WO1999015604A1 - Fire resistant laminates - Google Patents

Fire resistant laminates Download PDF

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Publication number
WO1999015604A1
WO1999015604A1 PCT/GB1998/002854 GB9802854W WO9915604A1 WO 1999015604 A1 WO1999015604 A1 WO 1999015604A1 GB 9802854 W GB9802854 W GB 9802854W WO 9915604 A1 WO9915604 A1 WO 9915604A1
Authority
WO
WIPO (PCT)
Prior art keywords
intumescent material
material according
fire resistant
metal phosphate
phosphate
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.)
Ceased
Application number
PCT/GB1998/002854
Other languages
French (fr)
Inventor
John Richard Holland
David William Holden
Karikath Sukumar Varma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pilkington Group Ltd
Original Assignee
Pilkington PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pilkington PLC filed Critical Pilkington PLC
Priority to AU91746/98A priority Critical patent/AU9174698A/en
Priority to AT98944073T priority patent/ATE263822T1/en
Priority to EP98944073A priority patent/EP1025185B1/en
Priority to DE69823050T priority patent/DE69823050T2/en
Publication of WO1999015604A1 publication Critical patent/WO1999015604A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • 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
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10311—Intumescent layers for fire protection
    • 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
    • B32B17/10706—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 being photo-polymerized
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
    • C09K15/14—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen containing a phenol or quinone moiety

Definitions

  • the invention relates generally to fire resistant laminates and in particular to intumescent interlayer materials for such laminates. Fire resistant laminated glazings are
  • the basic PYRODUR laminate comprises two sheets of glass bonded together
  • a curable interlayer material for example an epoxy resin.
  • the invention provides an intumescent material for fire resistant laminate interlayers comprising a metal phosphate, a char forming component and a binding agent.
  • the metal phosphate comprises a water soluble glass forming metal phosphate.
  • Zinc, aluminium, magnesium, tin, titanium or calcium phosphate are examples of
  • dehydrates when heated to form a solid carbon residue is also preferably soluble.
  • phosphate and char forming component solutions can therefore be mixed together to form an easily castable liquid.
  • the binding agent is required in order to gel the mixed solution once cast.
  • the inorganic component of the material that is the phosphate, is supported by
  • having a glass forming metal phosphate is that it melts when heated and flows over the carbon
  • the phosphate may be a mixed metal phosphate.
  • metal in the phosphate may be an alkali metal, such as lithium or potassium, which serves to
  • a second additional metal in the phosphate may be a multivalent metal, such as
  • interlayer material to flow and amass at the bottom of the laminate.
  • additional metals are
  • the char forming component is preferably sorbitol.
  • the binding agent is preferably a polymer.
  • Acrylamide has been found to be readily compatible with phosphate solutions.
  • the polymer is preferably UV cured, in which case the
  • material further comprises a photoinitiator, but could be heat cured.
  • Intumescence can be reduced from about
  • methylenebisacrylamide, cyanuric acid-triglycidyl ether and ethylene glycol dimethacrylate are all effective cross-linking agents, although N,N'-methylenebisacrylamide appears most
  • boric acid may be added. This appears to be used as an interlayer between sheets of glass, boric acid may be added. This appears to be used as an interlayer between sheets of glass, boric acid may be added. This appears to be used as an interlayer between sheets of glass, boric acid may be added. This appears to be used as an interlayer between sheets of glass, boric acid may be added. This appears to be used as an interlayer between sheets of glass, boric acid may be added. This appears to
  • the adhesion of the material to glass may be improved by coating the
  • the material may be used as an interlayer between sheets of sodium silicate glass,
  • interlayer which may be annealed, toughened or laminated, or borosilicate glass.
  • the interlayer will be between 0.5 mm and 15 mm thick.
  • the material may be used as an interlayer between
  • Figure 1 is a side view, shown partially in section, of a two-glass-sheet fire resistant laminated glazing including an interlayer material according to the invention.
  • Figure 2 is a side view, shown partially in section, of a four-glass-sheet, hybrid fire
  • a fire resistant laminated glazing indicated generally at 1 has
  • Phosphoric acid was placed in a flask, maintained at 80°C to 100°C, and zinc oxide
  • the laminate 1 was made by bonding the two sheets 2, 4 together around their edges
  • liquid intumescent is pumped into the cell after having been
  • the intumescent material was then gelled in situ by curing the acrylamide.
  • the laminate was exposed to UV radiation.
  • the laminate was tested on an electric furnace, following the fire test curve set out in
  • the interlayer formed a hard charred mass with no more than 100%
  • a hybrid fire resistant laminated glazing 10 was made up from two of the applicants PYRODUR fire resistant laminated glasses 12, 14 separated by an interlayer 16 of the same formulation as described with reference to figure 1.
  • PYRODUR glasses 12, 14 was 15 mm thick and had a 3 mm interlayer 18, 20 of sodium silicate.
  • the interlayer 16 between the PYRODUR glasses was 3 mm thick and the laminate

Landscapes

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

Abstract

An interlayer material for fire resistant laminates comprising a water soluble, glass forming metal phosphate, a water soluble char forming component and a binding agent. The material can be cast-in-place.

Description

FIRE RESISTANT LAMINATES
The invention relates generally to fire resistant laminates and in particular to intumescent interlayer materials for such laminates. Fire resistant laminated glazings are
known which comprise two or more sheets of glass bonded together by interlayers of a
material that intumesces when exposed to fire, that is, it expands so as to provide a heat barrier
whilst holding the sheets together thereby maintaining the integrity of the laminate and
preventing the spread of flames and smoke.
The applicants and their subsidiary companies currently produce a range of fire
resistant laminated glazings which are marketed under the trade names PYRODUR and
PYROSTOP. The basic PYRODUR laminate comprises two sheets of glass bonded together
with an interlayer of sodium silicate, and is made by pouring a sodium silicate solution on to
one of the sheets of glass, drying the solution and laminating a second sheet over the top.
Further detail on the production of PYRODUR-type laminates is disclosed in GB-A- 1585125. Whilst PYRODUR laminates and their PYROSTOP derivatives perform excellently and
have been commercially successful, there is scope for a fire resistant laminated glazing which is
simple, and hence relatively inexpensive, to fabricate. One way of keeping the fabrication
process simple would be to make use of the conventional cast-in-place laminating technique.
This is commonly used for making laminated architectural glazings and involves holding two
sheets of glass together at their edges, usually with an adhesive tape, so as to form a cell which
may be filled with a curable interlayer material, for example an epoxy resin. However, there
are difficulties associated with producing sodium silicate interlayers by the cast-in-place route,
most notably the need to remove in the region of 50% of the water from the sodium silicate
solution. Consequently, to make straightforward use of the cast-in-place technique, an
alternative intumescent interlayer material would be preferable. The invention provides an intumescent material for fire resistant laminate interlayers comprising a metal phosphate, a char forming component and a binding agent.
Preferably, the metal phosphate comprises a water soluble glass forming metal phosphate. Zinc, aluminium, magnesium, tin, titanium or calcium phosphate are examples of
such phosphates , although zinc phosphate is preferred. The char forming component, which
dehydrates when heated to form a solid carbon residue, is also preferably soluble. The
phosphate and char forming component solutions can therefore be mixed together to form an easily castable liquid. The binding agent is required in order to gel the mixed solution once cast.
In use, the inorganic component of the material, that is the phosphate, is supported by
the carbon residue and, in turn, the phosphate protects the carbon residue. The advantage of
having a glass forming metal phosphate is that it melts when heated and flows over the carbon
residue so as to protect it from oxidation. The greater the concentration of the phosphate
solution, the greater the protection afforded.
Further preferably, the phosphate may be a mixed metal phosphate. A first additional
metal in the phosphate may be an alkali metal, such as lithium or potassium, which serves to
lower the temperature at which the phosphate melts to form a glass. Hence, in use, the alkali
metal lowers the temperature at which the glass is able to offer protection for the carbon
residue. A second additional metal in the phosphate may be a multivalent metal, such as
aluminium, calcium or magnesium, which serves to increase the viscosity of the glass formed from the phosphate. In a laminate, viscosity is required in order to reduce the tendency of the
interlayer material to flow and amass at the bottom of the laminate. The additional metals are
preferably added as chlorides, wherein the metal phosphate forms a chlorophosphate. The
presence of the chloride has been found to significantly increase solubility. The char forming component is preferably sorbitol. A number of other carbohydrates,
particularly sugars, have been tried but only sorbitol appeared to be sufficiently soluble in a significant quantity.
The binding agent is preferably a polymer. Acrylamide has been found to be readily compatible with phosphate solutions. The polymer is preferably UV cured, in which case the
material further comprises a photoinitiator, but could be heat cured. Suitable photoinitiators
are available in the UK from the Ciba-Geigy company under the designations Darocure 4263 or Darocure 1173.
In addition, improved results have been obtained by adding a cross-linking agent which reduces the amount of polymer needed to bind the interlayer without significantly reducing its
strength and controls the degree of intumescence. Intumescence can be reduced from about
1000% to 100%, and can be controlled by altering the concentration of cross-linking agent.
By limiting intumescence, the stability of the laminate in use can be controlled. N,N'-
methylenebisacrylamide, cyanuric acid-triglycidyl ether and ethylene glycol dimethacrylate are all effective cross-linking agents, although N,N'-methylenebisacrylamide appears most
compatible.
It is known that the presence of boron oxide forming compounds in an intumescent
interlayer improves the adhesion between carbon residue and glass. Hence, if the material is to
be used as an interlayer between sheets of glass, boric acid may be added. This appears to
heighten fire performance by improving interlayer adhesion and to prevent cracking. However,
the addition of more than a small amount of boric acid is only possible in the presence of
sorbitol.
Furthermore, the adhesion of the material to glass may be improved by coating the
glass with hydrolysed methacryl functionalised organosilane, baking the glass and exposing it
to UV radiation. The material may be used as an interlayer between sheets of sodium silicate glass,
which may be annealed, toughened or laminated, or borosilicate glass. Typically the interlayer will be between 0.5 mm and 15 mm thick. The material may be used as an interlayer between
fire resistant laminates with sodium silicate interlayers, thereby forming a hybrid fire resistant
laminate. The performance of the hybrids is much better than would be expected, that is there appears to be a synergistic effect, because the material according to the invention, as well as
acting as an intumescent, appears to reduce water loss from the sodium silicate and thereby prolongs its fire resistance. Also of benefit to its use in fire resistant laminated glazing is the material's low flammability. Certain countries, for example Japan, have very strict regulations
concerning the flammability of fire resistant interlayers.
The invention will now be described, by way of example, with reference to the
drawings, in which:
Figure 1 is a side view, shown partially in section, of a two-glass-sheet fire resistant laminated glazing including an interlayer material according to the invention; and
Figure 2 is a side view, shown partially in section, of a four-glass-sheet, hybrid fire
resistant laminated glazing including an interlayer material according to the invention.
With reference to figure 1, a fire resistant laminated glazing indicated generally at 1 has
two sheets of silane coated, 3 mm thick sodium silicate float glass 2, 4, each 500 mm x 750
mm, which are separated by a 3 mm thick intumescent interlayer 6 of the following
formulation:
86% Mixed phosphate [ZnKo.5Mg0.25(H2PO4).HCl] solution 70 parts
85% Sorbitol solution 20 parts
Boric acid 10 parts
60% Acrylamide solution* 10 parts * 2% of solution was N,N'-methylenebisacrylamide cross-linking agent and 0.05% is Darocure 1173 photoinitiator.
The formulation was made as follows:
Phosphoric acid was placed in a flask, maintained at 80°C to 100°C, and zinc oxide
added with the acid refluxing gently until fully dissolved. The solution was cooled and
potassium chloride was added, followed by magnesium chloride. Sorbitol was dissolved at
90°C at a concentration of 85% in water. The full amount of boric acid was added to the sorbitol solution. The sorbitol solution was mixed with the phosphate solution at 70°C. Acrylamide was dissolved in water together with the requisite amount of N,N'-
methylenebisacrylamide and Darocure 1173 (added as 10% methanolic solution) to form 60%
(w/w) solution. The phosphate and acrylamide solutions were rapidly mixed, and extra water added.
The laminate 1 was made by bonding the two sheets 2, 4 together around their edges
with a foamed polyurethane tape 8 so as to form a cell between the two sheets 2, 4. A small
gap (not shown) was left in the tape 8 so as to enable the cell to be filled with the liquid
intumescent material. The liquid intumescent is pumped into the cell after having been
degassed by heating it to 50°C. Once the cell was filled, the gap was sealed with hot melt
adhesive. The intumescent material was then gelled in situ by curing the acrylamide. To do
this, the laminate was exposed to UV radiation.
The laminate was tested on an electric furnace, following the fire test curve set out in
British Standard BS 476. The laminate retained its integrity for in excess of 60 minutes, at a
temperature of 925°C. The interlayer formed a hard charred mass with no more than 100%
intumescence. With reference to figure 2, a hybrid fire resistant laminated glazing 10 was made up from two of the applicants PYRODUR fire resistant laminated glasses 12, 14 separated by an interlayer 16 of the same formulation as described with reference to figure 1. Each of the
PYRODUR glasses 12, 14 was 15 mm thick and had a 3 mm interlayer 18, 20 of sodium silicate. The interlayer 16 between the PYRODUR glasses was 3 mm thick and the laminate
10 was 1 m x 1 ra The laminate 10 was tested and accredited with an insulation value (F) of
89 minutes and an integrity value (G) of 105 minutes.

Claims

1. An intumescent material for fire resistant laminate interlayers comprising a metal phosphate, a char forming component and a binding agent.
2. An intumescent material according to claim 1 wherein the metal phosphate comprises a
water soluble glass forming metal phosphate.
3. An intumescent material according to claim 2 wherein the water soluble glass forming
metal phosphate is zinc, aluminium, magnesium, tin, titanium or calcium phosphate.
4. An intumescent material according to any of claims 1 to 3 wherein the char forming
component is water soluble.
5. An intumescent material according to any of claims 1 to 4 wherein the metal phosphate
is a mixed metal phosphate.
6. An intumescent material according to claim 5 wherein the mixed metal phosphate
comprises an alkali metal.
7. An intumescent material according to claim 6 wherein the alkali metal is lithium or
potassium.
8. An intumescent material according to claim 5 wherein the mixed metal phosphate
comprises a multivalent metal.
. An intumescent material according to claim 8 wherein the multivalent metal is aluminium, calcium or magnesium.
10. An intumescent material according to claim 4 wherein the char forming component is
sorbitol.
11. An intumescent material according to any preceding claim wherein the binding agent
comprises a polymer.
12. An intumescent material according to claim 11 wherein the polymer is acrylamide.
13. An intumescent material according to claim 11 or claim 12 wherein the polymer is UV
cured and the binding agent comprises a photoinitiator.
14. An intumescent material according to claim 11 wherein the binding agent comprises a
cross-linking agent.
15. An intumescent material according to claim 14 wherein the cross-linking agent
comprises N,N'-methylenebisacrylamide, cyanuric acid-triglycidyl ether or ethylene
glycol dimethacrylate.
16. An intumescent material according to any preceding claim comprising boric acid.
17. A fire resistant laminated glazing comprising sheet glazing materials separated by an interlayer of intumescent material according to any of claims 1 to 16.
18. A fire resistant laminated glazing according to claim 17 wherein the sheet glazing
materials are coated with an adhesion promoter.
19. A fire resistant laminated glazing according to claim 18 wherein the adhesion promoter
comprises silane.
20. A fire resistant laminated glazing according to claim 17 wherein one or more of the
sheet glazing materials comprises a laminated fire resistant glazing.
21. A method of making a fire resistant laminated glazing according to claim 17 or claim 20
wherein the interlayer material is cast-in-place.
22. A fire resistant laminated glazing substantially as herein described with reference to
figure 1 or figure 2 of the drawings.
PCT/GB1998/002854 1997-09-23 1998-09-21 Fire resistant laminates Ceased WO1999015604A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU91746/98A AU9174698A (en) 1997-09-23 1998-09-21 Fire resistant laminates
AT98944073T ATE263822T1 (en) 1997-09-23 1998-09-21 NON-FLAMMABLE COMPOSITE LAMINATE
EP98944073A EP1025185B1 (en) 1997-09-23 1998-09-21 Fire resistant laminates
DE69823050T DE69823050T2 (en) 1997-09-23 1998-09-21 NON-INCUBATIVE COMPOSITE LUBRICANT

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9720092.7 1997-09-23
GBGB9720092.7A GB9720092D0 (en) 1997-09-23 1997-09-23 Fire resistant laminates

Publications (1)

Publication Number Publication Date
WO1999015604A1 true WO1999015604A1 (en) 1999-04-01

Family

ID=10819434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/002854 Ceased WO1999015604A1 (en) 1997-09-23 1998-09-21 Fire resistant laminates

Country Status (6)

Country Link
EP (1) EP1025185B1 (en)
AT (1) ATE263822T1 (en)
AU (1) AU9174698A (en)
DE (1) DE69823050T2 (en)
GB (1) GB9720092D0 (en)
WO (1) WO1999015604A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008041030A1 (en) * 2006-10-05 2008-04-10 Pilkington Group Limited Fire resistant glazings

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008009484A1 (en) * 2008-02-15 2009-08-20 Schott Ag Fire-resistant glazing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1585125A (en) 1976-07-26 1981-02-25 Bfg Glassgroup Vitreous building elements
US4529467A (en) * 1983-10-25 1985-07-16 Ppg Industries, Inc. Fire protective intumescent mastic composition and method employing same
US4707304A (en) * 1985-12-23 1987-11-17 Monsanto Company Composition for imparting fire-resistance to laminating interlayers
EP0703067A2 (en) * 1994-09-21 1996-03-27 Corning Incorporated Transparent, protective glazing unit

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1585125A (en) 1976-07-26 1981-02-25 Bfg Glassgroup Vitreous building elements
US4529467A (en) * 1983-10-25 1985-07-16 Ppg Industries, Inc. Fire protective intumescent mastic composition and method employing same
US4707304A (en) * 1985-12-23 1987-11-17 Monsanto Company Composition for imparting fire-resistance to laminating interlayers
EP0703067A2 (en) * 1994-09-21 1996-03-27 Corning Incorporated Transparent, protective glazing unit

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008041030A1 (en) * 2006-10-05 2008-04-10 Pilkington Group Limited Fire resistant glazings

Also Published As

Publication number Publication date
AU9174698A (en) 1999-04-12
GB9720092D0 (en) 1997-11-19
EP1025185B1 (en) 2004-04-07
EP1025185A1 (en) 2000-08-09
DE69823050D1 (en) 2004-05-13
ATE263822T1 (en) 2004-04-15
DE69823050T2 (en) 2005-03-31

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