Source: https://patents.google.com/patent/US5449560A/en
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US5449560A - Composition suitable for glass laminate interlayer and laminate made therefrom - Google Patents
Composition suitable for glass laminate interlayer and laminate made therefrom Download PDF
US5449560A
US5449560A US08/173,405 US17340593A US5449560A US 5449560 A US5449560 A US 5449560A US 17340593 A US17340593 A US 17340593A US 5449560 A US5449560 A US 5449560A
US08/173,405
US5585709A (en
Nicole Antheunis
Andreas T. F. Wolf
1991-07-05 Priority to GB919114526A priority Critical patent/GB9114526D0/en
1991-07-05 Priority to GB914526 priority
1992-06-17 Priority to US89980192A priority
1993-12-23 Application filed by Dow Silicones Belgium SPRL filed Critical Dow Silicones Belgium SPRL
1993-12-23 Assigned to DOW CORNING S.A. reassignment DOW CORNING S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WOLF, ANDREAS THOMAS FRANZ, ANTHEUNIS, NICOLE
1993-12-23 Priority to US08/173,405 priority patent/US5449560A/en
1995-09-12 Publication of US5449560A publication Critical patent/US5449560A/en
A liquid curable composition prepared from a polydiorganosiloxane having ethylenically unsaturation, a polyhydrogenorganosiloxane, a catalyst for the addition of silicon-bonded hydrogen to ethylenically unsaturation, a particulate filler wherein the composition cured to an elastomeric state has a loss modulus, E", of at least 100 MPa at -120° C., a loss tangent of at least 0.15 at -120° C., and a tear strength of less than 10 kN/m at 23° C., makes an interlayer for a laminate of glass or other brittle which fails safely when receiving a breaking impact.
An object of this invention is to provide a low viscosity room-temperature-curable silicone composition which can be applied by cast-in-place techniques, which has minimal volume shrinkage upon cure, and which, when cast-in-place and cured has flawless optical clarity. Another object of this invention is to provide laminated glass structures, made from sheets of regular float glass and the above described composition, to pass at least the minimum fire and impact resistance tests applicable in the building industry.
Surprisingly, we have now found that impact and fire resistant laminated glass structures can be manufactured using comparatively soft and weak silicone materials as interlayer, provided the silicone material exhibits certain minimum values for loss modulus E" and loss factor tan delta at -120° C. Contrary to conventional laminated safety glass, in which the glass panes shatter and the high strength interlayer absorbs most of the impact energy by plastic or elastic deformation, laminated glass made according to the current invention relies on the fact that most of the impact energy is dissipated in the interlayer so that one of the glass panes will be able to carry the remaining impact energy without fracture by elastic deformation or "fail safely" (as defined in British Standard BS 6206).
This invention relates to a liquid curable composition comprising (A) at least one polydiorganosiloxane wherein the silicon-bonded organic substituents are monovalent hydrocarbon groups having from 1 to 14 carbon atoms, at least 70 percent of said organic substituents being methyl and there being present at least two silicon-bonded ethylenically-unsaturated groups per molecule on average, (B) at least one organohydrogensiloxane having at least two silicon-bonded hydrogen atoms per molecule on average, (C) a catalyst for the addition of SiH groups to silicon-bonded ethylenically unsaturated groups, and (D) a particulate filler which is at least partially insoluble in the composition, said composition having in the cured elastomeric state a loss modulus E" of at least 100 MPa at a temperature of -120° C., a loss factor (tan delta) of at least 0.15 at a temperature of -120° C., E" and tan delta being measured at 16 Hertz and 0.1% strain, and a tear strength of less than 10 kN/m at 23° C.
In the polydiorganosiloxane (A), at least 70 percent of the silicon-bonded substituents are methyl groups and at least two silicon-bonded substituents per molecule on average are ethylenically-unsaturated groups having from 2 to 14 carbon atoms, for example vinyl, allyl, hexenyl, or dodecenyl. Any remaining silicon-bonded substituents in the polydiorganosiloxane are monovalent hydrocarbon groups having from 2 to 14 carbon atoms and which are free of ethylenic unsaturation for example ethyl, propyl, hexyl, tetradecyl, phenyl, phenylethyl, and styryl. The preferred polydiorganosiloxanes are those wherein the ethylenically-unsaturated substituents are selected from vinyl and hexenyl and substantially all of the remaining substituents are methyl. Examples of the preferred polydiorganosiloxanes (A) therefore include copolymers of dimethylsiloxane units and methylvinylsiloxane units, copolymers of dimethylsiloxane units and dimethylvinylsiloxy units, copolymers of dimethylsiloxane, methylvinylsiloxane, and phenylmethylvinylsiloxy units, copolymers of dimethylsiloxane and methylhexenylsiloxane units, and copolymers of dimethyl-siloxane and dimethylhexenylsiloxy units. Preferably, the average number of ethylenically-unsaturated groups present per molecule lies within the range from 2 to 6.
