GB2074940A - Method for Making a Laminated Glass Article - Google Patents
Method for Making a Laminated Glass Article Download PDFInfo
- Publication number
- GB2074940A GB2074940A GB8113145A GB8113145A GB2074940A GB 2074940 A GB2074940 A GB 2074940A GB 8113145 A GB8113145 A GB 8113145A GB 8113145 A GB8113145 A GB 8113145A GB 2074940 A GB2074940 A GB 2074940A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyurethane
- sheet
- reaction mixture
- glass
- ether glycol
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000005340 laminated glass Substances 0.000 title claims abstract description 7
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- 239000004814 polyurethane Substances 0.000 claims abstract description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011541 reaction mixture Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001281 polyalkylene Polymers 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 238000010030 laminating Methods 0.000 claims abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 150000002009 diols Chemical class 0.000 abstract description 12
- 239000011229 interlayer Substances 0.000 description 14
- 239000005336 safety glass Substances 0.000 description 11
- -1 poly(butylene adipate) Polymers 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001692 polycarbonate urethane Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 241000209761 Avena Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/1077—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 polyurethane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
A method for making a laminated glass article comprises: a. casting into a sheet mold a single curable polyurethane reaction mixture which comprises: (1) a polyalkylene ether glycol; (2) an organic compound containing at least three active hydrogens per molecule e.g. a triol; (3) an organic compound containing two active hydrogens per molecule e.g. a diol; and (4) an aromatic diisocyanate; b. polymerizing the reaction mixture to form a self-supporting polyurethane sheet; c. removing the self-supporting polyurethane sheet from said mold; d. laminating said polyurethane sheet to a sheet of glass; and e. thermosetting the polyurethane. s
Description
SPECIFICATION
Method for Making a Laminated Glass Article
The invention relates to a method for making a laminated glass article.
Safety glass is a well-known term for a glass-plastic laminate designed to reduce the severity of lacerative injuries resulting from glass breakage upon impact. A polymeric film is laminated to a glass shear to that upon impact sufficient to break the glass, the film adheres to the glass fragments, minimizing their dispersion. To be useful as safety glass a laminate must have (1) high energy absorption to minimize concussive injuries on impact, (2) high shear and tear strength to prevent rupture of the film by glass fragments, (3) sufficient adhesion between the layers to minimize the dispersion of glass fragments to reduce the potential for lacerative injuries and (4) high optical quality.
Commercial safety glass, particuiarly for automobile windshields, is typically a trilayer laminate comprising two sheets of glass with an intermediate layer of plasticized polyvinyl butyral. However, there is a trend toward substituting other polymeric interlayer materials for polyvinyl butyral.
In U.S. Patent No. 3,509,015, Wismer et al describe a safety glass laminate with a cast-andcured-in-place polyurethane interlayer prepared by the reaction of an organic diisocyanate and a curing agent with a prepolymer formed by the reaction of an organic diisocyanate and a poly(oxypolymethylene)glycol. Suitable curing agents include poiyols, especially those with at least three hydroxyl groups, and preferably in conjunction with a diol, and polyamines, preferably utilized with a polyol. The reaction mixture is heated, degassed, placed in a casting cell and cured. Impact resistance of the resulting laminate, measured as the height from which a 1/2 pound steel ball may be dropped with the laminate withstanding the impact, is acceptable.
In U.S. Patent No. 3,620,905, Ahramjian discloses colorless, optically clear, thermoplastic polyurethanes suitable for use in safety laminates prepared from diisocyanate-dicyclohexylmethane, a polyether or polyester glycol, and a diol having a molecular weight less than 250. The polyurethanes may be prepared by one-shot, quasi-prepolymer, or conventional prepolymer procedures, all of which are well-known in the art.
U.S. Patent No. 3,764,457 to Chang et al discloses safety glass laminates comprising a thermoplastic polycarbonate urethane formed from a cycloaliphatic diisocyanate, a monomeric aliphatic diol, and an aliphatic polycarbonate such as polyoxyethylenecarbonate glycol.
