CA1202136A - Plasticizer-containing foils formed of the partially acetalised polyvinyl alcohol - Google Patents
Plasticizer-containing foils formed of the partially acetalised polyvinyl alcoholInfo
- Publication number
- CA1202136A CA1202136A CA000407413A CA407413A CA1202136A CA 1202136 A CA1202136 A CA 1202136A CA 000407413 A CA000407413 A CA 000407413A CA 407413 A CA407413 A CA 407413A CA 1202136 A CA1202136 A CA 1202136A
- Authority
- CA
- Canada
- Prior art keywords
- plasticizer
- ester
- polyvinyl alcohol
- glycol
- foils
- 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.)
- Expired
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- B32B17/10605—Type of plasticiser
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Glass Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention is concerned with foils made of partially acetalised polyvinyl alcohol, especially foils formed of polyvinyl butyral. These foils contain, as platicizers, esters of aroma-tic carboxylic acids whose ester components can possess up to 10 C-atoms, alone, or as mix-tures, or mixtures formed of these esters with esters formed of aliphatic carboxylic acids and glycols, chiefly di-, tri-or tetraethyleneglycol. These esters may be worked into the partially acetalised polyvinyl alcohol foils in higher pro-portions than the hitherto known plasticizers, without being exuded or influencing disadvantageously other important properties of the foils. They have the additional advantage that the laminated panes produceable therefrom possess a lower capacity for water uptake than hitherto known laminated glasses.
The present invention is concerned with foils made of partially acetalised polyvinyl alcohol, especially foils formed of polyvinyl butyral. These foils contain, as platicizers, esters of aroma-tic carboxylic acids whose ester components can possess up to 10 C-atoms, alone, or as mix-tures, or mixtures formed of these esters with esters formed of aliphatic carboxylic acids and glycols, chiefly di-, tri-or tetraethyleneglycol. These esters may be worked into the partially acetalised polyvinyl alcohol foils in higher pro-portions than the hitherto known plasticizers, without being exuded or influencing disadvantageously other important properties of the foils. They have the additional advantage that the laminated panes produceable therefrom possess a lower capacity for water uptake than hitherto known laminated glasses.
Description
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The present inven-ti.orl relates -to plastici~er-containing foils formed or partially acetalised polyvinyl alcohol which are employed as adhesive foils in laminated saEety glasses. In particular, the present invention is concerned with new polyvinyl butyral foils and the use of these foils Eor the production of laminated safety glasses.
Laminated saEety glasses consist in general o~ two silicate glass panes and an adhesive foil binding the glass panes. If desired, one of the silicate glass panes can be replaced by a plastic pane. Such laminated safety panes are chiefly employed as windscreens in vehicles, especially motor vehicles; they can however also be employed in the building industry, wherein according to their use, more than two silicate or plastics panes can be connected by adhesive foilO Such multiple laminates serve for example as lamina-ted armoured glasses.
Plasticized partially acetalised polyvinyl alcohol foils chiefly serve as adhesive foils in these laminated glasses. The partially acetal polyvinyl alcohols required for -their production are produced by a saponiEication of the polyvinyl acetate and then acetalisation with aliphatic aldehydes, such as for example formaldehyde, acetaldehyde, butyraldehyde and other aldehydes with 3 to 10 C atoms. The saponification is in general not carried ou-t completely, so that the polyvinyl alcohols contain generally still 0.5 to 5% by weight acetyl groups calculated as vinyl acetate groups.
Moreover the acetalisation is generally not completely carried through so that the partially acetalised polyvinyl alcohols employed for the production of the foils generally still contain free OH-groups; with the partially butyralised poly-vinyl alcohol, (hereafter designated as PVB), this OH-content can amount to 10 to 27% calculated as vinyl alcohol. A11 these resins fall within -the -term partially acetalised poly-vinyl alcohols in the sense of the present invention.
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In the production of lam:inated safety ylasses, these partially acetalised polyvinyl alcohols are employed as foils with a definite plasticizer content. The type and amount of -the plasticizers employed influences the properties of the laminated safety glass. In practice i-t therefore turns out -that a laminated safety glass especi.ally secure against splintering should have, as intermediate foil, a PVs-foil which possesses a plasticizer content of 15 to 40~
by weight, preferably 25 to 31% by weight and whose content of free OH-groups amoun-ts to 10 to 25% by weight, preferably 16 to 23~ by weight, related to plasticizer-free PVs-resin.
qlhe moisture content of such a PVB-foil should lie between o.2 and 0.9% by weight.
The triethyleneglycol esters of 2-ethyl-butyric acid are widely employed in practice as plasticizers for such PVs foils. The use of dibutylsebacate, di-(hexyl)-adipate and dioctylphthalate has been described.
In spite of the fact that still many more plasti-cizers are known for partially acetalised polyvinyl butyral, only a very few plasticizers have to date found widespread commercial use in intermediate la~ers of partially butyralised polyvinyl alcohol for laminated safety glass. The reason for this is that PVB is a complex resin which can be produced with a large variation in the amounts of butyral, hydroxyl and residual ester groups, with which the extent of variation is given via the different possible molecular weights and the kind of distribution of the hydroxyl groups on the polymer chain. Hence a large number of compatible or partially com-patible plasticizers for use in intermediate layers for lami-nated safety glass are eliminated since very strenuous per-formance requirements are to be fulfilled by the polymer and the plasticizer. For example d.ioc-tylphthalate, for these reasons cannot f:ind any practical use in PVB-intermediate layers.
.3~j Of the many performance requirements which are imposed on intermediate layers for laminated safety glass may be enumerated, inter alia, a high foil toughness, a good resistance to layer separation and edge stability which is characterised by the capacity to bind water. The tensile strength at 100% elongation therefore serves as a measure of the suitability for use as foils.
Indeed a series of phthalic acid esters has already been described in the literature as compatible with PVB, but in no way are there directions for their usability in PVB-intermediate layers for laminated safety glass. The passage relating to their compatibility, for example in Modern Plastics Encyclopedia 1975-1976 on pages 698 and 699 is hardly specific enough for it to be possible to lead to a direct practical application. It is not achieved in the examples provided under always the same suppositions. The man skilled in the art must draw the conclusion from these disclosures that among the compatible esters can be enumerated those of iso-C10-alcohols to iso-C13-alcohols, whereas esters with short chained iso-C7-alcohols to iso-C8-alcohols are of a limited compatibility.
Therefore it would be advantageous to have adhesive foils for laminated safety glass based on plasticizer-con-taining polyvinyl alcohols, with which , for example, phthalic acid esters can be used alone or in mixtures with glycol esters, which, compared with known adhesive foils for lami-nated safety glasses, possess a good edge stabilit~ or resist-ance to layer separation as a consequence of low water uptake, and excellent foil toughness with retention of the usual important mechanical propertles.
The present invention relates to plasti-cizer-containing foils formed from partially acetalised poly-vinyl alcohols which contain as plasticizers either a) esters of organic, cyclic acids and alcohols, the alcohols _ 3 _ having 4 to 10 C-atoms or b) mixtures of glycol esters which are derived from aliphatic monobasic acids, the acids having 4 to 10 C-atoms, with the esters named under a).
The present invention in particular provides a plasticizer-containing foil of partially acetalised poly-vinyl alcohol, characterized in that such foil contains as plasticizer a mixture consisting essentially of a) at least one ester of an organic, cyclic acid and an alcohol, said alcohol having 4 to 10 carbon atoms and b3 at least one ester of a glycol and an aliphatic monobasic acid, the monobasic acid having 4 to 10 carbon atoms, the ratio of a) to b) in said mixture being from 85:15 to 15:85.