In general, the molecular size of the polydiorganosiloxanes is not critical and they may vary from freely flowing liquids to gummy solids. However, the preferred method of employing the compositions is as cast- and cured-in-place interlayers. The preferred polydiorganosiloxanes (A) are therefore those having a viscosity in the range from about 100 to about 10,000 cS (10-4 to 10-2 m2 /s) at 25° C., thus facilitating the formulation of a composition having the desired pourable consistency. If desired, mixtures of polydiorgano-siloxanes of differing molecular size may be employed to achieve the desired viscosity characteristics or, in combination with filler (D), the desired values of E" and tan delta.
wherein R is for example methyl, ethyl, or phenyl and a is 1 or 2 either alone or combined with copolymeric siloxane units, for example dimethylsiloxane units or methylphenylsiloxane units. Having regard to the desired pourability of the curable composition, they are preferably of relatively low viscosity, but they may have viscosities as high as 20,000 cS (2×10-2 m2 /s) at 25° C. Preferred as organohydrogensiloxanes (B) are the methylhydrogensiloxanes, for example (CH3 HSiO)n, (n is an integer), copolymers of methylhydrogensiloxane CH3 HSiO units and trimethylsiloxy units, copolymers of dimethylsiloxane, methylhydrogensiloxane, and trimethylsiloxy units, copolymers of dimethylsiloxane and dimethylhydrogensiloxy units, and combinations of two or more of such siloxane homopolymers and copolymers. Mixtures of organohydrogensiloxanes having different molecular weights and/or different proportions of SiH content may be employed.
The filler (D) is a filler which is at least partially insoluble in the liquid curable composition, which has fire resistant properties and which provides in the cured composition the stated minimum values of E" and tan delta specified herein. Suitable fillers (D) include fumed and precipitated silicas which have been treated with siloxanes. Particularly suitable fillers are particulate, flowable materials consisting essentially of reinforcing silicas, having absorbed thereon a high proportion of a polydiorganosiloxane wherein at least 80 percent of the total organic substituents are methyl, any remaining organic substituents being selected from phenyl and vinyl groups. The absorbed polydiorganosiloxane should comprise at least 30%, and more preferably at least 50%, by weight of the weight of the filler. Such particulate filler materials may have up to 65 percent or more of the absorbed polydiorganosiloxane, provided that they remain in the essentially non-liquid state. The preferred reinforcing silicas are those having a high surface area to weight ratio, for example surface areas of from about 50 to about 500 square meters per gram. The molecular size of the absorbed polydiorganosiloxane is not critical, but polydiorganosiloxanes having viscosities within the range of 1,000 to 20,000 cS (0.001m2 /s to 0.02 m2 /s) at 25° C. are preferred having regard to availability and to ease of treatment of the silica substrate. Also particularly suitable and preferred as filler (D) are silicone elastomers in finely-divided particulate form. Such particulate elastomers may be prepared by spraying or emulsion techniques, for example as described by Shimizu in U.S. Pat. No. 4,742,142, Re-examination Certificate issued Sep. 3, 1991; by Yoshida et al in U.S. Pat. No. 4,743,670, issued May 10, 1988; and by Shimizu et al in U.S. Pat. No. 4,749,765, issued Jun.7, 1988. Fillers of particular utility in the compositions of this invention are available commercially from Dow Corning Toray Silicone Limited, Tokyo, Japan, under the trade name Trefil. The particle size of the filler Component (D) is not critical in terms of the impact and fire resistance performance of laminate structures made with the interlayer provided the filler allows achievement of the needed values of loss modulus, E", and loss factor, tan delta, and is in a flowable form which enables it to be incorporated homogeneously into the curable composition. However, in order to achieve interlayers of high translucency, the average particle size of the silica used in making the silica-polydiorgano-siloxane agglomerate filler has to be smaller than the wavelength of visible light. The particle size of the silicone elastomer particulate filler is not critical in terms of the translucency of the cured interlayer, provided the silicone elastomer particulate is fully compatible with the polydiorgano-siloxane matrix of the cured interlayer. In general, the preferred fillers are those having a particle size within the range of from 1 to 500 micrometers in the case of the polydiorganosiloxane fluid-silica agglomerate fillers and from 0.1 to 50 micrometers in the case of the silicone elastomer particulate fillers. As little as 0.05 per cent by weight of the filler (D) may be employed, but it is preferred that it should comprise at least one percent and more preferably from 2 to 15 percent of the total weight of the components (A) to (D). However, the proportion employed will be determined to some extent by the desired viscosity and pourability of the curable composition and degree of transparency required for the interlayer. Where the composition is employed to form a cast- and cured-in-situ interlayer it is preferred that its viscosity is less than 5,000 cS (0.005 m2 /s) at 25° C.