In U.S. Patent No. 3,900,446, McClung et al disclose laminated glazing units containing polyurethane interlayers prepared from an isomeric mixture of 4,4' - methylene - bis (cyclohexylisocyanate), a polyester having a melting point above 420C which is the condensation product of a dicarboxylic acid and a dihydric compound, and an alpha-omega diol having from 2 to 10 carbon atoms. The two-step method for making the polyurethanes involves prepolymer preparation and polymer preparation.
U.S. Patent No. 3,900,655 to Wolgemuth et al describes laminated safety glass made with a thermoplastic interlayer which is the polyurethane reaction product of a cyclic nitrile carbonate and at least one hydroxyl-containing compound such as a polyalkylene ether or polyester glycol or a diol having primary or secondary hydroxyl groups and a molecular weight less than 250. Such polyurethane elastomers can be prepared by a variety of methods well-known in the art such as one-shot, quasiprepolymer or full prepolymer procedures.
In U.S. Patent No. 3,931,113, Seeger et al disclose polyester urethanes having superior properties for use in safety glass windshields which are formed from a cycloaliphatic diisocyanate, a low molecular weight diol, and a hydroxy terminated polyester of polycaprolactone, poly(butylene adipate), poly(butylene azelate) or mixtures thereof. These urethanes are preferably prepared by the one-step bulk polymerization method which provides a flexible polymer having a random distribution of components.
In U.S. Patent No.4,024,113, Ammons discloses energy-absorbing safety glass laminates comprising a polycarbonate urethane formed from a cycloaliphatic diisocyanate, a low molecular weight diol, and a special polycarbonate diol synthesized from a mixture of linear aliphatic and cycloaliphatic diols. The polycarbonate urethanes can be prepared either by the "one-shot" bulk polymerization method or by the prepolymer method.
U.S. Patent No. 4,035,548 to Chang et al discloses safety glass laminates containing energyabsorbing interlayers made from a poly(lactone-urethanef in which the molecular weight and structure of the lactone moiety are carefully controlled in order to obtain optimum energy-absorbing and optical properties. The "one-shot" method of polymerization is preferred to the prepolymer method because of its simplicity and the lower initial viscosity of the reactants.
Many of the references reiating to transparent, energy-absorbing polyurethanes for interlayers in safety glass laminates teach that cycloaliphatic diisocyanates are preferred, particularly 4,4' methylene - bis - (cyclohexylisocyanate), because of their contribution to colorlessness, transparency and impact resistance. Unfortunately, these dissocyanates are rather expensive. Mixtures with minor amounts of less expensive diisocyanates, such as toluene diisocyanate (TDI) or diphenyl methane diisocyanate (MDI) and other aromatic diisocyanates, are usable only if the amount of aromatic diisocyanate employed is carefully controlled to avoid yellowing, translucence and reduced impact resistance.
According to the present invention a method is provided for making a laminated glass article comprising the steps of:
a. casting into a sheet mold a single curable polyurethane reaction mixture which comprises:
(1) a polyalkylene ether glycol;
(2) an organic compound containing at least three active hydrogens per molecule;
(3) an organic compound containing two active hydrogens per molecule; and
(4) an aromatic diisocyanate;
b. polymerizing the reaction mixture to form a self-supporting polyurethane sheet;
c. removing the self-supporting polyurethane sheet from said mold;
d. laminating said polyurethane sheet to a sheet of glass; and
e. thermosetting the polyurethane.
The polyurethane composition used in the present invention offers raw material cost advantages, simple processing, and better impact resistance than typical commercially available high-impact vinal interlayers.
The polyurethane interlayer of the present invention is prepared by a one-step bulk polymerization process, and offset casting, i.e. forming the interlayer sheet by casting the polymerization reaction mixture into a cell, forming a sheet of polymer, and removing the sheet from the cell for subsequent lamination to a glass sheet. The offset casting technique is possible because the polyurethane composition of the present invention is readily handleable in sheet form substantially before a full cure has been achieved. The partially cured sheets may be laminated shortly after removal from the casting cells or may be stored for future lamination.