The present invention also provides a plasticizer-eontaining foil of partially acetalised polyvinyl alcohol, said foil containing plasticizer in an amount of 10 to 40%
by weight based on the total weight of the Eoil charaeter-ised in that said foil eontains as plastieizer a mixture consisting essentially of a) at least one ester of an organic, cyclie acid and an aliphatie alcohol, said aliphatic aleohol having 4 to 10 carbon atoms and b) at leask one ester of a glycol and an aliphatic mono-basic acid, said monobasic acid having 4 to 10 carbon atoms, the weight ratio of a) to b) in said mixture being from 85:15 ~o 15.~5.
Foils of the said plasticized resins possess more advantageous mechanical properties and lower water uptake than foils which were produced with glycol esters alone.
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In DE-OS 28 20 780, there is described the use of phthalic acid esters whose compatibility with partially acetalised polyvinyl alcohol is so low, on account of their long chain alcohol components, that they are not usable on their own. Their use is only possible if they are mixed with esters of oxy-acids of phosphorus which gel well.
Ester plasticizers of organic cyclic acids for the present invention are prefexably esters oE phthalic acid with aliphatic and/or aromatic alcohols which contain 10 4 to 10 carbon atoms. Likewise suitable as ester mixtures are mixed esters of corresponding alcohol mixtures, of which the aliphatic alcohols can be straight-chained or branched alcohols, for example dibutyl-, diamyl-, dihexyl-, diheptyl-, dioctyl-, dinonyl-, didecyl-, dimethylglycol-, 15 diethylglycol, dibutylglycol-, dioctylhexyl-, dibenzyl-phthalate, butylbenzylphthalate, butylcyclohexylphthalate, butyloctylphthalate, hexyldecylphthalate etc. Esters of phthalic acid with glycolic acid esters can likewise be employed.
Esters of a polyethylene glycol with ethylbutyric, caproic, oenanthic, caprylic, ethylhexanoic, pelargonic or caprinic acid are suitable for example as glycolesters. The polyethyleneglycol is preferably a di-, tri- or tetra-ethyleneglycol. Triethyleneglycol-di-2-ethylbutyrate, tri-ethyleneglycol diheptanoate, diethyleneglycol dipelargonate or tetraethyleneglycol esters of valeric, ethylcaproic or ethylhexanoic acid are esters employable according to this --~
/
- 4a -~' invention. ~150 employable according to -the invention are either the esters of glycerol or of glycollic acld with -the above indicated acids.
The parti~lly acetalised polyvinyl alcohols employ-able according -to the invention can possess 5 to 30% by weight hydroxyl groups, calculated as vinyl alcohol. Prefer-ably the hydroxyl group content lies between 16 and 23~ by weight.
The amount of the plasticizer or plasticizer mix-ture can amount to 10 to ~0~ by weight,preferably 20 to 35%
by weight, related to the total foil weigh-t. It is adjusted inter alia according to the degree oi acetalisation of the polyvinyl alcohol and the aldehyde employed for the acetalisa-tion, as well as according to -the type of individual plasti-cizers employed. In general it is also so chosen that the Shore hardness A of the foils according to the invention lies between 100 and 50 at 23C.
The ratio between the esters of organic cyclic acids and the glycol esters can vary between 99:1 and 1:99.
It depends chiefly on the amount and compatibility of the esters in the partially acetalised polyvinyl alcohol. It depends furthermore on the properties of the individual plasticizers which are chosen and of the partially acetalised polyvinyl alcohol which is used, as well as the requirements imposed on the foil materials to be used. The preferred ratio lies between 85:15 and 15:85 (weight).
. In addition to the above indicated improvement of the mechanical properties and the lower capacity for binding water and.thereby to establish a better edge stability of the laminated safety glasses, the laminated safety glass -adhesive foils with glycol esters as plasticizers have the Eurther advantage that the required mixtures of glycol esters with esters of organic cyclic acids can be employed in larger amounts than glycol esters alone, without losing the good mechanical foil stxength values. As a resul-t of this -there exists -the possibility of e~trllding foils according -to the invention at lower material temperatures and of reducing the thermal stressing of the ma-terial.
The production of the foils according to the inven-tion can take place as required in known manner. After mixing the measured-out components, the foil material ob-tained is worked to the desired foils. The materials thereby produced may be extruded or calandered, injection moulded or pressed. Wastes may be reworked in outstanding manner and for example formed to foils by extrusion.
The foil materials may furh-termore be modified by use of suitable known auxiliaries and stabilisers, dyes; pig-ments, fillers, bonding and blocking influencing additives, so that correspondingly modified foils are also the subject or the present invention.
The plasticizer-containing foils in accordance with the present invention can be used -to make laminated safety glasses. In accordance with the present invention the plasticizer-containing foils can be used as adhesive foils for the one - or two - sided bonding of one or more silicate glass panes and/or transparent tough elastic panes.
In accordance with the present invention the plasticizer-containing foils may be characterized by possess-ing a Shore hardness A at 23C between lO0 and 20, preferably between 90 and 30.
The laminated safety glasses, to which the foil materials according to the invention are processed consist of at least one layer o~ this foil material according to the invention. They can be produced in known manner with unhard-ened, hardened, flat, ben-t, damped, printed, coloured, etched, structured silicate plate glass which optionally possesses a wire insert, as well as with colourless, coloured transparent, colour covered, printed foils according to the invention ~:P~1.9~
which optionally cOntaill in~aicl wires, wire meshes, webs or other objects which are produced in known manner. The thicknesses of the silicate glasses or -the foils produced according to the invention are variably selec-table according to the purpose of use, as well as likewise -the number of -the individual layers of the laminated object.
This makes possible the use oE the laminated glasses containing the foils according to the invention as adhesive foils in the building industry in doors and door surrounds, in windows and window surrounds, in parapets of bannisters, balconies or facades, in separating walls as room partitions, balcony dividers or fences for properties, in roofs or roof components of terraces, light transmitting roofs or guard houses, in cubicles for telephone or computer housing, shop windows, cashiers booths, prisons or in explosion or implo-sion susceptible chambers in each case as safety glass for protection against penetration~ breaking in, shooting, fire, sound, cold, warmth, heat, if necessary with alarm or hea-ting wires.
In the vehicle sector, the glazing of motor vehicles, road vehicles, ships and aircraft with windscreen, rear or side panes, doors, partitions etc may be mentioned.
The foil materials according to the invention are also suited in outstanding measure for the production of laminates with transparent tough elastic plastics.
In addition to polycarbonate, there can also be employed as transparent plastics panes those formed of poly-methylmethacrylate, polyethylene terephthalate, rigid P~C, polyamide, cellulose esters, s-tyrene-acryloni-trile polymers etc.
Tne following Examples illustrate the invention.
Example 1 (compara-tive example) DiEferent amoun-ts of triethyleneglycol di-2-ethyl-butyrate were mixed in wi-th a commercially available partially ~l~q~ t3 butyralised polyvinyl alcohol resin with a hydroxyl content of 20.7~ by weight, calculated as vinyl alcohol on a set of rollers. A number of foils of 0.76 mm -thickness were produced in a press from the rolled product with mat silk surface embossing and tested by storage a-t 23C and a rela-tive air humidity of 60% to see whether the premixed plasti-cizers underwent exudation. Furthermore the resis-tance to tearing, elongation at break, tensile strength at 100~ and cold impact value were determined. The measuring of the cold impact value was carxied out according to method VDCh 22-02 on shoulder samples (with a profile S 3 according to DIN 53 504) in the manner that the lowest temperature was sought with which at the most one of six samples bent to a loop is broken by a 200 g falling hammer, from a tes-t height of 200 mm.
The following values were obtained.
Plasticizer content 28 30 32 (~ by weigh-t) Exuded No No No Tear resistance (kp/cm ) 269 247 221 Tensile strength (kp/cm2) at 100% elongation 32 26 15 Cold impact value (O)-55 -55 -55 The plasticizer shows indeed a good compatibility with the PVB foil, if it is employed in amounts > 30~, al-though then the tear resistance and also, a-t a proportion of > 32%r the tensile strength is insufficient so that this plasticizer is not employable in amounts of > 30~ with reten-tion of good values.
Example 2 Different amoun-ts of different phthalic acid esters were mixed in with PVB resin with a hydroxyl group content of ~3~
20.7% b~ weight and foils were produced -therefrom, in the same manner as in Example 1. The resul-ts of the quali-ty -testing of such foils are set out in Table 1.
T a b 1 e Alcohol com- Amount Exuded Tear re- Cold Tensile streng-th ponents of (weight sistance impact kp/cm2 at 100%
the phthalic %) kp/cm2 value elongation acid esters C
n-C4-alcohol 28 no 251 -45 36 - 30 no 228 -50 28 32.5 no 194 -55 19 no 153 -55 15 n-C alcohol 28 no 273 -50 57 6 30 no 259 -50 42 32.5 no 218 -55 36 no 182 -55 23 n-C -alcohol 28 no 293 -50 74 7 30 no 281 -55 53 32.5 no 255 -55 40 no 222 -55 26 n-C -alcohol 28 no 294 -55 78 8 30 no 273 -55 58 32.5 yes 250 -55 48 yes 212 -55 35 80 % C 28 no 306 -45 92 10 % c6 30 no 282 -50 59 10 % c8 32.5 no 239 -55 34 no 221 -55 33 40 ~ C7 28 no 278 -50 98 40 % C 30 no 264 -55 48 20 ~ c8 32.5 no 242 -55 29 9 35 yes 217 -55 32 Example 3 A commercially obtainable PVB resin with a hydroxyl group content of 20.7~ by weight (calculated as vinyl alcohol) was mixed on the roller arrangement with different amounts of ~z~
-triethyleneglycol-cli.-2-ethylbutyrate (3 Gll) and a mixed ester (C 6/10) of phthalic acid and a mixture of C6-, C8-, C]0-alcohols (80:10:10). Foils 0.76 mm in thickness, whose properties appear in Table 2, were pressed from the rolled materials. The determination of the properties took place in the manner se-t out in Example 1. None of the compositions unde~went exuding.
T a b 1 e 2 Plas-ticizer content Tear Tensi2e strength Cold impact % by weight resistance kp/cm at 100~ value C
3 GH C6/10 Total kp/cm2 elongation 15.5 15.5 31 ~4g 27 -55 Samples of all the foils were then worked up to form laminated safety glasses, for which they were acclima-tised at 30~ relative humidity, then laid between twosilicate glass panes and subsequently the laminate was pro-duced by heating at 130 to 150C at a pressure of 12 bar.
The laminated safety glasses were tested for the adhesion between the silicate glass and the PVB foils according to the pummel method as described for example in German Patent Specification 2,410,153. All laminated safety glasses obtained showed pummel values of 10.
Example 4 In the same way as in Example 3, PVs foils with a hydroxyl group content of 20.7% by weight were produced with varying amounts of triethyleneglycol-diheptanoate (3 G 7) and phthalic acid heptyl ester (C 7) and their properties were determined. The results appear in Table 3. In all cases, the plasticizer mixtures were compa-tible with the PVB
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res.in.
T a b 1 e 3 Plasticlzer content Tear Tens.ile strength Cold impact % by weight resistance kp/cm2 at 100% value C
3 G 7 C 7 Total kp/cm2 elonga-tion 14 14 ~ 28 283 46 -50 14.5 14.5 29 263 31 -55 Laminated safety glasses made from these foils has a pummel adhesion of 10.
Example 5 In the same way as in Example 3, a PVB resin with a hydroxyl group content of 20.7% by weight, calculated as vinyl alcohol, was produced with triethyleneglycol diphepta-noate (3 G 7) and butylphthalate (C 4) present in different amounts in a total plasticizer content of 28~ by weight.
The results appear in Table 4. The plasticizer mixtures were compatible with the PVB resin in all cases.
T a b 1 e 4 Plasticizer content Tear Tensi~e strength Cold impact ~ by weight resis2tance kp/cm at 100% value C
3 G 7 C 4 Total kp/cm elongation 14 14 50:50 256 31 -50 12 16 43:57 256 28 -50 18 36:64 257 26 -50 8 20 29:71 254 27 -50 6 22 21:79 270 31 . -50 Example 6 In the same manner as in Example 3, a PVB resin with a hydroxyl group content of 20.7% by weight, calculated as vinyl alcohol, was produced with different plasticizers.
There are selected as glycol ester, as in Example 4, tri-ethyleneglycol dipheptanoate ~3 G 7) on -the one hand and as esters of organic cyclic acids, on the o-ther hand different phthalic acid esters. The mixiny ra-tio amoun-ted to 1:1.
The plasticizers employed and the properties of the foils ob-tained appear in Table 5. All plas-ticizers mixtures were compatible with the PVB resin.
T a b 1 e 5 Tear Tensile Cold resist strength impact ance 2 (kp/cm2) value ]cp/cm at 100% C
elonga-tion n-C7, C8, C9-Phthalate 257 40 -50 n-C8-Phthala-te 259 48 -50 i-C8-Phthalate 272 62 -45 n-C7, i-clo-phthalate 289 39 -50 n-C6' C7~ Cg~ C10~Phthalate 260 51 -55 n-C8, C10 Phthalate 279 43 -50 Butyl-, Benzylphthalate 268 43 -35 Butyl-, Cyclohexylphthalate 268 34 -45 Methylglycolphthalate 259 23 -50 Ethylglycolphthalate 280 27 -50 Butylglycolphthalate 270 32 -45 Laminated safety glasses made from these foils has a pummel adhesion of 10.
Example 7 A PVB resin with a hydroxyl group content of 18.4%
by weight, calculated as vinyl alcohol, was worked, in -the same way as in Example 3 with, in total, 30% by weight of
The present inven-ti.orl relates -to plastici~er-containing foils formed or partially acetalised polyvinyl alcohol which are employed as adhesive foils in laminated saEety glasses. In particular, the present invention is concerned with new polyvinyl butyral foils and the use of these foils Eor the production of laminated safety glasses.
Laminated saEety glasses consist in general o~ two silicate glass panes and an adhesive foil binding the glass panes. If desired, one of the silicate glass panes can be replaced by a plastic pane. Such laminated safety panes are chiefly employed as windscreens in vehicles, especially motor vehicles; they can however also be employed in the building industry, wherein according to their use, more than two silicate or plastics panes can be connected by adhesive foilO Such multiple laminates serve for example as lamina-ted armoured glasses.
Plasticized partially acetalised polyvinyl alcohol foils chiefly serve as adhesive foils in these laminated glasses. The partially acetal polyvinyl alcohols required for -their production are produced by a saponiEication of the polyvinyl acetate and then acetalisation with aliphatic aldehydes, such as for example formaldehyde, acetaldehyde, butyraldehyde and other aldehydes with 3 to 10 C atoms. The saponification is in general not carried ou-t completely, so that the polyvinyl alcohols contain generally still 0.5 to 5% by weight acetyl groups calculated as vinyl acetate groups.