In addition to the essential Components (A) to (D), the compositions of this invention may contain certain optional ingredients, for example "secondary" fillers which do not affect the minimum values of loss modulus E" and loss factor tan delta, additives for reducing the viscosity of the composition, additives which confer flame retardant properties in the cured interlayer, for example compounds of transition metals such as titanium butoxide, zirconium silicate, and zirconium octoate, adhesion promoting substances, and additives for inhibiting cure of the composition. Preferred "secondary" fillers for use in the compositions of this invention are resinous copolymers of R3 SiO0.5 units and SiO2 units, wherein R is selected from methyl groups and vinyl groups. Preferably, at least 70 per cent of R groups are methyl and at least one R group per molecule is vinyl.
The compositions of this invention can be employed to form interlayers for a variety of laminated structures using two or more panels of the same or different materials such as glass, glass to plastic (e.g. acrylic), or plastic to plastic. They are, however, particularly adapted for application as interlayer materials for use in fire and impact resistant safety glass structures comprising two or more sheets of glass. The compositions may be performed and cured into interlayer sheets and thereafter laminated with the glass panes. A more preferred method of forming the laminated structures, however, comprises introducing the liquid curable compositions into the space defined between the glass panes and thereafter allowing the composition to cure at normal ambient or slightly elevated temperatures (up to 50° C). If desired, the bonding of the curable composition to the glass or other members of the laminated structure may be enhanced by pretreating of the surface of the member with a primer or other adhesion promoting substance.
Compositions of this invention have in the cured elastomeric state a loss modulus E" of at least 100 MPa at a temperature of -120 ° C., preferably from 200 to 500 MPa; a loss factor (tan delta) of at least 0.15 at a temperature of -120° C., preferably from 0.2 to 0.3; and a tear strength of less than 10 kN/m at 23° C. E" and tan delta are measured at 16 Hertz and 0.1% strain. The preferred compositions used as an interlayer to make impact resistant glass laminates have a tear strength of less than 1 kN/m.
In practice, the elastic storage modulus E', the loss modulus E", and the loss factor (tangent delta) of cured (solid) polymeric materials can be measured on automated dynamic mechanical analyzers, such as the Rheometrics Solid Analyzer RSA II. The Rheometrics RSA II allows measurement of the viscoelastic properties of solid materials over ranges of temperatures (-150° C. to 500° C.) and oscillatory strain frequencies (0.01 to 100 rad/sec or 100 to 0.01 sec time scales, respectively). The test procedure used to examine the interlayer formulations was as follows: The test samples were cooled from ambient temperature down to -150° C. by a stream of cold nitrogen while exposing them to an oscillatory elongation strain. It was important to keep the elongational strain amplitude low, especially when measuring at lower temperature or higher oscillatory frequencies, to ensure that the material was in its linear stress-strain region, i.e. that the loss modulus was not a function of strain. The strain amplitude was, therefore, decreased linearly from 0.5% to 0.1% with the temperature decrease. The oscillatory frequency was swept from 1 rad/s to 100 rad/s at a given temperature. The sample temperature was then adjusted by 4° C.; a soak time of 5 minutes was allowed to this temperature change.
The following experimental conditions were chosen in determining the viscoelastic properties of the cured silicone interlayers. The materials were cured for 4 weeks at ambient temperature (23° C.) prior to the measurement.
______________________________________Test System:   Rheometrics RSA II in elongationTemperature Range:          +20° C. to -150° C.Frequency Range:          1 to 100 rad/secTemperature Soak:          5 minutesStrain Amplitude:          0.5% to 0.1%______________________________________
Improvements in the impact resistance of glass laminates made with silicone interlayers were first studied in a screening test. For this purpose, two square panes of regular float glass with 300 mm edge length and 3 mm glass thickness were laminated together with the silicone composition by holding the glass panes with suitable spacers 2 mm apart and casting the silicone composition into place. The test units were stored at ambient temperature (23° C.) for four weeks. The glass laminates were then placed on a timber box in such a way, that the glass "bite" on the timber frame (the overlap between the laminated glass pane and the timber frame) was 10 mm. The screening test consisted of allowing a metal cannon ball with a mass of 2000 g to accelerated in free fall from 1000 or 2000 mm heights before impacting on the center of the test units. It had been previously determined that a good correlation exists between the screening test on above described small test units and British Standard BS 6206 ("Specification for Impact Performance Requirements for Flat Safety Glass and Safety Plastics for Use in Buildings") carried out on full-sized test units (865 mm edge length, 3 mm glass thickness, 2 mm interlayer thickness). Dropping the cannon ball from 1000 mm or 2000 mm heights was found to generate the same results as the BS 6206 test for Class C (135 Joule impact) or Class B (202 Joule impact), respectively. Interlayers that passed the screening test were also evaluated in the full-size BS 6206 mock-up. In order to pass the impact resistance tests, at least one of the glass panes had to withstand the impact without breaking, or both glass panes had to fail "safely", as defined in BS 6206.
The laminate test units were prepared by a casting process. For small sized laboratory units of about 300×300 mm, a polyisobutylene tape fabricated with a co-extruded rubber core (seal), was applied along three sides of the perimeter of one glass pane. Each extremity of the tape was covered on a length of 100 mm by a plastic film to avoid adhesion of the tape to the glass, and thus, allowed for a larger thickness of the interlayer during the casting process. Then a second glass pane was carefully attached to the first pane by pressing it against the polyisobutylene seal. The glass unit was then set at a 60 degree angle and a liquid composition for preparing the interlayer was cast into the space between the two glass panes by pouring the liquid composition through a funnel attached to the fourth (open) side of the unit. The liquid composition flowed into the glass unit following the gravitational force. The filling process was completed within about one-half of the the "pot-life" of the composition used for preparing the specified laminate. After the filling process was completed, the plastic film was carefully removed from the polyisobutylene seal, and the laminated glass was evenly compressed to a defined thickness. Excess composition exuded from the open fourth side and was scraped off. The unit was then stored in the horizonal position to allow the glass panes to straighten out into a perfect parallel position. After several hours of cure at room temperature, the unit was placed into a vertical position and stored for completion of the cure.
Fire resistance of the laminated glass structure was evaluated in indicative fire tests according to BS 476, Part 22 ("Fire Tests on Building Materials and Structures, Part 22: Methods for Determination of the Fire Resistance of Non-Loadbearing Elements of Construction") and DIN 4102, Part 5 ("Behavior of Building Materials and Components in Fire; Fire Resistant Glazings"). Laminated glass structures were constructed as described before and glazed either into timber or steel frames using conventional fire resistant glazing techniques. After storing the laminated structures for four weeks at ambient temperature (23° C.), the units were fixed into the opening of an indicative fire test rig in accordance with either BS 476, part 22, or DIN 4102, part 5, and exposed to the heating cycle (time-temperature curve) as set out in these standards. Integrity failure time was recorded as defined in these standards, which typically was reached by flaming occurring at the outer pane (the one being remote from the fire). Various laminate configurations (two or three glass panes with one or two interlayers) and various laminate dimensions were studied.
The viscosity of the liquid composition was determined about 5 minutes after completing the mixing of a base composition, crosslinker composition, and if used, a paste composition. The measurement was carried out at ambient conditions (23° C. and 55% rH) on a Brookfield viscometer with a cone and spindle configuration at 10 rpm.
The pot-life of the liquid composition was determined by measuring how long it took for the viscosity to increase at ambient conditions (23° C. and 55% rH) by 100% over its initial value, which was measured about 5 minutes after mixing the base composition, the crosslinker composition, and if used the paste composition.
Tensile strength and elongation at break were determined in accordance with ASTM D-412 after curing the liquid composition specimen at ambient conditions (23° C. and 55% relative humidity) for about 5 hours in a metallic mold, followed by demolding the specimen and allowing it to cure for 3 weeks at ambient conditions between two sheets of polyethylene. The tear strength was determined in accordance with ASTM D-624 and the test specimens were prepared using the same curing conditions as for the tensile strength and elongation at break.
1. Accelerated Weathering (35° C./75° C./100% rH)
Laminated glass units (150×150 mm or 150×75 mm in size) were placed into a humidity chamber conditioned at 100% relative humidity (rH) and thermally cycled between 35° C. and 75° C. The cycle consisted of a 4.5 hour "ramp-up" from 35° C. to 75° C., and a 1.5 hour "ramp-down" from 75° C. to 35° C. The units were expected to pass a minimum of 300 cycles.
2. QUV Aging (QUV/40° C.)
Laminated glass units (150×75 mm in size) were exposed in a QUV weathering tester to a continuous cycle of 16 hours of UV-B radiation (313 nm lamps) at 65° C., followed by 8 hours of water condensation at 40° C. The units were expected to pass a minimum of 30 cycles.
3. Heat Aging (70° C.)
Laminated glass units (150×150 mm or 150×75 mm in size) were stored in a ventilated convection-type oven at a temperature of 70° C. The units were expected to pass a minimum of 30 days test duration.
4. Temperature Cycling (-20° C./+23° C.)
Laminated glass units (150×150 mm or 150×75 mm in size) were exposed to a thermal cycle of 16 hours at -20° C. and 8 hours at ambient conditions (23° C., 55% rH) by storing the units in a freezer and under laboratory conditions respectively. The units were expected to pass a minimum of 30 cycles.
Laminated glass units (300×300 mm in size) were exposed in Seneffe, Belgium, by mounting them on racks with a 45 degree inclination angle in such a manner that the edge of the unit, where the interlayer was freely exposed to the climate, was on top. The units were expected to pass a minimum of 90 days test duration.
Adhesion to glass was evaluated by using ISO 8339 test samples (International Standard ISO 8339, "Building Construction--Jointing--Products--Sealants--Determination of Tensile Properties, " International Organization for Standardization, Geneva, Switzerland, 1984). The test samples were constructed from two pieces of glass (75×12×6 mm in dimensions), previously primed with DC 1200 primer, by casting the liquid composition into a glass/timber mold, to form a 12×12×50 mm joint between the glass supports. After allowing the sample to cure for 3 weeks at ambient conditions (23° C. and 55% rH), the timber mold was removed. The tensile strength and maximum elongation of the test specimen were then determined in accordance with ISO 8339 with a ZWICK extensiometer.
The light transmittance in the visible spectrum (400-800 nm) was determined using a Near-Infrared Spectrophotometer (NIR System 6500, NIRSystem, Perstorp Inc., Siver Springs, Md.). The specimen consisted of two 3 mm thick panes of glass sandwiching a 2 mm thick cast-in-place interlayer. The measurement was carried out after allowing the samples to cure for 3 weeks at ambient conditions (23° C., 55% rH).
The following examples are presented for illustrative purposes and should not be construed as limiting the invention which is properly delineated in the claims. In the following examples, "part" or "parts" are expressed by weight, and viscosities are measured at 23° C.
______________________________________INGREDIENTIDENTIFIER     INGREDIENT DESCRIPTION______________________________________A         Dimethylvinylsiloxy-endstopped polydimethyl-     siloxane (4.5 × 10.sup.-4 m.sup.2 /s).B         Trimethylsiloxy-endstopped polymethyl-     hydrogensiloxane (3 × 10.sup.-5 m.sup.2 /s).C         Copolymer of dimethylsiloxane & methyl-     hydrogensiloxane (5 × 10.sup.-6 m.sup.2 /s).D         Methylvinylcyclotetrasiloxane.E         Dimethylvinylsiloxy-endstopped polydimethyl-     siloxane (2 × 10.sup.-3 m.sup.2 /s).F         Complex of chloroplatinic acid and divinyltetra-     methyldisiloxane having a platinum content of     0.7 weight percent.G         Silicone elastomer particulate powder of     spherical morphology and an average particle     size of 3 micrometers (particle size distribution     of 1 to 15 micrometers). This powder had a true     specific gravity of 0.97, a bulk specific gravity     of 0.18, and a water content of less than 0.5     weight percent.H         Dry powder made from fumed silica and a     0.0125 m.sup.2 /s trimethylsiloxy endblocked poly-     dimethylsiloxane fluid. Agglomerates were of     irregular morphology, had a 10 to 300 micro-     meter particle size distribution, and contained     60% weight percent of the polydimethylsiloxane     fluid. This powder had a true specific gravity of     1.5, a bulk specific gravity of 0.4, and a water     content of less than 0.5 weight percent. The     fumed silica, prior to preparation of the     agglomerate, had a BET surface area of     200 ± 25 m.sup.2 /g, as measured by DIN 66131,     and an average primary particle size of 0.012     micrometer.I         Dry powder made from precipitated silica and a     0.0125 m.sup.2 /s trimethylsiloxy endblocked     polydimethylsiloxane fluid. Agglomerates were     of irregular morphology, had a 10 to 300 micro-     meter particle size distribution, and contained     60% weight percent of the polydimethylsiloxane     fluid. The powder had a true specific gravity     of 1.5, a bulk specific gravity of 0.4, and a water     content of less than 5%. The precipitated silica,     prior to the agglomeration, had a BET surface     area of 380 ± 30 m.sup.2 /g, as measured by DIN     66131, and 42% of the primary aggregates had     less than 1 micrometer in particle size.J         Terpolymer of trimethylsiloxy units, dimethyl-     vinylsiloxy units, and SiO.sub.2 units having a ratio     of combined trimethylsiloxy units and dimethyl-     vinylsiloxy units per SiO.sub.2 units of about     0.7/1.K         Zirconium octoate in trimethylsiloxy endblocked     polydimethylsiloxane fluid having a viscosity of     0.00002 m.sup.2 /s (1.56 weight percent zirconium     octoate in the fluid),______________________________________
Table I contains the results of testing the liquid Compositions 1, 2, 3, 4, 5 and 6. The properties tested were as shown in Table I. Liquid Composition 1 was a comparative composition. The glass laminate made using an interlayer of the Liquid Composition 1 failed the Class C impact resistance test and from Table I, the value of the loss modulus, E", was 60 MPa which was well below the needed 100 MPa.
TABLE I__________________________________________________________________________         COMPOSITIONPROPERTY      2    3    4    5    6     1**__________________________________________________________________________Viscosity, m.sup.2 /s         0.002              0.002                   0.002                        0.002                             0.00085                                   0.002Pot Life, hours         1    1    1    1    0.9   1Tensile Strength         0.1  0.4  0.3  0.5  0.35  0.4at break, MPaElongation    100  90   120  110  45    50at break, %Tear Strength, kN/m         0.5  0.6  0.6  0.6  0.6   0.6Adhesive Strengthon Glass, T/A jointsTensile Strength, MPa         0.1  0.1  0.1  0.1  0.05  0.05Elongation at Break, %         25   20   25   25   25    25tan delta (-120° C.)         0.25 0.20 0.25 0.22 0.20  0.2E' (MPa) (-120° C.)         2000 2500 2000 900  1500  300E" (MPa) (-120° C.)         500  500  500  200  300   60Light Transmittance, %         --   --   >95  --   >90   --of 3/2/3 laminateover 400-800 rm rangeFire Resistance BS 476         19   24   27   --   15    12(900 × 900 mm 3/2/3 mmlaminate (minutes)Impact Resistance         Class B              Class C                   Class C                        Class C                             Class C                                   failsBS 6206 Class                           Class C(3/2/3 mm laminate)Accelerated Aging6 months 75° C./100% rH         pass pass pass pass pass  pass6 months QUV/40° C.         pass pass pass pass pass  pass6 months 70° C. heat         pass pass pass pass pass  pass6 months -20° C./+25° C.         pass pass pass pass pass  pass12 months outdoors         pass pass pass pass pass  pass24 months outdoors         --   --   pass --   pass  --__________________________________________________________________________
__________________________________________________________________________         COMPOSITIONPROPERTY      7**  8**  9    10   11   12***__________________________________________________________________________Viscosity, m.sup.2 /s         0.0055              0.005                   0.005                        0.003                             0.005                                  >1Pot Life, hours         1    1    1    2.5  1    --Tensile Strength         6.2  6.5  6.2  1.0  1.7  8.5at break, MPaElongation    100  --   --   120  135  750at break, %Tear Strength, kN/m         2.7  4.6  4.5  1.2  1.8  20tan delta (-120° C.)         0.12 0.23 0.33 0.33 0.3  0.1E' (MPa) (-120° C.)         500  400  600  600  1000 2000E" (MPa) (-120° C.)         60   90   200  200  300  200Fire Resistance ES 476         --   --   --   >30  >30  12(900 × 900 mm 3/2/3 mmlaminate (minutes)Impact Resistance         fails              fails                   Class C                        Class C                             Class C                                  Class BBS 6206 Class Class C              Class C(3/2/3 mm laminate)Accelerated Aging6 months 75° C./100% rH         --   --   --   pass pass --6 months QUV/40° C.         --   --   --   pass pass --6 months 70° C. heat         --   --   --   pass pass --6 months -20° C./+25° C.         --   --   --   pass pass --6 months outdoors         --   --   --   pass pass --__________________________________________________________________________ ***This composition was prepared by mixing 56 parts of a dimethylvinylsiloxy terminated polydimethylsiloxane/methylvinylsiloxane copolymer containing 0.142 mole percent of methylvinylsiloxane units and having a Williams Plasticity Number of 150, 10 parts of a hydroxyl terminated polydimethylsiloxane having a Williams Plasticity Number of 150, and 32 parts of a silica filler made in accordance with the procedur described in U.S. Pat. No. 4,985,525. This composition is presented as a comparative composition. Composition 12 was too viscous to be castin-plac and had to be sheeted and then the laminate was prepared by sandwiching the sheeted composition between two glass panes.
This example illustrates the need for high loss modulus (E") and loss factor (tan delta) values at -120° C. in order to pass the BS 6206 Class C impact resistance test with low tensile and low tear strength interlayers. Viscoelastic properties were as shown in Table 3 in which liquid composition of this invention were compared to compositions outside the scope of this invention such as the high strength composition identified as Composition 12 which was a very high viscosity material.
TABLE 3______________________________________  1      2       4    7    8    9    11   12BS 6206  fail   pass    pass fail fail pass pass passClass C______________________________________T (°C.) E' (MPa)       E" (MPa) tan delta______________________________________COMPOSITION 1-120  300            60       0.20-100  300            60       0.20 -75  300            60       0.20 -50  0.4            0.035    0.09 -25  0.4            0.025    0.06  0   0.4            0.020    0.05COMPOSITION 2-120  2000           500      0.25-100  800            100      0.13 -75  700            50       0.07 -50  0.8            0.03     0.04 -25  0.6            0.01     0.02COMPOSITION 4-120  2000           500      0.25-100  800            100      0.13 -75  400            40       0.10 -50  0.6            0.01     0.02 -25  0.6            0.01     0.02COMPOSITION 7-120  500            60       0.12-100  90             20       0.22 -75  30             6        0.20 -50  9              3        0.33 -25  4              1        0.25  0   3              0.5      0.17COMPOSITION 8-120  400            90       0.23-100  90             25       0.28 -75  20             5.5      0.28 -50  5              2        0.40 -25  2.5            0.7      0.28  0   1.5            0.3      0.20COMPOSITION 9-120  600            200      0.33-115  300            130      0.43-100  so             23       0.29 -75  17             5        0.29 -50  6              2        0,33 -25  3              0.75     0.25  0   1.7            0.3      0.18COMPOSITION 11-120  1000           300      0.30-125  600            250      0.42-100  90             22       0.24 -75  18             5        0.28 -50  6              2        0.33 -25  3              0.7      0.23COMPOSITION 12.sup.a-120  2000           200      0.10-100  900            90       0.10 -75  400            50       0.13 -70  50             10.5     0.21 -50  13             2        0.15 -25  10             1.2      0.12  0   6              1        0.17 +25  5              0.9      0.18______________________________________ .sup.a The tan delta for Composition 12 went through a maximum at about -70° C. and showed that the composition at lower temperatures was in what may be termed "a frozen state.
This example illustrates the effect of laminate configuration, laminate size, and frame size on the fire test results (Fire tests: DIN 4102, Part 5 and BS 476, Part 22). The test results were as shown in Table 4.
TABLE 4__________________________________________________________________________        LAMINATECOMPOSITION 4        A      B     C     D      E__________________________________________________________________________Laminate Configuration        G/I/G  G/I/C G/I/G G/I/C  G/I/G/I/G(in mm)      3/2/3  3/2/3 3/2/3 3/2/3  3/2/3/2/3Glass Dimensions (in mm)        1000 × 1000               210 × 310                     750 033 09 650                           2010 × 1015                                  300 × 300Frame Material        Steel  Steel Steel Wood   SteelTest         DIN    BS476 BS476 BS476  DINFire Resistance (in min)        41     >30   >30   22     >30__________________________________________________________________________
______________________________________              LAMINATECOMPOSITION 5      F______________________________________Laminate Configuration              G/I/G(in mm)            3/2/3Glass Dimensions (in mm)              1050 × 900Frame Material     WoodTest               BS476Fire Resistance (in min)              26______________________________________
Compositions 2, 3, 4, 5, 6, 9, 10 and 11 passed the BS 6206 Class C impact resistance test in 3/2/3 glass laminates and Composition 2 passed the Class B impact resistance requirements in a 3/2/3 glass laminate. These compositions had a loss modulus of 200 MPa or higher and a loss factor of 0.15 or higher; both properties being measured at -120° C. Glass laminates (3/2/3) made with these compositions passed a screening fire resistance test with more than IS minutes fire endurance. Glass laminates made with these compositions exceeded all accelerated and natural aging durability requirements and exhibited excellent transparency, as demonstrated by Compositions 4 and 6.
Glass laminates (3/2/3) made with the Comparative Compositions 1, 7, and 8 failed the impact resistance requirements of BS 6206 Class C. These comparative compositions exhibited a loss modulus, measured at -120° C., of below 100 MPa, which, based on the experimentation, is believed to be the minimum value required to pass the impact resistance test. Comparative Composition 7 exhibited a tan delta, measured at -120° C., of 0.12, which was below 0.15, which, based on the experimentation, is believed to be the minimum value required to pass the impact resistance test.
Compositions 2, 3, and 4 when compared to Comparative Composition 1 showed the effect of fillers G, H, and I on the properties of the cured interlayer compositions and of the glass laminates made therefrom. Both storage modulus and loss moduli, measured at -120° C., increased significantly upon addition of these fillers. The tear strength, measured at room temperature, was not affected by the filler addition. The filled compositions achieved somewhat higher elongations at break, however, the tensile strengths of these compositions was not improved. The filled compositions of this invention passed the impact resistance requirements (BS 6206 Class C or B) in 3/2/3 glass laminates, while the unfilled comparative compositions did not pass the BS 6206 Class C requirements.
From these comparisons, the improvements in the impact resistance was related to the better damping characteristics (higher loss modulus and higher tan delta), measured at -120° C., of the filled compositions, and not to changes in their physical properties at room temperature. The improved damping characteristics, measured at -120° C., were directly attributed to the use of fillers (G, H, and I.
The high strength Comparative Composition 12 also passed the requirements of BS 6206 Class B impact resistance test, however, as shown below, this performance was attributed to the high tear strength of this composition, and not to its damping properties at -120° C. It is also noted that, due to its gummy character, this composition was only available as performed (calendered) interlayer sheets.
The loss factor of Compositions 2 and 4 increased steadily with decreasing measurement temperatures, while the loss factor Compositions 9 and 11 went through a side maximum at about -55° C., followed by a side minimum at about -100° C., then rapidly increased with decreasing measurement temperatures to its absolute maximum at -115° C. The loss factor of unfilled Comparative Composition 1 reached its maximum at about -75° C. and remained constant with further decreasing measurement temperatures. The loss factor of Comparative Compositions 7 and 8 went through its absolute maximum at about -50° C., and then rapidly decreased toward lower measurement temperatures.
The high strength interlayer (Composition 12) did not provide for a strong molecular relaxation mechanism at temperatures below -100° C. as shown by the values in Example III. The loss factor went through a maximum at about -75° C. and then decreased rapidly with decreasing temperature. The fact that Composition 12 exhibited a loss modulus of 200 MPa at -120° C. was only attributed to its high storage modulus at that temperature, because the loss factor was low (0.1). The high strength interlayer Composition 12, thus, passed the BS 6206 Class B impact resistance test not because of its high tear strength. The toughness of Composition 12 interlayer was attributed to the use of the highly disperse silica described by Lutz in U.S. Pat. No. 4,344,800. Its use in compositions of this invention would not result in an improvement of the damping characteristics at temperatures below -100° C., because the maximum of the loss modulus of Composition 12 at -75° C. was attributed to this filler.
As seen from the above discussion of the experimental results, there are two criteria that need to be met in order to achieve good impact resistance in the glass laminate via molecular energy dissipation in the interlayer: (a) the loss modulus of the interlayer composition at temperatures below about -100° C. needs to be as high as possible; based on experimentation, a minimum loss modulus of 100 MPa needs to be achieved at -120° C., (b) the loss factor of the interlayer composition at temperatures below about -100° C. needs to be as high as possible; based on experimentation, a minimum loss factor of 0.15 needs to be achieved at -120° C.
1. A pourable curable composition comprising
(A) at least one polydiorganosiloxane wherein the silicon-bonded organic substituents are monovalent hydrocarbon groups having from 1 to 14 carbon atoms, at least 70 per cent of said organic substituents being methyl and there being present at least two silicon-bonded ethylenically-unsaturated groups per molecule on average, and a kinematic viscosity at 25° C. of 0.0001 to 0.01 m2 /s,
(B) at least one organohydrogensiloxane having at least two silicon-bonded hydrogen atoms per molecule on average,
(C) a catalyst for the addition of SiH groups to silicon-bonded ethylenically-unsaturated groups, and
(D) a particulate filler which is at least partially insoluble in the composition, said filler being present in an amount of 2 to 15 weight percent based on the total weight of components (A) through (D),
said composition having in the cured elastomeric state a loss modulus E" of at least 100 MPa at a temperature of -120° C., a loss factor (tan delta) of at least 0.15 at a temperature of -120° C., E" and tan delta being measured at 16 Hertz and 0.1% strain, and a tear strength of less than 10 kN/m at 23° C.
3. The composition according to claim 1, wherein the filler (D) is selected from the group consisting of (i) a particulate material consisting essentially of a reinforcing silica having absorbed thereon at least 30 percent by weight, based on the weight of the silica, of a polydiorganosiloxane having a viscosity at 25° C. of 0.001 to 0.02 m2 /s, and wherein at least 80 per cent of the total silicon-bonded organic groups are methyl, any remaining silicon-bonded organic groups being phenyl or vinyl groups, and (ii) a silicone elastomer in particulate form.
4. The composition according to claim 2, wherein the filler (D) is selected from the group consisting of (i) a particulate material consisting essentially of a reinforcing silica having absorbed thereon at least 30 percent by weight, based on the weight of the silica, of a polydiorganosiloxane having a viscosity at 25° C. of 0.001 to 0.02 m2 /s, and wherein at least 80 per cent of the total silicon-bonded organic groups are methyl, any remaining silicon-bonded organic groups being phenyl or vinyl groups, and (ii) a silicone elastomer in particulate form.
9. The composition according to claim 1 where the composition has a viscosity after mixing components (A) through (D) of less than 0.005 m2 /s at 25° C. when measured with a cup and spindle configuration at 10 rpm on a Brookfield viscometer.
10. The composition according to claim 4 where the composition has a viscosity after mixing components (A) through (D) of less than 0.005 m2 /s at 25° C. when measured with a cup and spindle configuration at 10 rpm on a Brookfield viscometer.
14. The composition according to claim 1 further comprising a resinous copolymer comprising R3 SiO0.5 units and SiO2 units, wherein each R is selected from methyl radical and vinyl radical, at least one R group per molecule being vinyl.
15. A laminate structure comprising at least two panels of glass having sandwiched between at least two of said panels cured product of a pourable curable composition comprising
said composition having in the cured elastomeric state a loss modulus E" of at least 100 MPa at a temperature of -120° C., a loss factor (tan delta) of at least 0.15 at a temperature of -120° C., E" and tan delta being measured at 16 Hertz), and a tear strength of less than 10 kN/m at 23° C., and
said laminate when receiving a panel breaking impact fails safely.
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