In accordance with a preferred embodiment of the invention a colorless liquid reaction mixture is prepared comprising an aromatic diisocyanate, a low molecular weight triol, e.g. a monomeric aliphatic triol, a monomeric aliphatic diol and a polyalkylene ether glycol of the general formula:
wherein n is preferably from about 3 to about 6 and m preferably is such that the molecular weight of the polyalkylene ether glycol is from about 400 to about 2000. Polytetramethylene ether glycol having a molecular weight of about 1000 is preferred.
The low molecular weight triol is included to provide branching sites in the polyurethane structure. Preferred triols include monomeric aliphatic triols. The molecular weight and proportion of triol in the reaction mixture is determined in accordance with the desired molecular weight between branch points in the polyurethane to give optimum properties. A particularly preferred triol is trimethylolpropane. Other trifunctional compounds e.g. triamines may be used to provide for branching in the polyurethane.
Aliphatic monomeric diols useful as chain extenders for the polyurethane according to the present invention preferably have the general formula: HO(CH2)nOH wherein n is from about 2 to about 10 and preferably from about 4 to about 6. Other aliphatic diols including cycloaliphatic, substituted, and secondary alcohols may also be used but are less preferred, as are difunctional chain extenders other than diols, e.g. diamines. A preferred chain extender is 1,4butanediol.
Aromatic diisocyanates useful in preparing polyurethanes are well-known in the art. A preferred aromatic diisocyanate for preparing polyurethanes according to the present invention is toluene diisocyanate. A commercially available mixture of 65 percent 2,4-toluene diisocyanate and 35 percent 2,6-toluene diisocyanate is preferred over the 80/20 isomer mixture, since the higher proportion of 2,6-toluene diisocyanate appears to improve the performance of the polyurethane at low temperatures. The proportion of diisocyanate in the reaction mixture is preferably approximately equivalent to the total of polyalkylene ether glycol, triol branching agent and diol chain extender.
However, a stoichiometric imbalance up to about 5 percent excess isocyanato groups does not seriously degrade the quality of the polyurethane.
The above materials are blended together to form a colorless, transparent, single-phase, low viscosity liquid reaction mixture at room temperature. Preferably, the polyalkylene ether glycol, polycaprolactone triol and monomeric aliphatic diol are heated slowly to avoid turbulence or bubbling in a vacuum and then placed in a reaction kettle under dry nitrogen. The toluene diisocyanate is added to the above mixture while stirring. The final mixture, preferably containing adhesion control agents as shown in U.S. Patent No. 3,900,686 is degassed and cast into sheet molds wherein the reaction mixture polymerizes to form polyurethane interlayer sheets. Preferably the reaction proceeds to a degree of polymerization of at least about 50 before the polyurethane interlayer sheets are removed from the casting cells.
The polyurethane interlayers, which preferably have a number average degree of polymerization between about 50 and about 125, are subsequently laminated to glass sheets, preferably in accordance with U.S. Patent No. 3,808,077. The polyurethane achieves a full cure during a typical autoclave lamination cycle, e.g. a temperature of about 3000F (about 1 490C) and a pressure of about 200 pounds per square inch for about 45 minutes. Alternatively, the polyurethane may be substantially cured prior to lamination since it has been found, unexpectedly since the polyurethane is crosslinked, that a fully cured interlayer can be laminated to glass to yield a laminate of acceptable optical quality.
The present invention will be further understood from the description of a specific example which follows.
Example I
A polytetramethylene ether glycol having a molecular weight of about 1000, which is a semisolid at room temperature, is heated. The polytetramethylene ether glycol, available as polymeg 1000 from the Quaker Oats Company, becomes completely liquid at about 1000F (about 380C) and remains liquid for a long time at room temperature, and indefinitely in a mixture of trimethylolpropane and butane diol. A mixture containing 0.278 equivalents of polytetramethylene ether glycol, 0.617 equivalents of 1,4-butane diole and 0.105 equivalents of trimethylolpropane is placed in a reaction kettle under vacuum with overhead stirring. With the kettle contents at about 860F (about 300C) the vacuum is broken with dry nitrogen and 1.000 equivalent of toluene diisocyanate is added.The toluene diisocyanate is the preferred isomer mixture containing 65 percent 2,4-toluene diisocyanate and 35 percent 2,6-toluene diisocyanate, available as Hylene TM 65 from duPont. THe reaction kettle is again evacuated to degas the reaction mixture. As quickly as possible after the vacuum is broken with dry nitrogen, the reaction mixture is cast into 14 by 14 inch (about 35.6 centimeter square) cells made from Teflons (polytetrafluoroethylene) coated glass sheets spaced at 30 mils (about 0.76 millimeter).
After 2 hours in the cells at a temperature 2700F (about 1 320C), the polyurethane sheets are cured to an easily handleable stage and can be removed from the cells for subsequent lamination. The polymer has a urethane content of 23 percent and a molecular weight between branch points of about 4850.
The impact resistance of this polyurethane is compared with the impact resistance of polyvinyl butyral in Table I.
Table I
Mean Penetration Velocities (mph) for Safety Glass Laminates
Temperature
Interlayer OOF 700F 1200F
Polyurethane (Example I) 23 27.6 17
Polyvinyl butyral (high impact vinal) 17 24 12
The above example is offered only to illustrate the present invention. While the polyurethane described above generally has an essentially stoichiometric OH/NCO ratio, a urethane content between about 1 5 and 25 percent, and a molecular weight between branch points within the range of 4000 to 8000, other polyurethanes having the requisite properties could of course be used in its place.
Claims (11)
1. A method for making a laminated glass article comprising the steps of:
a. casting into a sheet mold a single curable polyurethane reaction mixture which comprises:
(1) a polyalkylene ether glycol;
(2) an organic compound containing at least three active hydrogens per molecule;
(3) an organic compound containing two active hydrogens per molecule; and
(4) an aromatic diisocyanate;
b. polymerizing the reaction mixture to form a self-supporting polyurethane sheet;
c. removing the self-supporting polyurethane sheet from said mold;
d. laminating said polyurethane sheet to a sheet of glass; and
e. thermosetting the polyurethane.
2. A method according to claim 1, wherein the reaction mixture comprises:
a. a polyalkylene ether glycol having from 3 to 6 carbon atoms per alkylene moiety;
b. a low molecular weight triol;
c. a monomeric aliphatic diol; and
d. toluene diisocyanate.
3. A method according to claim 2, wherein the reaction mixture comprises:
a. a polytetramethylene ether glycol having a molecular weight from about 400 to about 2000;
b. a monomeric aliphatic triol;
c. a monomeric aliphatic diol having from 4 to 6 carbon atoms; and
d. an isomeric mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.
4. A method according to claim 3, wherein the reaction mixture comprises:
a. a polytetramethylene ether glycol having a molecular weight of about 1000;
b. trimethylolpropane;
c. 1,4-butane diol; and
d. an isomeric mixture of 2,4-toluene diisocyanate and at least about 35 percent 2,6-toluene diisocyanate.
5. A method according to any of claims 1 to 4 wherein the proportion of diisocyanate is approximately equal to the total of the polyalkylene ether glycol, the compound containing at least three active hydrogens per molecule and the compound containing two active hydrogens per molecule.
6. A method according to any of claims 1 to 5 wherein the polyurethane has a number average degree of polymerization of about 50 to about 125.
7. A method according to any of claims 1 to 6 wherein the step of laminating the self-supporting polyurethane sheet to a sheet of glass is performed prior to thermosetting the polyurethane.
8. A method according to any of claims 1 to 6 wherein the step of laminating the self-supporting polyurethane sheet to a sheet of glass is performed subsequent to thermosetting the polyurethane.
9. A method according to any of claims 1 to 8 wherein the polyurethane sheet is laminated between glass sheets at a temperature of about 3000F (about 1 49 OC) and a pressure of about 200 pounds per square inch.
10. A method according to any of claims 1 to 9 wherein the thickness of the polyurethane sheet is from 20 to 60 mils (about 0.5 to 1.5 millimeters).