Moreover the acetalisation is generally not completely carried through so that the partially acetalised polyvinyl alcohols employed for the production of the foils generally still contain free OH-groups; with the partially butyralised poly-vinyl alcohol, (hereafter designated as PVB), this OH-content can amount to 10 to 27% calculated as vinyl alcohol. A11 these resins fall within -the -term partially acetalised poly-vinyl alcohols in the sense of the present invention.
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In the production of lam:inated safety ylasses, these partially acetalised polyvinyl alcohols are employed as foils with a definite plasticizer content. The type and amount of -the plasticizers employed influences the properties of the laminated safety glass. In practice i-t therefore turns out -that a laminated safety glass especi.ally secure against splintering should have, as intermediate foil, a PVs-foil which possesses a plasticizer content of 15 to 40~
by weight, preferably 25 to 31% by weight and whose content of free OH-groups amoun-ts to 10 to 25% by weight, preferably 16 to 23~ by weight, related to plasticizer-free PVs-resin.
qlhe moisture content of such a PVB-foil should lie between o.2 and 0.9% by weight.
The triethyleneglycol esters of 2-ethyl-butyric acid are widely employed in practice as plasticizers for such PVs foils. The use of dibutylsebacate, di-(hexyl)-adipate and dioctylphthalate has been described.
In spite of the fact that still many more plasti-cizers are known for partially acetalised polyvinyl butyral, only a very few plasticizers have to date found widespread commercial use in intermediate la~ers of partially butyralised polyvinyl alcohol for laminated safety glass. The reason for this is that PVB is a complex resin which can be produced with a large variation in the amounts of butyral, hydroxyl and residual ester groups, with which the extent of variation is given via the different possible molecular weights and the kind of distribution of the hydroxyl groups on the polymer chain. Hence a large number of compatible or partially com-patible plasticizers for use in intermediate layers for lami-nated safety glass are eliminated since very strenuous per-formance requirements are to be fulfilled by the polymer and the plasticizer. For example d.ioc-tylphthalate, for these reasons cannot f:ind any practical use in PVB-intermediate layers.
.3~j Of the many performance requirements which are imposed on intermediate layers for laminated safety glass may be enumerated, inter alia, a high foil toughness, a good resistance to layer separation and edge stability which is characterised by the capacity to bind water. The tensile strength at 100% elongation therefore serves as a measure of the suitability for use as foils.
Indeed a series of phthalic acid esters has already been described in the literature as compatible with PVB, but in no way are there directions for their usability in PVB-intermediate layers for laminated safety glass. The passage relating to their compatibility, for example in Modern Plastics Encyclopedia 1975-1976 on pages 698 and 699 is hardly specific enough for it to be possible to lead to a direct practical application. It is not achieved in the examples provided under always the same suppositions. The man skilled in the art must draw the conclusion from these disclosures that among the compatible esters can be enumerated those of iso-C10-alcohols to iso-C13-alcohols, whereas esters with short chained iso-C7-alcohols to iso-C8-alcohols are of a limited compatibility.
Therefore it would be advantageous to have adhesive foils for laminated safety glass based on plasticizer-con-taining polyvinyl alcohols, with which , for example, phthalic acid esters can be used alone or in mixtures with glycol esters, which, compared with known adhesive foils for lami-nated safety glasses, possess a good edge stabilit~ or resist-ance to layer separation as a consequence of low water uptake, and excellent foil toughness with retention of the usual important mechanical propertles.
The present invention relates to plasti-cizer-containing foils formed from partially acetalised poly-vinyl alcohols which contain as plasticizers either a) esters of organic, cyclic acids and alcohols, the alcohols _ 3 _ having 4 to 10 C-atoms or b) mixtures of glycol esters which are derived from aliphatic monobasic acids, the acids having 4 to 10 C-atoms, with the esters named under a).
The present invention in particular provides a plasticizer-containing foil of partially acetalised poly-vinyl alcohol, characterized in that such foil contains as plasticizer a mixture consisting essentially of a) at least one ester of an organic, cyclic acid and an alcohol, said alcohol having 4 to 10 carbon atoms and b3 at least one ester of a glycol and an aliphatic monobasic acid, the monobasic acid having 4 to 10 carbon atoms, the ratio of a) to b) in said mixture being from 85:15 to 15:85.
The present invention also provides a plasticizer-eontaining foil of partially acetalised polyvinyl alcohol, said foil containing plasticizer in an amount of 10 to 40%
by weight based on the total weight of the Eoil charaeter-ised in that said foil eontains as plastieizer a mixture consisting essentially of a) at least one ester of an organic, cyclie acid and an aliphatie alcohol, said aliphatic aleohol having 4 to 10 carbon atoms and b) at leask one ester of a glycol and an aliphatic mono-basic acid, said monobasic acid having 4 to 10 carbon atoms, the weight ratio of a) to b) in said mixture being from 85:15 ~o 15.~5.
Foils of the said plasticized resins possess more advantageous mechanical properties and lower water uptake than foils which were produced with glycol esters alone.
~( ~Z~ '3~`
, . . ,~ ~
In DE-OS 28 20 780, there is described the use of phthalic acid esters whose compatibility with partially acetalised polyvinyl alcohol is so low, on account of their long chain alcohol components, that they are not usable on their own. Their use is only possible if they are mixed with esters of oxy-acids of phosphorus which gel well.
Ester plasticizers of organic cyclic acids for the present invention are prefexably esters oE phthalic acid with aliphatic and/or aromatic alcohols which contain 10 4 to 10 carbon atoms. Likewise suitable as ester mixtures are mixed esters of corresponding alcohol mixtures, of which the aliphatic alcohols can be straight-chained or branched alcohols, for example dibutyl-, diamyl-, dihexyl-, diheptyl-, dioctyl-, dinonyl-, didecyl-, dimethylglycol-, 15 diethylglycol, dibutylglycol-, dioctylhexyl-, dibenzyl-phthalate, butylbenzylphthalate, butylcyclohexylphthalate, butyloctylphthalate, hexyldecylphthalate etc. Esters of phthalic acid with glycolic acid esters can likewise be employed.
Esters of a polyethylene glycol with ethylbutyric, caproic, oenanthic, caprylic, ethylhexanoic, pelargonic or caprinic acid are suitable for example as glycolesters. The polyethyleneglycol is preferably a di-, tri- or tetra-ethyleneglycol. Triethyleneglycol-di-2-ethylbutyrate, tri-ethyleneglycol diheptanoate, diethyleneglycol dipelargonate or tetraethyleneglycol esters of valeric, ethylcaproic or ethylhexanoic acid are esters employable according to this --~
/
- 4a -~' invention. ~150 employable according to -the invention are either the esters of glycerol or of glycollic acld with -the above indicated acids.
The parti~lly acetalised polyvinyl alcohols employ-able according -to the invention can possess 5 to 30% by weight hydroxyl groups, calculated as vinyl alcohol. Prefer-ably the hydroxyl group content lies between 16 and 23~ by weight.
The amount of the plasticizer or plasticizer mix-ture can amount to 10 to ~0~ by weight,preferably 20 to 35%
by weight, related to the total foil weigh-t. It is adjusted inter alia according to the degree oi acetalisation of the polyvinyl alcohol and the aldehyde employed for the acetalisa-tion, as well as according to -the type of individual plasti-cizers employed. In general it is also so chosen that the Shore hardness A of the foils according to the invention lies between 100 and 50 at 23C.
The ratio between the esters of organic cyclic acids and the glycol esters can vary between 99:1 and 1:99.
It depends chiefly on the amount and compatibility of the esters in the partially acetalised polyvinyl alcohol. It depends furthermore on the properties of the individual plasticizers which are chosen and of the partially acetalised polyvinyl alcohol which is used, as well as the requirements imposed on the foil materials to be used. The preferred ratio lies between 85:15 and 15:85 (weight).
. In addition to the above indicated improvement of the mechanical properties and the lower capacity for binding water and.thereby to establish a better edge stability of the laminated safety glasses, the laminated safety glass -adhesive foils with glycol esters as plasticizers have the Eurther advantage that the required mixtures of glycol esters with esters of organic cyclic acids can be employed in larger amounts than glycol esters alone, without losing the good mechanical foil stxength values. As a resul-t of this -there exists -the possibility of e~trllding foils according -to the invention at lower material temperatures and of reducing the thermal stressing of the ma-terial.
The production of the foils according to the inven-tion can take place as required in known manner. After mixing the measured-out components, the foil material ob-tained is worked to the desired foils. The materials thereby produced may be extruded or calandered, injection moulded or pressed. Wastes may be reworked in outstanding manner and for example formed to foils by extrusion.
The foil materials may furh-termore be modified by use of suitable known auxiliaries and stabilisers, dyes; pig-ments, fillers, bonding and blocking influencing additives, so that correspondingly modified foils are also the subject or the present invention.
The plasticizer-containing foils in accordance with the present invention can be used -to make laminated safety glasses. In accordance with the present invention the plasticizer-containing foils can be used as adhesive foils for the one - or two - sided bonding of one or more silicate glass panes and/or transparent tough elastic panes.
In accordance with the present invention the plasticizer-containing foils may be characterized by possess-ing a Shore hardness A at 23C between lO0 and 20, preferably between 90 and 30.
The laminated safety glasses, to which the foil materials according to the invention are processed consist of at least one layer o~ this foil material according to the invention. They can be produced in known manner with unhard-ened, hardened, flat, ben-t, damped, printed, coloured, etched, structured silicate plate glass which optionally possesses a wire insert, as well as with colourless, coloured transparent, colour covered, printed foils according to the invention ~:P~1.9~
which optionally cOntaill in~aicl wires, wire meshes, webs or other objects which are produced in known manner. The thicknesses of the silicate glasses or -the foils produced according to the invention are variably selec-table according to the purpose of use, as well as likewise -the number of -the individual layers of the laminated object.
This makes possible the use oE the laminated glasses containing the foils according to the invention as adhesive foils in the building industry in doors and door surrounds, in windows and window surrounds, in parapets of bannisters, balconies or facades, in separating walls as room partitions, balcony dividers or fences for properties, in roofs or roof components of terraces, light transmitting roofs or guard houses, in cubicles for telephone or computer housing, shop windows, cashiers booths, prisons or in explosion or implo-sion susceptible chambers in each case as safety glass for protection against penetration~ breaking in, shooting, fire, sound, cold, warmth, heat, if necessary with alarm or hea-ting wires.
In the vehicle sector, the glazing of motor vehicles, road vehicles, ships and aircraft with windscreen, rear or side panes, doors, partitions etc may be mentioned.
The foil materials according to the invention are also suited in outstanding measure for the production of laminates with transparent tough elastic plastics.
In addition to polycarbonate, there can also be employed as transparent plastics panes those formed of poly-methylmethacrylate, polyethylene terephthalate, rigid P~C, polyamide, cellulose esters, s-tyrene-acryloni-trile polymers etc.
Tne following Examples illustrate the invention.
Example 1 (compara-tive example) DiEferent amoun-ts of triethyleneglycol di-2-ethyl-butyrate were mixed in wi-th a commercially available partially ~l~q~ t3 butyralised polyvinyl alcohol resin with a hydroxyl content of 20.7~ by weight, calculated as vinyl alcohol on a set of rollers. A number of foils of 0.76 mm -thickness were produced in a press from the rolled product with mat silk surface embossing and tested by storage a-t 23C and a rela-tive air humidity of 60% to see whether the premixed plasti-cizers underwent exudation. Furthermore the resis-tance to tearing, elongation at break, tensile strength at 100~ and cold impact value were determined. The measuring of the cold impact value was carxied out according to method VDCh 22-02 on shoulder samples (with a profile S 3 according to DIN 53 504) in the manner that the lowest temperature was sought with which at the most one of six samples bent to a loop is broken by a 200 g falling hammer, from a tes-t height of 200 mm.
The following values were obtained.
Plasticizer content 28 30 32 (~ by weigh-t) Exuded No No No Tear resistance (kp/cm ) 269 247 221 Tensile strength (kp/cm2) at 100% elongation 32 26 15 Cold impact value (O)-55 -55 -55 The plasticizer shows indeed a good compatibility with the PVB foil, if it is employed in amounts > 30~, al-though then the tear resistance and also, a-t a proportion of > 32%r the tensile strength is insufficient so that this plasticizer is not employable in amounts of > 30~ with reten-tion of good values.
Example 2 Different amoun-ts of different phthalic acid esters were mixed in with PVB resin with a hydroxyl group content of ~3~
20.7% b~ weight and foils were produced -therefrom, in the same manner as in Example 1. The resul-ts of the quali-ty -testing of such foils are set out in Table 1.
T a b 1 e Alcohol com- Amount Exuded Tear re- Cold Tensile streng-th ponents of (weight sistance impact kp/cm2 at 100%
the phthalic %) kp/cm2 value elongation acid esters C
n-C4-alcohol 28 no 251 -45 36 - 30 no 228 -50 28 32.5 no 194 -55 19 no 153 -55 15 n-C alcohol 28 no 273 -50 57 6 30 no 259 -50 42 32.5 no 218 -55 36 no 182 -55 23 n-C -alcohol 28 no 293 -50 74 7 30 no 281 -55 53 32.5 no 255 -55 40 no 222 -55 26 n-C -alcohol 28 no 294 -55 78 8 30 no 273 -55 58 32.5 yes 250 -55 48 yes 212 -55 35 80 % C 28 no 306 -45 92 10 % c6 30 no 282 -50 59 10 % c8 32.5 no 239 -55 34 no 221 -55 33 40 ~ C7 28 no 278 -50 98 40 % C 30 no 264 -55 48 20 ~ c8 32.5 no 242 -55 29 9 35 yes 217 -55 32 Example 3 A commercially obtainable PVB resin with a hydroxyl group content of 20.7~ by weight (calculated as vinyl alcohol) was mixed on the roller arrangement with different amounts of ~z~
-triethyleneglycol-cli.-2-ethylbutyrate (3 Gll) and a mixed ester (C 6/10) of phthalic acid and a mixture of C6-, C8-, C]0-alcohols (80:10:10). Foils 0.76 mm in thickness, whose properties appear in Table 2, were pressed from the rolled materials. The determination of the properties took place in the manner se-t out in Example 1. None of the compositions unde~went exuding.
T a b 1 e 2 Plas-ticizer content Tear Tensi2e strength Cold impact % by weight resistance kp/cm at 100~ value C
3 GH C6/10 Total kp/cm2 elongation 15.5 15.5 31 ~4g 27 -55 Samples of all the foils were then worked up to form laminated safety glasses, for which they were acclima-tised at 30~ relative humidity, then laid between twosilicate glass panes and subsequently the laminate was pro-duced by heating at 130 to 150C at a pressure of 12 bar.
The laminated safety glasses were tested for the adhesion between the silicate glass and the PVB foils according to the pummel method as described for example in German Patent Specification 2,410,153. All laminated safety glasses obtained showed pummel values of 10.
Example 4 In the same way as in Example 3, PVs foils with a hydroxyl group content of 20.7% by weight were produced with varying amounts of triethyleneglycol-diheptanoate (3 G 7) and phthalic acid heptyl ester (C 7) and their properties were determined. The results appear in Table 3. In all cases, the plasticizer mixtures were compa-tible with the PVB
~i7~
res.in.
T a b 1 e 3 Plasticlzer content Tear Tens.ile strength Cold impact % by weight resistance kp/cm2 at 100% value C
3 G 7 C 7 Total kp/cm2 elonga-tion 14 14 ~ 28 283 46 -50 14.5 14.5 29 263 31 -55 Laminated safety glasses made from these foils has a pummel adhesion of 10.
Example 5 In the same way as in Example 3, a PVB resin with a hydroxyl group content of 20.7% by weight, calculated as vinyl alcohol, was produced with triethyleneglycol diphepta-noate (3 G 7) and butylphthalate (C 4) present in different amounts in a total plasticizer content of 28~ by weight.
The results appear in Table 4. The plasticizer mixtures were compatible with the PVB resin in all cases.
T a b 1 e 4 Plasticizer content Tear Tensi~e strength Cold impact ~ by weight resis2tance kp/cm at 100% value C
3 G 7 C 4 Total kp/cm elongation 14 14 50:50 256 31 -50 12 16 43:57 256 28 -50 18 36:64 257 26 -50 8 20 29:71 254 27 -50 6 22 21:79 270 31 . -50 Example 6 In the same manner as in Example 3, a PVB resin with a hydroxyl group content of 20.7% by weight, calculated as vinyl alcohol, was produced with different plasticizers.
There are selected as glycol ester, as in Example 4, tri-ethyleneglycol dipheptanoate ~3 G 7) on -the one hand and as esters of organic cyclic acids, on the o-ther hand different phthalic acid esters. The mixiny ra-tio amoun-ted to 1:1.
The plasticizers employed and the properties of the foils ob-tained appear in Table 5. All plas-ticizers mixtures were compatible with the PVB resin.
T a b 1 e 5 Tear Tensile Cold resist strength impact ance 2 (kp/cm2) value ]cp/cm at 100% C
elonga-tion n-C7, C8, C9-Phthalate 257 40 -50 n-C8-Phthala-te 259 48 -50 i-C8-Phthalate 272 62 -45 n-C7, i-clo-phthalate 289 39 -50 n-C6' C7~ Cg~ C10~Phthalate 260 51 -55 n-C8, C10 Phthalate 279 43 -50 Butyl-, Benzylphthalate 268 43 -35 Butyl-, Cyclohexylphthalate 268 34 -45 Methylglycolphthalate 259 23 -50 Ethylglycolphthalate 280 27 -50 Butylglycolphthalate 270 32 -45 Laminated safety glasses made from these foils has a pummel adhesion of 10.
Example 7 A PVB resin with a hydroxyl group content of 18.4%
by weight, calculated as vinyl alcohol, was worked, in -the same way as in Example 3 with, in total, 30% by weight of
2~3~;
diEferent glycol es-ters and esters of oryanic cyclic acids in a mixing ratio oE 1:1 -to produce foils. The tear resist-ances are given in Table 6. In all cases, the plasticizer mixtures were compatible wi-th the PVs resins. Laminated safety glasses were produced from these foils; the pummel adhesion was 10.
T a b 1 e 6 PVA-content Tear (~ by weight) resis2tance of PVB resin Plasticizer kp/cm 18.4 Triethyleneglycol~diheptanoate 122 Dibutylphthalate 18.4 Triethyleneglycol-diheptanoate 158 Hexyldecylphthalate 18.4 Triethyleneglycol-diheptanoate 203 Octyldecylphthalate 18.4 Triethyleneglycol-caprylate/ 187 caprinate Hexyldecylphthalate 18.4 Triethyleneglycol-caprylate/ 194 caprinate Octyldecylphthalate ExampIe 8 PVB resins with a hydroxyl content oE 20.7% by weight, 22.3% by weight or 26.8% by weight respec-tively calculated as a vinyl alcohol were worked up to foils in like manner to Example 3 with, in total, 30% by wei~ht of different glycol esters and esters of organic cyclic acids.
In all cases, no exuding of the plasticizer was established.
. The tear resistances are compiled .in Table 7. The laminated safety glasses of these foils had a pummel adhesion of 10.
~2~3'~L3~
T a b 1 e 7 PVA~content Tear (% by weight) resistance of PVB resin Plas-ticizer kp/cm2 22.3 Triethyleneglycol-dihep-tanoate 258 Dibutylphthalate 26.8 Triethyleneglycol-diheptanoate 279 Dibutylphthala-te 22.3 Triethyleneylycol-diheptanoate 248 llexyldecylphthalate 22.3 Txiethyleneglycol-di-2-ethyl- 242 butyrate Dibutylphthalate 26.8 Triethy].ene~lycol-di-2-ethyl- 271 butyrate Dibutylphthalate 20.7 Tetraethyleneglycol-di-2-ethyl- 221 hexanoate Dibutylphthala-te Example 9 Different foils from Examples 1, 2, 3 and 5 were worked up to laminated safety glass as described in Example
diEferent glycol es-ters and esters of oryanic cyclic acids in a mixing ratio oE 1:1 -to produce foils. The tear resist-ances are given in Table 6. In all cases, the plasticizer mixtures were compatible wi-th the PVs resins. Laminated safety glasses were produced from these foils; the pummel adhesion was 10.
T a b 1 e 6 PVA-content Tear (~ by weight) resis2tance of PVB resin Plasticizer kp/cm 18.4 Triethyleneglycol~diheptanoate 122 Dibutylphthalate 18.4 Triethyleneglycol-diheptanoate 158 Hexyldecylphthalate 18.4 Triethyleneglycol-diheptanoate 203 Octyldecylphthalate 18.4 Triethyleneglycol-caprylate/ 187 caprinate Hexyldecylphthalate 18.4 Triethyleneglycol-caprylate/ 194 caprinate Octyldecylphthalate ExampIe 8 PVB resins with a hydroxyl content oE 20.7% by weight, 22.3% by weight or 26.8% by weight respec-tively calculated as a vinyl alcohol were worked up to foils in like manner to Example 3 with, in total, 30% by wei~ht of different glycol esters and esters of organic cyclic acids.
In all cases, no exuding of the plasticizer was established.
. The tear resistances are compiled .in Table 7. The laminated safety glasses of these foils had a pummel adhesion of 10.
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T a b 1 e 7 PVA~content Tear (% by weight) resistance of PVB resin Plas-ticizer kp/cm2 22.3 Triethyleneglycol-dihep-tanoate 258 Dibutylphthalate 26.8 Triethyleneglycol-diheptanoate 279 Dibutylphthala-te 22.3 Triethyleneylycol-diheptanoate 248 llexyldecylphthalate 22.3 Txiethyleneglycol-di-2-ethyl- 242 butyrate Dibutylphthalate 26.8 Triethy].ene~lycol-di-2-ethyl- 271 butyrate Dibutylphthalate 20.7 Tetraethyleneglycol-di-2-ethyl- 221 hexanoate Dibutylphthala-te Example 9 Different foils from Examples 1, 2, 3 and 5 were worked up to laminated safety glass as described in Example
3 and the water content of the foils in the laminate was de-termined infra-red spectroscopically. Table 8 sets out the results. The numerical values indicate the differential susceptibility of the foils to water uptake.
T a b 1 e 8 Total Plasticizer Mixing Water plasticizer type ratio content content %
by weight 28 3 G 7 - 0.54 28 C 4 - 0.49 T a b 1 e 8 lcontinued) Total Plastici.zerMixing Water plas-tic.izer type ratio content con-tent ~
by weiyh-t 28 ~ C 7 - 0.42 ~8 C 8 - 0.43 28 C 6/10 - 0.42 28 C 7/9 - 0.42 28 3 G 7 ~ C 7 50:50 0.47 28 3 G 7 + C 7 43:57 0.46 28 3 G 7 -~ C 7 36:64 0.45 28 3 G 7 ~ C 7 29:71 0.45 28 3 GH + C 6/1050:50 0.46 28 3 GH + C 6/1029:71 0.44 3 GH ~ C 6/1050:50 0.46 31 3 GH ~ C 6/1050:50 0.46 32 3 GH ~ C 6/1050:50 0.47 3 GH = Triethyleneglycol-di-2-e-thylbutyrate 3 G 7 = Triethyleneglycol-diheptanOate C 7 = Heptylphthalate C 8 = Octylphthalate C 6/10 = Hexyl-decylphthalate Example 10 0.76 mm thick foils were extruded from a) 72 parts of a commercially available PVB resin and 28 parts of triethyleneglycol-di-2-ethylbutyrate (composi-tion a) b) 72 parts of the same PVB resin and 28 parts of a plasti-cizer mixture, consisting of like parts of triethylene-glycol-di-2-ethylbutyrate and a mixed ester of phthalic ester and a mixture of hexanol, octanol and decanol ~g,~q'~,93L~36 (composition b) c) 69 parts o -the same PVB resin and 31 par-ts of the plasticlzer mixture described under b) (composition c).
The three types of foil contained so much anti-sticking ma-terial as such -that the pummel adhesion after acclimatising and working up -to laminated safety glass described in Example 3 lay at a value between 2 and 4.
The mechanical properties of the three types of foils were determined and the three types of laminated safety glass were subjected -to a dropping ball experiment accord~ng to DIN 52 306. The following results were obtained from these experiments.
Plasticizer composition a b c Tear resistance (kp/cm2) 250 245 230 Elongation at break (%) 270 275 280 Tensile strength (kp/cm2) at 100%
elongation 26 25 25 Pumme]. value 3 4 3 Water content (% by weight) 0.52 0.46 0.48 Dropping height ~m)6.50 6.50 6.50
T a b 1 e 8 Total Plasticizer Mixing Water plasticizer type ratio content content %
by weight 28 3 G 7 - 0.54 28 C 4 - 0.49 T a b 1 e 8 lcontinued) Total Plastici.zerMixing Water plas-tic.izer type ratio content con-tent ~
by weiyh-t 28 ~ C 7 - 0.42 ~8 C 8 - 0.43 28 C 6/10 - 0.42 28 C 7/9 - 0.42 28 3 G 7 ~ C 7 50:50 0.47 28 3 G 7 + C 7 43:57 0.46 28 3 G 7 -~ C 7 36:64 0.45 28 3 G 7 ~ C 7 29:71 0.45 28 3 GH + C 6/1050:50 0.46 28 3 GH + C 6/1029:71 0.44 3 GH ~ C 6/1050:50 0.46 31 3 GH ~ C 6/1050:50 0.46 32 3 GH ~ C 6/1050:50 0.47 3 GH = Triethyleneglycol-di-2-e-thylbutyrate 3 G 7 = Triethyleneglycol-diheptanOate C 7 = Heptylphthalate C 8 = Octylphthalate C 6/10 = Hexyl-decylphthalate Example 10 0.76 mm thick foils were extruded from a) 72 parts of a commercially available PVB resin and 28 parts of triethyleneglycol-di-2-ethylbutyrate (composi-tion a) b) 72 parts of the same PVB resin and 28 parts of a plasti-cizer mixture, consisting of like parts of triethylene-glycol-di-2-ethylbutyrate and a mixed ester of phthalic ester and a mixture of hexanol, octanol and decanol ~g,~q'~,93L~36 (composition b) c) 69 parts o -the same PVB resin and 31 par-ts of the plasticlzer mixture described under b) (composition c).
The three types of foil contained so much anti-sticking ma-terial as such -that the pummel adhesion after acclimatising and working up -to laminated safety glass described in Example 3 lay at a value between 2 and 4.
The mechanical properties of the three types of foils were determined and the three types of laminated safety glass were subjected -to a dropping ball experiment accord~ng to DIN 52 306. The following results were obtained from these experiments.
Plasticizer composition a b c Tear resistance (kp/cm2) 250 245 230 Elongation at break (%) 270 275 280 Tensile strength (kp/cm2) at 100%
elongation 26 25 25 Pumme]. value 3 4 3 Water content (% by weight) 0.52 0.46 0.48 Dropping height ~m)6.50 6.50 6.50
Claims (17)
1. A plasticizer-containing foil of partially acetalised polyvinyl alcohol, characterised in that said foil contains as plasticizer a mixture consisting essen-tially of a) at least one ester of an organic, cyclic acid and an alcohol, said alcohol having 4 to 10 carbon atoms and b) at least one ester of a glycol and an aliphatic mono-basic acid, the monobasic acid having 4 to 10 carbon atoms, the ratio of a) to b) in said mixture being from 85:15 to 15:85.
2. A plasticizer-containing foil according to claim 1, characterised in that it contains as an ester of an organic cyclic acid, an ester of phthalic acid and as an ester of a glycol, an ester of di-, tri- or tetraethylene-glycol.
3. A plasticizer-containing foil according to claim 1, characterised in that the partially acetalised polyvinyl alcohol possesses a hydroxyl group content of 5 to 30% by weight calculated as polyvinyl alcohol.
4. A plasticizer-containing foil according to claim 1, characterised in that the partially acetalised polyvinyl alcohol possesses a hydroxyl group content of 16 to 23% by weight calculated as polyvinyl alcohol.
5. A plasticizer-containing foil according to claim 1, characterised in that it possesses a Shore hardness A at 23°C between 100 and 20.
6. A plasticizer-containing foil according to claim 1, characterised in that it possesses a Shore hard-ness A at 23°C between 90 and 30.
7. A plasticizer-containing sheet according to claim 1, wherein the ester of an organic cyclic acid is n-heptyl phthalate and the ester of a glycol is triethylene glycol diheptanoate.
8. A plasticizer-containing sheet according to claim 1, wherein the ester of an organic cyclic acid is hexyl decyl phthalate and the ester of a glycol is triethylene glycol di-2-ethyl butyrate.
9. A plasticizer-containing foil of partially acetalised polyvinyl alcohol, said foil containing plasti-cizer in an amount of 10 to 40% by weight based on the total weight of the foil characterised in that said foil contains as plasticizer a mixture consisting essentially of a) at least one ester of an organic, cyclic acid and an aliphatic alcohol, said aliphatic alcohol having 4 to 10 carbon atoms and b) at least one ester of a glycol and an aliphatic mono-basic acid, said monobasic acid having 4 to 10 carbon atoms, the weight ratio of a) to b) in said mixture being from 85:15 to 15:85.
10. A plasticizer-containing foil according to claim 9, characterised in that it contains as an ester of an organic cyclic acid, an ester of phthalic acid and as an ester of a glycol, an ester of di-, tri- or tetraethylene-glycol.
11. A plasticizer-containing foil according to claim 9, characterise in that it contains the plastizer in amounts of 20 to 35% by weight based on the total weight of the foil.
12. A plasticizer-containing foil according to claim 9, characterised in that the partially acetalised polyvinyl alcohol possesses a hydroxyl group content of 5 to 30% by weight calculated as polyvinyl alcohol.
13. A plasticizer-containing foil according to claim 9, characterised in that the partially acetalised polyvinyl alcohol possesses a hydroxyl group content of 16 to 23% by weight calculated as polyvinyl alcohol.
14. A plasticizer-containing foil according to claim 9 f characterised in that it possesses a Shore hardness A at 23°C between 100 and 20.
15. A plasticizer-containing foil according to claim 9, characterised in that it possesses a Shore Hard-ness A at 23°C between 90 and 30.
16. A plasticizer-containing foil according to claim 9, 11 or 12, wherein the ester of an organic cyclic acid is n-heptyl phthalate and the ester of a glycol is triethylene glycol diheptanoate.
17. A plasticizer-containing sheet according to claim 9, 11 or 12, wherein the ester of an organic cyclic acid is hexyl decyl phthalate and the ester of a glycol is triethylene glycol di-2-ethyl butyrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3128530.9 | 1981-07-18 | ||
| DE19813128530 DE3128530A1 (en) | 1981-07-18 | 1981-07-18 | SOFTENING FILMS FROM PARTLY ACETALIZED POLYVINYL ALCOHOLS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1202136A true CA1202136A (en) | 1986-03-18 |
Family
ID=6137269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407413A Expired CA1202136A (en) | 1981-07-18 | 1982-07-16 | Plasticizer-containing foils formed of the partially acetalised polyvinyl alcohol |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0070394B1 (en) |
| JP (1) | JPS5865742A (en) |
| AT (1) | ATE21916T1 (en) |
| AU (1) | AU552306B2 (en) |
| BR (1) | BR8204160A (en) |
| CA (1) | CA1202136A (en) |
| CS (1) | CS235954B2 (en) |
| DE (2) | DE3128530A1 (en) |
| ES (1) | ES514044A0 (en) |
| IE (1) | IE53527B1 (en) |
| IN (1) | IN157515B (en) |
| SU (1) | SU1090260A3 (en) |
| ZA (1) | ZA825099B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013779A (en) * | 1989-12-08 | 1991-05-07 | Monsanto Company | Plasticized polyvinyl butyral and interlayer thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3537255A1 (en) * | 1985-10-19 | 1987-04-23 | Ver Glaswerke Gmbh | FIRE RESISTANT GLAZING UNIT |
| EP0457190B1 (en) * | 1990-05-14 | 1995-02-01 | Sekisui Chemical Co., Ltd. | Interlayers for use in sound-insulating laminated glasses |
| DE4024330A1 (en) * | 1990-07-31 | 1992-02-06 | Huels Troisdorf | Photochromic film prodn. for laminated safety glass - by extruding plasticised, acetalised polyvinyl-alcohol contg. photochromic cpds. which are pre-mixed with polymer and-or plasticiser |
| AT406053B (en) * | 1997-09-10 | 2000-02-25 | Petruzalek Ges M B H | USE OF BIODEGRADABLE, FOAMED POLYMERS AS PACKAGING MATERIALS |
| DE10129422A1 (en) * | 2001-06-19 | 2003-01-02 | Huels Troisdorf | Plasticized PVB film |
| CN1558927A (en) | 2001-09-25 | 2004-12-29 | ����ɭ���ڻ�ѧר����˾ | Plasticised polyvinyl chloride |
| DE10343385A1 (en) * | 2003-09-19 | 2005-04-14 | Kuraray Specialities Europe Gmbh | Composition containing polyvinyl acetal with a high content of polyvinyl alcohol units, used for the production of film for use in laminated glass, e.g. for car windscreens |
| DE102004000058A1 (en) * | 2004-12-01 | 2006-06-08 | Kuraray Specialities Europe Gmbh | Organophosphine-stabilized polymer blends |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD115103A5 (en) * | 1974-03-02 | 1975-09-12 | ||
| DE2453780C3 (en) * | 1974-11-13 | 1980-01-03 | Hoechst Ag, 6000 Frankfurt | Polyvinyl butyral mixture for the production of intermediate films for laminated glasses |
| JPS5934142B2 (en) * | 1978-02-09 | 1984-08-20 | 積水化学工業株式会社 | laminated safety glass |
| DE2820780A1 (en) * | 1978-05-12 | 1979-11-15 | Dynamit Nobel Ag | SOFTENING FILMS FROM PARTLY ACETALIZED POLYVINYL ALCOHOLS |
| DE2846837A1 (en) * | 1978-10-27 | 1980-05-08 | Hoechst Ag | POLYVINYLBUTYRAL FILM |
| US4292372A (en) * | 1980-06-02 | 1981-09-29 | E. I. Du Pont De Nemours And Company | Polyvinylbutyral sheeting |
-
1981
- 1981-07-18 DE DE19813128530 patent/DE3128530A1/en not_active Withdrawn
-
1982
- 1982-06-18 DE DE8282105351T patent/DE3273017D1/en not_active Expired
- 1982-06-18 AT AT82105351T patent/ATE21916T1/en not_active IP Right Cessation
- 1982-06-18 EP EP82105351A patent/EP0070394B1/en not_active Expired
- 1982-07-15 JP JP57122274A patent/JPS5865742A/en active Pending
- 1982-07-15 CS CS825441A patent/CS235954B2/en unknown
- 1982-07-15 AU AU86038/82A patent/AU552306B2/en not_active Ceased
- 1982-07-16 SU SU823464551A patent/SU1090260A3/en active
- 1982-07-16 ES ES514044A patent/ES514044A0/en active Granted
- 1982-07-16 ZA ZA825099A patent/ZA825099B/en unknown
- 1982-07-16 CA CA000407413A patent/CA1202136A/en not_active Expired
- 1982-07-16 IE IE1713/82A patent/IE53527B1/en unknown
- 1982-07-16 BR BR8204160A patent/BR8204160A/en unknown
- 1982-07-17 IN IN823/CAL/82A patent/IN157515B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013779A (en) * | 1989-12-08 | 1991-05-07 | Monsanto Company | Plasticized polyvinyl butyral and interlayer thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3128530A1 (en) | 1983-02-03 |
| AU8603882A (en) | 1983-01-27 |
| IE53527B1 (en) | 1988-12-07 |
| ES8403149A1 (en) | 1984-03-01 |
| JPS5865742A (en) | 1983-04-19 |
| IE821713L (en) | 1983-01-18 |
| CS235954B2 (en) | 1985-05-15 |
| ES514044A0 (en) | 1984-03-01 |
| BR8204160A (en) | 1983-07-12 |
| IN157515B (en) | 1986-04-12 |
| SU1090260A3 (en) | 1984-04-30 |
| DE3273017D1 (en) | 1986-10-09 |
| ATE21916T1 (en) | 1986-09-15 |
| AU552306B2 (en) | 1986-05-29 |
| EP0070394B1 (en) | 1986-09-03 |
| ZA825099B (en) | 1983-04-27 |
| EP0070394A1 (en) | 1983-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |