0.05 5.50 5.50 MTG silane 3 0.06 5.25 5.25
1) 3-( ethyltriethylenglykoxi)-propylsilan-tris-methyltri- ethylenglykolester1) 3- (ethyltriethylenglykoxi) propylsilane-tris-methyltriethylene glycol ester
2) 2-(Methyltriethylenglykoxi)-ethylsilan-tris-methyltriethy- 1englykoles er2) 2- (Methyltriethylenglykoxi) -ethylsilan-tris-methyltriethy-1englykoles he
3) 4-(Methyltriethylenglykoxi)-butylsilan-tris-methyltriethy- lenglykolester3) 4- (methyltriethylene glycol) -butylsilane-tris-methyltriethylene glycol ester
4) bezogen auf das Gesamtgewicht der Polymer-Weichmacher-Mi¬ schung Tabelle 44) based on the total weight of the polymer-plasticizer mixture Table 4
Zusatzstoff Konzentration Randeintrüb. Bemerk, zurAdditive concentration marginally cloudy. Notice to
Gew.-% 4 I Δb (mm) Randeintrüb.% By weight 4 I Δb (mm)
KaliumacetatPotassium acetate
(als Vergl.- 0,12 3,34 1,85 6,5 dauerhaft beispiel)(as comparison - 0.12 3.34 1.85 6.5 permanent example)
MTG-Silan 1 0,04 2,08 1,20 2 innerhalb 14 Tagen nicht mehr vorhandenMTG silane 1 0.04 2.08 1.20 2 no longer available within 14 days
MTG-Silan J 0,05 2,17 1,26 1,5MTG silane J 0.05 2.17 1.26 1.5
MTG-Silan - 0,06 2,09 1,21 1MTG silane - 0.06 2.09 1.21 1
MTG-Silan2 0,04 2,11 1,24 1,5 MTG-Silan2 0,05 2,02 1,18 1MTG silane 2 0.04 2.11 1.24 1.5 MTG silane 2 0.05 2.02 1.18 1
MTG-Silan2 0,06 2,06 1,22 1MTG silane 2 0.06 2.06 1.22 1
MTG-Silan3 0,04 2,15 1,26 1 MTG-Silan^ 0,05 2,10 1,22 1 MTG-Silan3 0,06 2,12 1,24 1,5MTG silane 3 0.04 2.15 1.26 1 MTG silane ^ 0.05 2.10 1.22 1 MTG silane 3 0.06 2.12 1.24 1.5
1 3-(Methyltriethylenglykoxi)-propylsilan-tris-methyltri- ethylenglykolester 1 3- (methyltriethylene glycol) -propylsilane-tris-methyltriethylene glycol ester
2) 2-(Methyltriethylenglykoxi)-ethylsilan-tris-methyltriethy- lenglykolester2) 2- (methyltriethylene glycol) -ethylsilane-tris-methyltriethylene glycol ester
3) 4-(Methyltriethylenglykoxi)-butylsilan-tris-methyltriethy- lenglykolester 3) 4- (methyltriethylene glycol) -butylsilane-tris-methyltriethylene glycol ester

Claims

Patentansprüche Claims
1. Formmasse zur Herstellung von Folien o. dgl. für Verbund¬ sicherheitsscheiben auf der Basis von weichgemachtem teil- acetalisiertem Polyvinylalkohol, insbesondere Polyvinylbu¬ tyral (PVB) mit Silanverbindungen als haftungsregulieren- den Zusätzen, dadurch gekennzeichnet, daß als Silanverbin- dung ein Organosilan der allgemeinen Formel1. Molding composition for the production of films or the like for composite safety panes based on plasticized, partially acetalized polyvinyl alcohol, in particular polyvinyl butyral (PVB) with silane compounds as adhesion-regulating additives, characterized in that an organosilane is used as the silane compound the general formula
I) R3-(0-R4 ιrιO-R5-SiR1R2[-0-(R -OtmR3]I) R 3 - (0-R 4 ιrι OR 5 -SiR 1 R 2 [-0- (R -Ot m R 3 ]
eingesetzt wird, wobeiis used, whereby
R1 und R2 jeweils unabhängig voneinander eine ggf. ver- zweigte Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder eine Gruppe der Formel -0-(R4-OrmR3 sind; R jeweils eine ggf. verzweigte Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder Wasserstoff ist, wo- bei die Gruppen R3 gleich oder verschieden sein können; R jeweils eine ggf. verzweigte Alkylengruppe mit 2 bis 4 Kohlenstoffatomen ist, wobei die Gruppen R4 gleich oder verschieden sein können; R5 eine ggf. verzweigte Alkylengruppe mit 1 bis 6R 1 and R 2 are each, independently of one another, an optionally branched alkyl group with 1 to 4 carbon atoms or a group of the formula -0- (R 4 -Or m R 3 ; R in each case is an optionally branched alkyl group with 1 to 4 carbon atoms or is hydrogen, where the groups R 3 can be identical or different; R is in each case an optionally branched alkylene group having 2 to 4 carbon atoms, where the groups R 4 can be identical or different; R 5 has an optionally branched alkylene group 1 to 6
Kohlenstoffatomen und m jeweils unabhängig voneinander eine der Zahlen von 0 bis 16 ist.Carbon atoms and m are each independently one of the numbers from 0 to 16.
2. Formmasse nach Anspruch 1, dadurch gekennzeichnet, daß in der allgemeinen Formel I2. Molding composition according to claim 1, characterized in that in the general formula I
R eine geradkettige Alkylengruppe mit 2 bis 4 Kohlenstoffatomen ist, wobei die Gruppen R4 gleich sind;R is a straight chain alkylene group having 2 to 4 carbon atoms, the groups R 4 being the same;
R eine geradkettige Alkylgruppe mit 1 bis 4 Kohlen¬ stoffatomen ist;R is a straight-chain alkyl group with 1 to 4 carbon atoms;
R eeiinnee ggeerraaddkkeettttiiggie Alkylengruppe mit 2 bis 6 Koh- lenstoffatomen ist. R eeiinnee ggeerraaddkkeettttiiggie alkylene group with 2 to 6 carbon atoms.
3. Formmasse nach einem der Ansprüche 1 oder 2, dadurch ge¬ kennzeichnet, daß in der allgemeinen Formel I3. Molding composition according to one of claims 1 or 2, characterized in that in the general formula I
R1 und R2 jeweils eine Gruppe der Formel -0-(R -Oτ~ τlR3 und untereinander gleich sind.R 1 and R 2 are each a group of the formula -0- (R -Oτ ~ τl R 3 and are identical to one another.
4. Formmasse nach einem der Ansprüche 1 bis 3, dadurch ge¬ kennzeichnet, daß in der allgemeinen Formel I4. Molding composition according to one of claims 1 to 3, characterized in that in the general formula I
10 R4 eine Alkylengruppe mit 2 Kohlenstoffatomen (Ethylen- gruppe) ist.10 R 4 is an alkylene group with 2 carbon atoms (ethylene group).
5. Forπimasse nach einem der Ansprüche 1 bis 4, dadurch ge¬ kennzeichnet, daß in der allgemeinen Formel I5. Forπimasse according to any one of claims 1 to 4, characterized in that in the general formula I
15 R3 jeweils eine Methylgruppe und m jeweils 3 ist.15 R 3 are each a methyl group and m is 3 each.
6. Formmassse nach einem der Ansprüche 1 bis 5, dadurch ge¬ kennzeichnet, daß man ein oder mehrere Silane aus der Gruppe, bestehend aus 20 a) 3-(Methyltriethylenglykoxi)-propylsilan-tris-methyl- triethylenglykolester der Struktur6. Molding composition according to one of claims 1 to 5, characterized ge indicates that one or more silanes from the group consisting of 20 a) 3- (methyltriethylene glycol) -propylsilane-tris-methyl-triethylene glycol ester of the structure
CH3-(OC2H4)3-0-(CH2)3-Si-[(OC2H4)3-OCH3]3,CH 3 - (OC 2 H 4 ) 3 -0- (CH 2 ) 3-Si - [(OC 2 H 4 ) 3-OCH3] 3,
b) 2-(Methyltriethylenglykoxi)-ethylsilan-tris-methyl- 25 triethylenglykolester der Strukturb) 2- (methyltriethylene glycol) -ethylsilane-tris-methyl-25 triethylene glycol ester of the structure
CH3-(OC2H4)3-O-(CH2)2-Si-[(0C2H4)3-O-CH3]3CH3- (OC 2 H 4 ) 3-O- (CH 2 ) 2 -Si - [(0C 2 H 4 ) 3-O-CH3] 3
undand
30 c) 4-(Methyltriethylenglykoxi)-butylsilan-tris- ethyl- triethylenglykolester der Struktur30 c) 4- (methyltriethylene glycol) -butylsilane-trisethyl-triethylene glycol ester of the structure
CH3-(OC2H4)3-0-(CH2)4-Si-[(OC2H4)3-0-CH3]3 verwendet.CH 3 - (OC 2 H 4 ) 3-0- (CH 2 ) 4 -Si - [(OC 2 H 4 ) 3-0-CH 3 ] 3 was used.
35 7. Formmasse nach einem der Ansprüche 1 bis 6, dadurch ge- > kennzeichnet, daß man das Silan in einer Menge von 0,003 bis 0,8 Gew.-%, bevorzugt bis 0,3 Gew.-% und insbesondere 0,01 bis 0,1 Gew.-%, bezogen auf das weichgemachte Polyvi¬ nylbutyral, einsetz .35 7. Molding composition according to one of claims 1 to 6, character-> characterized in that the silane in an amount of 0.003 to 0.8 wt .-%, preferably up to 0.3 wt .-% and in particular 0.01 up to 0.1% by weight, based on the plasticized polyvinyl butyral, are used.
40 40
8. Foπnmasse nach einem der Ansprüche 1 bis 7, dadurch ge¬ kennzeichnet, daß das Polyvinylbutyralharz einen Anteil von 10 bis 28 Gew.-%, vorzugsweise 15 bis 23 Gew.-%, Vi- nylalkoholeinheiten, bezogen auf das Polymerisat, besitzt.8. film composition according to one of claims 1 to 7, characterized ge indicates that the polyvinyl butyral resin has a proportion of 10 to 28 wt .-%, preferably 15 to 23 wt .-%, vinyl alcohol units, based on the polymer.
9. Formmasse nach einem der Ansprüche 1 bis 8, dadurch ge¬ kennzeichnet, daß das weichmacherhaltige Polyvinylbuty¬ ralharz einen Weichmachergehalt aufweist von etwa 15 bis 45 Gew.-%, vorzugsweise 24 bis 32 Gew.-%, bezogen auf die Polymerisat/Weichmachermischung.9. Molding composition according to one of claims 1 to 8, characterized ge indicates that the plasticizer-containing polyvinylbutal resin has a plasticizer content of about 15 to 45% by weight, preferably 24 to 32% by weight, based on the polymer / plasticizer mixture .
10. Verwendung einer aus einer Formmasse nach einem der An¬ sprüche 1 bis 9 extrudierten Folie als Zwischenschicht in Verbundglasscheiben.10. Use of a film extruded from a molding composition according to one of claims 1 to 9 as an intermediate layer in laminated glass panes.
11. Verfahren zur Herstellung von Verbundsicherheitsscheiben, bei dem zwei oder mehr Scheiben mittels einer Kunststoffo¬ lie auf der Basis von weichgemachtem teilacetalisiertem Polyvinylalkohol, insbesondere Polyvinylbutyral, miteinan- der verbunden werden und wobei die Haftung zwischen den11. A process for the production of composite safety panes, in which two or more panes are connected to one another by means of a plastic oil based on plasticized partially acetalized polyvinyl alcohol, in particular polyvinyl butyral, and the liability between the
Scheiben und der Kunststoffolie durch einen haftungsregu- lierenden Zusatz, der auf die Scheibenoberflächen und/oder - auf die Folienoberflächen aufgebracht und/oder in die Folie eingearbeitet wird, beeinflußt wird, dadurch gekennzeichnet, daß als haftungs- regulierender Zusatz ein Organosilan nach einem der An¬ sprüche 1 bis 6 verwendet wird. Disks and the plastic film is influenced by an adhesion-regulating additive which is applied to the pane surfaces and / or - on the film surfaces and / or incorporated into the film, characterized in that an organosilane according to one of the conventions is used as the adhesion-regulating additive ¬ sayings 1 to 6 is used.
EP90904810A 1989-03-25 1990-03-21 Moulding material for the manufacture of films for laminated glass panes Withdrawn EP0464070A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3909876 1989-03-25
DE3909876A DE3909876A1 (en) 1989-03-25 1989-03-25 MOLDING FOR THE PRODUCTION OF FILMS FOR COMPOSITE SAFETY WINDOWS

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FR2720683B1 (en) * 1994-06-02 1996-07-05 Saint Gobain Vitrage Fire resistant interlayer film and its use in laminated glass.
DE19643404A1 (en) * 1996-10-21 1998-04-23 Huels Troisdorf Process for the production of composite safety washers
CA2494021A1 (en) * 2002-07-31 2004-02-05 E. I. Du Pont De Nemours And Company Polyvinylbutyral interlayer sheet with improved adhesion to glass and a process for preparing same
ES2365590T3 (en) * 2007-12-18 2011-10-07 Kuraray Co., Ltd. INTERMEDIATE FILM FOR LAMINATED GLASS, PROCEDURE FOR MANUFACTURING AND LAMINATED GLASS CONTAINING IT.
JP5351227B2 (en) * 2011-08-31 2013-11-27 富士フイルム株式会社 Resin composition for laser engraving, relief printing plate precursor for laser engraving and method for producing the same, plate making method for relief printing plate, and relief printing plate
JP2016107632A (en) * 2014-11-10 2016-06-20 株式会社クラレ Laminate and glass laminate
US9809009B2 (en) * 2014-12-08 2017-11-07 Solutia Inc. Multiple layer interlayer having improved optical and sound insulation properties

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DE2650120A1 (en) * 1976-10-30 1978-05-03 Dynamit Nobel Ag Manufacture of laminated security glass for windscreens etc. - using silane(s) to bind olefin polymer(s) to glass
DE2549474A1 (en) * 1975-11-05 1977-05-12 Dynamit Nobel Ag METHOD FOR MANUFACTURING LAMINATED SAFETY GLASS
DE2820780A1 (en) * 1978-05-12 1979-11-15 Dynamit Nobel Ag SOFTENING FILMS FROM PARTLY ACETALIZED POLYVINYL ALCOHOLS
US4567221A (en) * 1983-03-31 1986-01-28 Kuraray Co., Ltd. Water resistant compositions
DE3347040C2 (en) * 1983-12-24 1987-01-29 Dynamit Nobel Ag, 5210 Troisdorf Process for the production of light-resistant polyvinyl butyral films and the use of the films
US4544724A (en) * 1984-06-19 1985-10-01 E. I. Du Pont De Nemours And Company Silylated vinyl alcohol polymers

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KR920701334A (en) 1992-08-11
BR9007252A (en) 1992-03-17

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