11. A laminated glass article prepared according to a method as claimed in any of the preceding claims. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14507480A | 1980-04-30 | 1980-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2074940A true GB2074940A (en) | 1981-11-11 |
| GB2074940B GB2074940B (en) | 1984-03-28 |
Family
ID=22511500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8113145A Expired GB2074940B (en) | 1980-04-30 | 1981-04-29 | Method for making a laminated glass article |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS56164042A (en) |
| BE (1) | BE888612A (en) |
| CA (1) | CA1174577A (en) |
| DE (1) | DE3112541A1 (en) |
| FR (1) | FR2481690A1 (en) |
| GB (1) | GB2074940B (en) |
| IT (1) | IT1137546B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131523A2 (en) * | 1983-07-11 | 1985-01-16 | Saint Gobain Vitrage International | Safety glass laminates |
| FR2548956A1 (en) * | 1983-07-11 | 1985-01-18 | Saint Gobain Vitrage | SHEET OF TRANSPARENT PLASTIC MATERIAL OF HIGH OPTICAL QUALITY |
| FR2549036A1 (en) * | 1983-07-11 | 1985-01-18 | Saint Gobain Vitrage | SECURITY SHEET GLAZING |
| US4732725A (en) * | 1985-01-15 | 1988-03-22 | Saint-Gobain Vitrage | Process and device for the production of a safety pane |
| GB2211194A (en) * | 1987-12-17 | 1989-06-28 | Gore & Ass | Two component polyurethane composition for casting |
| EP0607794A1 (en) * | 1993-01-20 | 1994-07-27 | BASF Aktiengesellschaft | Non-tacky, high elastic mono- and multifilament polyurethane yarns, process for their production, their uses and partially cross-linked thermoplastic polyurethane therefor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4592947A (en) * | 1984-06-04 | 1986-06-03 | Sierracin Corporation | Low temperature laminatable polyurethane |
| JPS61177241A (en) * | 1985-02-04 | 1986-08-08 | 旭硝子株式会社 | Laminated safety glass and manufacture thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE610315A (en) * | 1965-02-24 | 1900-01-01 | ||
| US3620905A (en) * | 1969-10-21 | 1971-11-16 | Du Pont | Optically clear thermoplastic polyurethanes |
| GB1263880A (en) * | 1970-09-17 | 1972-02-16 | Du Pont | Improvements in and relating to safety glass |
| BE787039A (en) * | 1971-08-02 | 1973-02-01 | Ppg Industries Inc | TRANSPARENT SHEET PRODUCTS, WITH GOOD IMPACT RESISTANCE, IN POLYETHER-URETHANE |
| BE788868A (en) * | 1971-09-16 | 1973-03-15 | Ppg Industries Inc | METHOD OF MANUFACTURING A SAFETY SHEET GLASS |
| BE794206A (en) * | 1972-01-19 | 1973-07-18 | Monsanto Co | POLYURETHANE SPACER FOR LAMINATED SAFETY GLASS |
| DE2240580A1 (en) * | 1972-08-18 | 1974-02-28 | Ppg Industries Inc | Laminated windscreen with a polyurethane layer - to protect it against shatt-ering on impact, for aircraft and armoured vehicles |
| US4085092A (en) * | 1974-05-30 | 1978-04-18 | Ppg Industries, Inc. | Transparent, optically clear poly(lactone-urethane) interlayers for laminated safety glass |
| US4035548A (en) * | 1974-05-30 | 1977-07-12 | Ppg Industries, Inc. | Laminated articles prepared from transparent, non-blooming poly(lactone-urethane) interlayers |
-
1981
- 1981-02-10 CA CA000370515A patent/CA1174577A/en not_active Expired
- 1981-03-03 JP JP3110181A patent/JPS56164042A/en active Granted
- 1981-03-18 FR FR8105395A patent/FR2481690A1/en active Granted
- 1981-03-30 DE DE19813112541 patent/DE3112541A1/en not_active Withdrawn
- 1981-04-22 IT IT21327/81A patent/IT1137546B/en active
- 1981-04-29 GB GB8113145A patent/GB2074940B/en not_active Expired
- 1981-04-29 BE BE0/204638A patent/BE888612A/en not_active IP Right Cessation
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0131523A2 (en) * | 1983-07-11 | 1985-01-16 | Saint Gobain Vitrage International | Safety glass laminates |
| FR2549037A1 (en) * | 1983-07-11 | 1985-01-18 | Saint Gobain Vitrage | SECURITY SHEET GLAZING |
| FR2548956A1 (en) * | 1983-07-11 | 1985-01-18 | Saint Gobain Vitrage | SHEET OF TRANSPARENT PLASTIC MATERIAL OF HIGH OPTICAL QUALITY |
| FR2549036A1 (en) * | 1983-07-11 | 1985-01-18 | Saint Gobain Vitrage | SECURITY SHEET GLAZING |
| EP0132198A1 (en) * | 1983-07-11 | 1985-01-23 | Saint Gobain Vitrage International | Safety glass laminates |
| EP0133090A1 (en) * | 1983-07-11 | 1985-02-13 | Saint Gobain Vitrage International | High optical quality transparent plastics film |
| EP0131523A3 (en) * | 1983-07-11 | 1985-02-20 | Saint-Gobain Vitrage | Safety glass laminates |
| US4732725A (en) * | 1985-01-15 | 1988-03-22 | Saint-Gobain Vitrage | Process and device for the production of a safety pane |
| GB2211194A (en) * | 1987-12-17 | 1989-06-28 | Gore & Ass | Two component polyurethane composition for casting |
| GB2211194B (en) * | 1987-12-17 | 1991-01-09 | Gore & Ass | Two component polyurethane composition for casting |
| EP0607794A1 (en) * | 1993-01-20 | 1994-07-27 | BASF Aktiengesellschaft | Non-tacky, high elastic mono- and multifilament polyurethane yarns, process for their production, their uses and partially cross-linked thermoplastic polyurethane therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0323495B2 (en) | 1991-03-29 |
| FR2481690B1 (en) | 1984-12-21 |
| FR2481690A1 (en) | 1981-11-06 |
| CA1174577A (en) | 1984-09-18 |
| IT8121327A0 (en) | 1981-04-22 |
| IT1137546B (en) | 1986-09-10 |
| JPS56164042A (en) | 1981-12-16 |
| GB2074940B (en) | 1984-03-28 |
| DE3112541A1 (en) | 1982-01-28 |
| BE888612A (en) | 1981-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4241140A (en) | Laminated safety glass with polyurethane film | |
| US4085092A (en) | Transparent, optically clear poly(lactone-urethane) interlayers for laminated safety glass | |
| US4160853A (en) | Catalyst for making polycarbonate diols for use in polycarbonate urethanes | |
| US4103070A (en) | Safety glass laminates with aliphatic/cycloaliphatic polycarbonate urethanes | |
| US3931113A (en) | Impact-resistant thermoplastic polyester urethanes | |
| US4139674A (en) | Novel transparent polyurethane polyureas for lamination of glazing materials | |
| US3764457A (en) | Transparent impact resistant poly(carbonate-urethane)laminates | |
| US3965057A (en) | Adhesion control for safety glass laminates via polyurethane composition | |
| EP0285859B1 (en) | Reaction curable composition and products comprising a cured product of the composition | |
| US4010311A (en) | Impact-resistant glass-polyesterurethane laminates | |
| EP0781792B1 (en) | Cross-linked polyurethane resin sheet and laminated product employing it | |
| FI77601C (en) | Multi-layer safety glass. | |
| EP0839643A1 (en) | Improved aircraft transparency | |
| US4666758A (en) | Low temperature laminatable polyurethane | |
| US3900686A (en) | Adhesion control for safety glass laminates | |
| US4035548A (en) | Laminated articles prepared from transparent, non-blooming poly(lactone-urethane) interlayers | |
| EP0295596B1 (en) | Low modulus interlayer | |
| US3900655A (en) | Laminated safety glass and/or plastic | |
| EP0098961B1 (en) | Laminated safety glass | |
| GB2074940A (en) | Method for Making a Laminated Glass Article | |
| US4174240A (en) | Novel transparent polyurethane polyureas for lamination of glazing materials | |
| US4062887A (en) | Transparent, optically clear poly(lactone-urethane) interlayers for laminated safety glass | |
| FI77253C (en) | For its optical quality, high quality transparent plastic film. | |
| US4166149A (en) | Novel transparent polyurethane polyureas for lamination of glazing materials | |
| US4663417A (en) | Low temperature laminatable polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |