WO2009010423A1 - Multicomponent thiol-ene compositions for laminate materials - Google Patents

Multicomponent thiol-ene compositions for laminate materials Download PDF

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Publication number
WO2009010423A1
WO2009010423A1 PCT/EP2008/058856 EP2008058856W WO2009010423A1 WO 2009010423 A1 WO2009010423 A1 WO 2009010423A1 EP 2008058856 W EP2008058856 W EP 2008058856W WO 2009010423 A1 WO2009010423 A1 WO 2009010423A1
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WO
WIPO (PCT)
Prior art keywords
composition
thiol
laminate
carbon
glass
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Application number
PCT/EP2008/058856
Other languages
French (fr)
Inventor
Christopher Wayne Miller
Jonathan Shaw
Original Assignee
Cytec Surface Specialties, S.A.
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Publication date
Application filed by Cytec Surface Specialties, S.A. filed Critical Cytec Surface Specialties, S.A.
Publication of WO2009010423A1 publication Critical patent/WO2009010423A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/1055Layered 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
    • B32B17/10706Layered 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02Polythioethers
    • C08G75/04Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/10009Layered 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 number, the constitution or treatment of glass sheets
    • B32B17/10036Layered 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 number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered 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
    • B32B17/10Layered 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
    • B32B17/10005Layered 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
    • B32B17/10807Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10908Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form
    • B32B17/10917Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form between two pre-positioned glass layers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/12Polythioether-ethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/02Polythioethers; Polythioether-ethers

Definitions

  • This invention relates to the use of thiol-ene based radiation curable formulations for laminate applications. More specifically, this invention relates to the use of binary, ternary, and/or multi-component chemical systems comprising thiol-enes as radiation-curable formulations.
  • the thiol-ene comprising formulations are suitable for use as the polymeric interlayers for glass laminate applications including, but not limited to, typical applications such as hurricane windows, doors, and curtainwalls; acoustical dampening windows, doors and curtainwalls; ballistic resistant glass, and safety glass.
  • glass is used to designate objects made of glass or of glass appearance. Glass appearance objects such as polycarbonate panels can be used but are less preferred because of their poor behavior in case of fire.
  • the glass objects can be made of ordinary float glass, whether heat treated or not, or of special glass such as borosilicate glass.
  • Laminating protects people from splinters in case of glass breaking, and it also provides additional properties to the glazing.
  • laminated glass is industrially produced either by a polymer film system, or by liquid cast-in-place resin polymerized in situ.
  • the film lamination technology often comprises the insertion of an organic, polymeric film between two glass panes, and bonding them at an elevated temperature under an elevated pressure. Different materials can be used, for example polyvinylbutyral (PVB) as the organic film.
  • PVB polyvinylbutyral
  • the foil is positioned on a glass pane, and a second pane positioned upon the film. The so- formed sandwich has to be passed through an oven, to weaken the film and create a preliminary adhesion.
  • the sandwich then undergoes a batch-wise heating and pressure cycle, in order to bring the film in close contact with the glass and to develop adhesion onto the glass surfaces.
  • This operation is done in an autoclave, at 120 to 150°C and with increased pressure, typically between 10 to 17 kg/cm 3 , in order to bring the film in close contact with the glass and to develop adhesion onto the glass surfaces.
  • Residence time in the autoclave at the required temperature is 30 to 45 minutes, longer for bent or multiple laminates.
  • the total residence time, including heating and subsequent cooling is about 2 hours.
  • the PVB film lamination process is described in 'Encyclopedia of Chemical Technology' - KIRK-OTHMER - 4 th edition, Volume 14, page 1059 - 1074.
  • the main restrictions to this system are the high investment costs, while also the size of the autoclave can be restrictive in the case of larger panels and bent glazing.
  • the film lamination is a batch-wise process and requires a high-energy input. A large size apparatus is required, and the total operation time is long. Also, it is more difficult to apply on certain glass surfaces, e.g. toughened glass that is not completely flat. In such situations, the film is not elastic enough to adapt to the uneven surface. Also for bent glass it is more difficult to apply, when the curving of both glass panes would not be identical.
  • a possible solution to compensate for glass surface unevenness is to apply more film layers, 4 or 6 or more layers instead of the 1 or 2 layers as typically used. However, in this way significantly more organic combustible material is incorporated.
  • An alternative lamination technique is by the use of liquid resin, cured in situ.
  • Two glass panes are bound together by a double-sided adhesive tape that also functions as a spacer.
  • the cavity between the two sheets is then filled up with a liquid resin.
  • the envelope is positioned at an angle of at least 60° during filling.
  • the filled sandwich is slowly returned to horizontal, allowing the liquid to flow throughout the entire cavity.
  • the opening is sealed with hot melt material. Any entrapped air is then removed with a small syringe.
  • the liquid resin is then polymerized, the so-called "curing" step. Curing can be accomplished either by radiation, or chemically by appropriate catalysts and accelerators.
  • Polymerization chemically changes the liquid resin into a solid polymeric interlayer.
  • the equipment needed for resin lamination may be as little as one or two tilting tables to allow the assembly of the envelope, a dosing pump and, in case of radiation cure, a radiation source.
  • a strong technical advantage of the liquid resin system is that the cavity between the two glasses is completely filled up with the liquid resin, thus the influence of the shape or roughness of the glass surfaces on the bonding with the resin interlayer is significantly reduced.
  • adhesion promoters most often appropriate silanes, allows for a chemical bond to be created between the silanol (- Si - OH) functions on the glass surface, and the interlayer.
  • a chemical bond is stronger than simple physical adhesion, and is typically more stable over time.
  • liquid resins used for glass lamination can be of different kinds, for example polyester, polyurethane, silicone or, most often, acrylic. The latter is preferred for its high resistance against outdoor weathering conditions, i.e. UV radiation, heat and humidity.
  • An example of a polyester-based liquid resin system, for manufacturing acoustic glazing is described in French patent 1367977, "Acoustic Laminates", by Saint-Gobain Industries of France.
  • An example of a urethane acrylate-based liquid resin system, for manufacturing clear glazing is given in EP0108631, by DeltaGlass S.A.
  • Curing of the liquid resin can be initiated directly by inclusion of one or more catalysts, accelerants, or highly reactive components in the liquid resin mixture, or indirectly by heating, irradiation with UV or visible electromagnetic radiation, or exposure to electron-beam radiation.
  • one or more catalysts and an accelerator are added to the base resin, this is the so-called multi-component system.
  • Each of the above mentioned chemical types of resins could be multi-component.
  • the reaction starts after the blending of the catalyst(s) and the accelerator with the resin, after a period of time that depends on the resin composition, the concentrations of catalyst(s) and accelerator, and the temperature of the substrates and the environment.
  • IR radiation sources can be applied to increase reaction speed. Polymerization of radiation curable resins is initiated by irradiation of photosensitive components in the resin formulation with electromagnetic radiation typically in the ultraviolet and/or visible spectral regions, or by exposure of the resin to electron beam radiation. Most typically, in the case of radiation cure, the radiation source comprises one or more fluorescent bulbs, arc lamps, light emitting diodes (LEDs), or microwave lamps in an assembly that when energized irradiates the filled laminate with electromagnetic radiation primarily in the ultraviolet and visible spectral range. In some cases, the radiation source comprises a device that irradiates the filled laminate with a beam of electrons to initiate polymerization. UV curable liquid resin systems are described in i.e. EP0108631.
  • UV resins for glass laminates are initiated by the action of UV light of low intensity with an exposure time of typically 15 to 30 minutes.
  • (Meth)acrylate -based UV curable polymer precursors for glass laminates typically contain:
  • a reactive oligomer i.e. a (meth)acrylated urethane oligomer
  • reactive diluents i.e. (meth)acrylated monomers
  • the monomers can be one or more of the following: 2-ethylhexyl acrylate, 1,6- hexanediol diacrylate, n- hexyl acrylate, n-hexyl methacrylate, 2 -hydroxy ethyl acrylate, 2- hydroxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, n-lauryl acrylate, n-lauryl methacrylate, methyl methacrylate (MAM), butyl acrylate, acrylic acid, methacrylic acid, isobutyl acrylate, cyclohexyl acrylate, 2-butoxyethyl acrylate, cyclohexyl acrylate, N-vinyl pyrrolidone, and the like, with he preferred ones in the field of glass laminates being mono -functional monomers that are low in viscosity and
  • Laminated glass is used in the automotive and the building industry. Its functions can be manifold, although typically the main objectives are sound insulation and safety and security performance. Glazing in the building industry has several functions, more or less dependent on its application:
  • film or resin laminated glass fulfils most of these functions, in particular film or resin laminated glass may have very good properties as to sound reduction and impact resistance.
  • multi-component formulations are pre- mixed or mixed in-situ and injected into a gap between glazing layers (lites) (preferably glass to glass, but can be glass to polymer, or polymer to polymer, etc.), and subsequently polymerized through irradiation (preferably UV-A type irradiation) to form a polymeric interlayer between the lites of glass (or polymer).
  • lites preferably glass to glass, but can be glass to polymer, or polymer to polymer, etc.
  • irradiation preferably UV-A type irradiation
  • the polymerized interlayer serves to adhere one lite to the other and also serves to dissipate energy under high shear (i.e. from ballistic impact), while also providing rigidity under low shear deformation (e.g. window pressure cycling) of the laminate structure.
  • the interlayer prevents release of dangerously small and ballistic shards of glass (or polymer) upon impact of a projectile or other breakage of the glass.
  • the present invention is directed to a laminate composition, comprising (1) one or more thiol-functional compounds; (2) one or more oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds; and (3) one or more monomeric compounds containing one or more carbon-carbon double bonds or triple bonds.
  • the present invention is directed to a method of producing a glass laminate, comprising the steps of (1) providing at least two juxtaposed panes of glass and/or polymer having a gap between them; (2) applying the above laminate composition into the gap; and (3) curing the composition.
  • the present invention is directed to a glass laminate comprising at least two juxtaposed panes of glass having a gap between them, the gap filled with the above composition in a cured state.
  • the present invention is also directed to methods of producing glass and/or polymer laminates using the above composition, glass and/or polymer laminates made from the method, and machines or articles of manufacture incorporating the above laminates.
  • UVEKOL R type radiation-curable materials for manufacturing laminated glass windows offers many advantages including a fast curing process that is not temperature dependent, a one-component product that requires no mixing, and solvent-free materials that facilitate easy disposal and clean-up.
  • certain parameters of these systems are less advantageous. For example, viscoelastic properties, impact dissipation properties, and rigidity of the formed products are not always suitable for certain applications.
  • compositions of the present invention overcome these limitations.
  • Specific advantages of thiol-ene component chemical systems disclosed in the present invention include tailored viscoelastic properties of the cured interlay er that may provide for a significantly higher level of energy absorption and dissipation by the interlayer under ballistic impact as well as tailored rigidity under low-shear deformation of the laminate.
  • This chemistry demonstrates a step-change in performance relative to the existing UVEKOL ® -type formulations.
  • the thiol-ene formulations of the present invention also provide advantages for reduced photodegradation, reduced handling hazards relative to the commercial (meth)acrylate formulations, improved cure times, resistance to oxygen inhibition, and capability for curing very thick segments.
  • the technical basis of this step-change in application performance is tailoring of the rheological characteristics of the cured interlayer, for example by manipulation of the temperature and width of the glass transition temperature of the polymer interlayer through morphological design.
  • the morphological design is achieved by intelligent selection of thiol component as well as one or more types of "ene” components, wherein variables are optimized including: (1) reactivity ratios of the enes for radical copolymerization relative to homopolymerization relative to Michael addition relative to thiol-ene step-growth polymerization (2) structural features of the "ene” such as aromaticity, flexibility, molecular weight, ene functionality (i.e.
  • the present invention is directed to a laminate composition, comprising: (1) one or more thiol-functional compounds, (2) one or more oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds (the "ene” component); and (3) one or more monomeric compounds containing or more carbon- carbon double bonds or triple bonds.
  • a laminate composition comprising: (1) one or more thiol-functional compounds, (2) one or more oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds (the "ene” component); and (3) one or more monomeric compounds containing or more carbon- carbon double bonds or triple bonds.
  • the thiol-functional component of the invention may be any poly-thiol functional molecule, oligomer, or polymer. Thiol functionality of 3 or more thiol groups per molecule is preferred. More than one thiol functional compound may be used in any particular formulation of this invention. Examples of preferred thiols are shown in Table 1 and Figure 1.
  • the amounts of the thiol-functional component of the invention preferably ranges from 0.5 to 75wt%, more preferably from 5 to 60 wt%, and most preferably from 20 to 50 wt%., all based on the total weight of the composition.
  • the ene components of the invention may be any unsaturated compound capable of undergoing free-radical homopolymerization, copolymerization, or polymerization with a thiol through Michael addition and/or free-radical step-growth reactions including vinyl ethers, vinyl esters, allyl esters, allyl ethers, allyl amines, vinyl amines, vinyl amides, esters and amides of (meth)acrylic acid, esters of maleic and fumaric acids, maleimides, et al.
  • One preferred class of enes is (meth)acrylate functional compounds including (meth)acrylated monomers, oligomers, and polymers.
  • the ene component of the formulations of the invention(s) may be comprised of one or more enes of similar or dissimilar types.
  • Preferred embodiments of the ene components of the present invention(s) include aliphatic urethane (meth)acrylates (ex.
  • the ene component of the formulation may also contain one or more oligomeric, polymeric, or monomeric enes that do not readily homopolymerize through free-radical chemical processes such as vinyl ethers, N-vinylamides, et al. Norbornenes are also a preferred type of ene in the invention.
  • Enes may be reacted with other enes and/or with thiols to produce poly-enes of various useful structures.
  • cycloaddition reactions can be utilized to prepare norbornenes through, for example, [4+2] cycloaddition of cyclopentadiene to (meth)acrylates.
  • enes with thio-ether functionality may be prepared through Michael addition of poly-thiols with a stoichiometric excess of di or poly-enes such as (meth)acrylates, vinyl acrylate, et al. Selected enes of the invention are listed in Table 2 and Figure 2. Table 2. Examples of Ene Compounds
  • the molecular weight of the ene component is preferably 500 g/mol to 20,000 g/mol, and the viscosity is preferably 1000 cP to 10 6 cP (at 25°C).
  • the amounts of the ene component of the invention preferably ranges from 15 to 95 wt%, more preferably from 25 to 75 wt%, and most preferably from 35 to 60 wt%., based on the total weight of the composition. Viscosity being a prime factor in the practical utility of the compositions of the invention, preferred embodiments of the invention also include diluting monomers to control formulation viscosity.
  • diluting monomers comprise low molecular weight ethylenically unsaturated compounds with molecular weight lower than about 500g/mole and viscosity lower than about 50OcP at 25°C, and may include for example: vinyl ethers, vinyl esters, allyl esters, allyl ethers, allyl amines, vinyl amines, vinyl amides, esters and amides of (meth)acrylic acid, esters of maleic and fumaric acids, maleimides, and the like.
  • Preferred diluting monomers include, for example: HDODA, BDODA, PETA, TMPTA, di-TMPTA, TRPGDA, NPGDA, DPGDA, IBOA, ODA-N, EBECRYL® 1040, EBECRYL® 1039, OTA-480, DPHA, acrylate of Cardura E-IOP, et al. as well as the corresponding methacrylates.
  • (Meth)acrylic acid is also a preferred diluting monomer of the invention and may functions as an ene and/or as an adhesion promoter.
  • the molecular weight of the diluting monomeric component is preferably 500 g/mol or less, and the viscosity is preferably 1000 cP or less (at 25°C).
  • the amounts of the diluting monomeric component of the invention ranges from 5 to 90 wt%, more preferably from 20 to 70 wt%, and most preferably from 35 to 55 wt%., based on the total weight of the composition.
  • hybrid and/or dual-cure formulations may be utilized wherein one or more cationically (glycidyl ethers, cycloaliphatic epoxides, etc.), or anionically polymerizable compounds, or compounds that can be polymerized via free-radical and cationic reactions (e.g. vinyl ethers, styryloxy's, propenylethers, et al.) may be advantageously included in the mixture with the thiol or thiol-ene components.
  • cationically glycol ethers, cycloaliphatic epoxides, etc.
  • anionically polymerizable compounds or compounds that can be polymerized via free-radical and cationic reactions
  • free-radical and cationic reactions e.g. vinyl ethers, styryloxy's, propenylethers, et al.
  • the formulations of the invention optionally may contain a compound that initiates the chemical reactions upon exposure to radiation (visible, UV, infrared, or electron beam), or that initiates the reaction upon exposure to heat.
  • a preferred embodiment of the invention comprises thiol-ene formulations containing free-radical generating cleavage and hydrogen-abstraction type photoinitiators such as Additol TPO (Cytec Industries Inc.); Additol BCPK (Cytec Industries Inc.); Additol BDK (Cytec Industries Inc.); Additol HDMAP (Cytec Industries Inc.); Additol ITX (Cytec Industries Inc.); Additol CPK (Cytec Industries Inc.); Additol BP (Cytec Industries Inc.); and the like.
  • a photo-acid generating initiator may optionally included, selected from, for example, sulphonium salts, iodoium salts, and other compounds known or reasonably expected to initiate a cationic polymerization.
  • one or more photo-base generators which produce Lewis base upon irradiation may be used, particularly in anionically polymerizable hybrid formulations of the invention.
  • the formulations of the inventions may also contain stabilizers to prevent premature reaction of the formulation.
  • stabilizers may be antioxidants, free-radical scavengers, UV- absorbers, and/or other known stabilizers including for example compounds selected from: hydroquinone type compounds, phenolics, nitrosoamines, thiazines, thioesters, phosphites, antimony compounds, hindered amine light stabilizers (HALS), and the like, including for example: hydroquinone (HQ); 4-methoxyphenol (MEHQ); 2,6-di-t-butyl-4-methylphenol (BHT); 2-methyl-1,4-benzenediol (THQ); phenothiazine (PTZ), tris(N-nitroso-N- phenylhydroxyamine) aluminum salt (NPAL, Albemarle Corp.); CYAN OX ® 425 (Cytec
  • an acid-scavenging stabilizer may be included to prevent premature cationic polymerization or oligomerization of the formulation.
  • a shelf-stable fully formulated thiol-ene component resin mixture is preferred, a possible embodiment may include a multi-component system that must be mixed by the end-user just prior to use.
  • composition of the invention(s) optionally may contain additives to increase adhesion of the cured interlayer to the glass or polymer lites.
  • additives may be selected from a range of compound types may include for example, free-radically or cationically polymerizable compounds with secondary functionality selected from one or more of the following types: silane, siloxane, phosphonate, phosphate, sulfonate, amine, thio-ether, urethane, urea, thiocarbamate, thiourea, carboxylic acid.
  • additives such as colorants, flow-aides, dispersing aides, foam-control agents, surfactants, antioxidants, light stabilizers, and others known in the field including inert fillers such as silica, alumnia, titanium dioxide, pigments, dyes, clays, acrylic polymers, and similar materials may optionally be included in the compositions of the invention.
  • the amounts of these additional ingredients preferably ranges from 0.005 to 25 wt%, more preferably from 0.01 to 10 wt%, and most preferably from 0.025 to 5 wt%.
  • the compositions of the present invention are prepared using methods known in the art.
  • glass laminates are made by sandwiching two panes (lites) of heat treated or annealed glass wherein the lites are separated around the perimeter by a spacer tape with thickness of 0.76 mm to 3mm, and then filling the interstitial volume with the compositions of the invention by pumping the resin into the cavity with the sandwiched lites standing at an angle of at least 60°. After filling with the proper volume of liquid, the filled sandwich is slowly returned to horizontal, allowing the liquid to flow throughout the entire cavity. When the liquid reaches the filling opening, the opening is sealed with hot melt material. Any entrapped air is then removed with a small syringe. The polymer interlayer is then formed through exposure of the sandwiched resin composition to irradiation under a bank of fluorescent UV-A bulbs for 20 minutes.
  • Polymerization, or cure, of the formulations of the invention may be accomplished by exposure of the resin mixture to electromagnetic radiation in the ultraviolet, visible, or infrared spectral regions. Polymerization may also be conducted thermally alone, or in combination with electromagnetic irradiation. Optionally the formulations of the invention may be cured via electron-beam irradiation. While the most preferred method of cure is irradiation by UV-A fluorescent bulbs, preferred methods also include exposure to solar radiation (e.g. sunshine), LED lamps, or emissions from doped or undoped mercury arc lamps (medium pressure, high pressure), microwave lamps (Fusion D, H, V, excimer bulbs), and other gas plasma sources.
  • solar radiation e.g. sunshine
  • LED lamps or emissions from doped or undoped mercury arc lamps (medium pressure, high pressure), microwave lamps (Fusion D, H, V, excimer bulbs), and other gas plasma sources.
  • the laminates of the invention are preferably constructed to be translucent to the curing radiation from either face of the laminate.
  • the laminates may be opaque on both faces, in which case the cure may be accomplished thermally, by electron beam, or by exposure of the laminate edge to irradiation.
  • Products that may be made from the composition of the invention include laminate structures wherein two or more glass and/or polymeric substrates are adhered together in a layered arrangement such that the polymerized compositions of this invention form one or more polymeric interlayer(s) interspaced between adjacent glass or polymeric substrates.
  • two glass panes could form a sandwich of the composition of the invention.
  • two polymeric panes could be used to form such a sandwich, or a combination of glass and polymeric panes.
  • Construction of the products of the invention may be conducted via standard UVEKOL ® S type manufacturing processes or other processes known in the art.
  • the substrate layers may be colored or colorless, translucent, opaque, reflective, painted, decorated, or printed.
  • the polymeric interlayer(s) may be colored or colorless, translucent or opaque.
  • the present invention also includes machines or articles of manufacture incorporating the above laminates.
  • the composition of the invention is particularly useful in the production of glass laminates for hurricane glass, bullet resistant glazing and/or polymer laminates for window or structural applications, acoustical dampening laminates for window applications, and safety glass for automotive or architectural applications.
  • Particular applications of the composition of the invention is in producing windows designed for protection against ballistic impact of bullets or other projectiles, and windows designed for protection against overpressures generated by detonation of bombs and other explosive devices.
  • Composition 1 includes tetrathiol/triallylether components in a 1:1 equivalent ratio plus 30% by wt. di/tri methacrylate as follows:
  • Composition 1 is prepared by admixture of 31.6g trimethylolpropane diallylether with 1Og trimethylolpropane trimethacrylate, 2Og 1,6-hexanedioldimethacrylate, Ig [3- (methacryloyloxy)propyl] trimethoxysilane, and 36.1g of pentaerythritol tetrakis(3- mercaptopripionate) under low-shear mixing conditions at for 1 hour at 25°C. To this homogeneous mixture is added Ig NPAL (Albemarle Corp.) and 0.3g Additol CPK (Cytec Industries, Inc.) followed by further mixing at 25°C until homogeneous.
  • Ig NPAL Albemarle Corp.
  • Additol CPK Cosmetic Industries, Inc.
  • Composition 2 includes tetrathiol/tetra allylether urethane in a 1: 1 equivalent ratio plus 20% by wt. dimethacrylate as follows:
  • Composition 2 is prepared as follows. 16.34g TMXDI diisocyanate (CYTEC) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0.1 g dibutyltindilaurate and 0.2g methoxyphenol are added to the mixture and mixed until homogenous. 28.66g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated TMXDI-tetrallylether.
  • CYTEC TMXDI diisocyanate
  • 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C.
  • 0.1 g dibutyltindilaurate and 0.2g methoxyphenol are added to the
  • Ig NPAL Albemarle Corp.
  • Additol CPK Cytec Industries, Inc.
  • Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
  • Composition 3 includes tetrathiol/tetraallyl ether urethane in a 1: 1 equivalent ratio plus 20% by wt dimethacrylate as follows:
  • Composition 3 is prepared as follows. 17.29g Desmodur W diisocyanate (Bayer) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0. Ig dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 28.2 Ig trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether.
  • Ig NPAL Albemarle Corp.
  • Additol CPK Cytec Industries Inc.
  • Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
  • COMPOSITION 4 Composition 4 includes trithiol/tetraallylether urethane in a 1: 1 equivalent ratio plus 30% by wt. di/tetra methacrylate as follows:
  • Composition 4 is prepared as follows. 14.55g Desmodur W diisocyanate (Bayer) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0.1 g dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 23.75g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether.
  • Composition 5 includes tetrathiol/tetraallylether urethane in a 1: 1 equivalent ratio plus 20% dimethacrylate plus 20% UA oligomer as follows:
  • Composition 5 is prepared as follows. 12.84g Desmodur W diisocyanate (Bayer) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0. Ig dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 20.96g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether.
  • Composition 6 includes tetrathiol urethane/triazine triallylether (1 :1 equivalents) plus 30% HDDDA, 20% EB230 as follows:
  • Composition 6 is prepared as follows. 28.14g trimethyolopropane tris(3- mercaptoproprionate) is added to a reaction flask. 0.05g dibutyltindilaurate and 0.2g 4- methoxyphenol are added and mixed at 25°C until homogenous. 7.86g isophorone diisocyanate (Bayer) is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated IPDI tetra thiol.
  • Composition 7 includes tetrathiol urethane/triazine triallylether (1 :1 equivalents) plus 30% HDDMA, 15% EBECRYL ® 230, 10% EBECRYL ® 3720-TM40 as follows:
  • Composition 7 is prepared as follows. 25.17g trimethyolopropane tris(3- mercaptoproprionate) is added to a reaction flask. 0.05g dibutyltindilaurate and 0.2g 4- methoxyphenol are added and mixed at 25°C until homogenous. 7.03g isophorone diisocyanate (Bayer) is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated IPDI tetra thiol.
  • Composition 8 includes tetrathiol/tetraallylether urethane (1: 1 equivalents) plus 25%
  • Composition 8 is prepared as follows. 8.97g TMXDI diisocyanate (Cytec Industries, Inc.) and 1Og methylmethacrylate are added to a reaction flask and mixed at 25°C. 0.02g dibutyltindilaurate and O.lg 4-methoxyphenol are added to the mixture and mixed until homogenous. 15.73g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated TMXDI-tetrallylether.
  • Composition 9 includes tetrathiol/hexylallylether urethane (1: 1 equivalents) plus 20% TMPTMA, 20% EHA, 5% MAA, and 10% EBECRYL ® 230.
  • Composition 9 is prepared as follows. 5.09g hexamethylene diisocyanate (Bayer) and 2Og ethylhexylacrylate are added to a reaction flask and mixed at 25°C. 0.02g dibutyltindilaurate and 0.1 g 4-methoxyphenol are added to the mixture and mixed until homogenous. 15.51 g pentaerythritol tetraallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designatedHDI hexa-allylether.
  • Composition 10 includes tetrathiol/tetraallylether urethane (1: 1 equivalents) plus 20% TMPTMA, 15% MMA, and 20% EBECRYL ® 8302.
  • Composition 10 is prepared as follows. 6.72g Desmodur W diisocyanate (Bayer) and 15g methylmethacrylate are added to a reaction flask and mixed at 25°C. 0.05g dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 10.98g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether.
  • Ig NPAL Albemarle Corp.
  • Additol CPK Citec Industries Inc.
  • 2Og EBECRYL ® 8302 CYTEC
  • 2Og trimethylolpropane trimethacrylate 25g pentaerythritol tetrakis(3-mercaptopripionate)
  • Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
  • Composition 11 includes tetrathiol urethane/triallylamine (1 :1 equivalents) plus 20% DiTMPTMA, 15% MMA, and 20% EBECRYL ® 8405.
  • Composition 11 is prepared as follows. 29.78g trimethyolopropane tris(3- mercaptoproprionate) is added to a reaction flask. 0.05g dibutyltindilaurate and 0.2g 4- methoxyphenol are added and mixed at 25°C until homogenous. 8.32g isophorone diisocyanate (Bayer) is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated IPDI tetra thiol.

Abstract

The present invention is directed to a laminate composition, comprising (1) one or more thiol-functional compounds; (2) one or more oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds; and (3) one or more monomeric compounds containing or more carbon-carbon double bonds or triple bonds. The present invention is also directed to methods of producing glass and/or polymer laminates using the above composition, glass and/or polymer laminates made from the method, and machines or articles of manufacture incorporating the above laminates.

Description

MULTICOMPONENT THIOL-ENE COMPOSITIONS FOR LAMINATE MATERIALS
BACKGROUND OF THE INVENTION 1. Field of the Invention
This invention relates to the use of thiol-ene based radiation curable formulations for laminate applications. More specifically, this invention relates to the use of binary, ternary, and/or multi-component chemical systems comprising thiol-enes as radiation-curable formulations. The thiol-ene comprising formulations are suitable for use as the polymeric interlayers for glass laminate applications including, but not limited to, typical applications such as hurricane windows, doors, and curtainwalls; acoustical dampening windows, doors and curtainwalls; ballistic resistant glass, and safety glass.
2. Brief Description of the Related Art The technique of laminating glass panes, i.e. binding two or more glass panes together in a permanent way by an interlayer, is well known and generally applied. Such glass laminates are used for example in automotive and building applications.
In the present description, the term "glass" is used to designate objects made of glass or of glass appearance. Glass appearance objects such as polycarbonate panels can be used but are less preferred because of their poor behavior in case of fire. The glass objects can be made of ordinary float glass, whether heat treated or not, or of special glass such as borosilicate glass.
Laminating protects people from splinters in case of glass breaking, and it also provides additional properties to the glazing. Basically, laminated glass is industrially produced either by a polymer film system, or by liquid cast-in-place resin polymerized in situ. The film lamination technology often comprises the insertion of an organic, polymeric film between two glass panes, and bonding them at an elevated temperature under an elevated pressure. Different materials can be used, for example polyvinylbutyral (PVB) as the organic film. The foil is positioned on a glass pane, and a second pane positioned upon the film. The so- formed sandwich has to be passed through an oven, to weaken the film and create a preliminary adhesion. The sandwich then undergoes a batch-wise heating and pressure cycle, in order to bring the film in close contact with the glass and to develop adhesion onto the glass surfaces. This operation is done in an autoclave, at 120 to 150°C and with increased pressure, typically between 10 to 17 kg/cm3, in order to bring the film in close contact with the glass and to develop adhesion onto the glass surfaces. Residence time in the autoclave at the required temperature is 30 to 45 minutes, longer for bent or multiple laminates. The total residence time, including heating and subsequent cooling is about 2 hours. The PVB film lamination process is described in 'Encyclopedia of Chemical Technology' - KIRK-OTHMER - 4th edition, Volume 14, page 1059 - 1074. The main restrictions to this system are the high investment costs, while also the size of the autoclave can be restrictive in the case of larger panels and bent glazing. Moreover, the film lamination is a batch-wise process and requires a high-energy input. A large size apparatus is required, and the total operation time is long. Also, it is more difficult to apply on certain glass surfaces, e.g. toughened glass that is not completely flat. In such situations, the film is not elastic enough to adapt to the uneven surface. Also for bent glass it is more difficult to apply, when the curving of both glass panes would not be identical.
A possible solution to compensate for glass surface unevenness is to apply more film layers, 4 or 6 or more layers instead of the 1 or 2 layers as typically used. However, in this way significantly more organic combustible material is incorporated.
An alternative lamination technique is by the use of liquid resin, cured in situ. Two glass panes are bound together by a double-sided adhesive tape that also functions as a spacer. The cavity between the two sheets is then filled up with a liquid resin. Typically the envelope is positioned at an angle of at least 60° during filling. After complete filling, the filled sandwich is slowly returned to horizontal, allowing the liquid to flow throughout the entire cavity. When the liquid reaches the filling opening, the opening is sealed with hot melt material. Any entrapped air is then removed with a small syringe. The liquid resin is then polymerized, the so-called "curing" step. Curing can be accomplished either by radiation, or chemically by appropriate catalysts and accelerators.
Polymerization, the so-called "curing" step, chemically changes the liquid resin into a solid polymeric interlayer. There is basically no visual differentiation between foil laminated glazing and resin laminated glazing. The equipment needed for resin lamination may be as little as one or two tilting tables to allow the assembly of the envelope, a dosing pump and, in case of radiation cure, a radiation source. A strong technical advantage of the liquid resin system is that the cavity between the two glasses is completely filled up with the liquid resin, thus the influence of the shape or roughness of the glass surfaces on the bonding with the resin interlayer is significantly reduced. The incorporation of adhesion promoters(s), most often appropriate silanes, allows for a chemical bond to be created between the silanol (- Si - OH) functions on the glass surface, and the interlayer. A chemical bond is stronger than simple physical adhesion, and is typically more stable over time.
The chemical nature of the liquid resins used for glass lamination can be of different kinds, for example polyester, polyurethane, silicone or, most often, acrylic. The latter is preferred for its high resistance against outdoor weathering conditions, i.e. UV radiation, heat and humidity. An example of a polyester-based liquid resin system, for manufacturing acoustic glazing, is described in French patent 1367977, "Acoustic Laminates", by Saint-Gobain Industries of France. An example of a urethane acrylate-based liquid resin system, for manufacturing clear glazing, is given in EP0108631, by DeltaGlass S.A.
Curing of the liquid resin can be initiated directly by inclusion of one or more catalysts, accelerants, or highly reactive components in the liquid resin mixture, or indirectly by heating, irradiation with UV or visible electromagnetic radiation, or exposure to electron-beam radiation. For direct chemical initiation one or more catalysts and an accelerator are added to the base resin, this is the so-called multi-component system. Each of the above mentioned chemical types of resins could be multi-component. The reaction starts after the blending of the catalyst(s) and the accelerator with the resin, after a period of time that depends on the resin composition, the concentrations of catalyst(s) and accelerator, and the temperature of the substrates and the environment.
Additionally, IR radiation sources can be applied to increase reaction speed. Polymerization of radiation curable resins is initiated by irradiation of photosensitive components in the resin formulation with electromagnetic radiation typically in the ultraviolet and/or visible spectral regions, or by exposure of the resin to electron beam radiation. Most typically, in the case of radiation cure, the radiation source comprises one or more fluorescent bulbs, arc lamps, light emitting diodes (LEDs), or microwave lamps in an assembly that when energized irradiates the filled laminate with electromagnetic radiation primarily in the ultraviolet and visible spectral range. In some cases, the radiation source comprises a device that irradiates the filled laminate with a beam of electrons to initiate polymerization. UV curable liquid resin systems are described in i.e. EP0108631.
Most often UV resins for glass laminates are initiated by the action of UV light of low intensity with an exposure time of typically 15 to 30 minutes.
Different chemical types of polymer precursors are possible, while most commonly, ethylenically unsaturated resins based upon esters of (meth)acrylic acid and derivatives thereof containing polyester, urethane, or polyether functionality are used.
(Meth)acrylate -based UV curable polymer precursors for glass laminates typically contain:
- a reactive oligomer, i.e. a (meth)acrylated urethane oligomer, - reactive diluents, i.e. (meth)acrylated monomers,
- the monomers can be one or more of the following: 2-ethylhexyl acrylate, 1,6- hexanediol diacrylate, n- hexyl acrylate, n-hexyl methacrylate, 2 -hydroxy ethyl acrylate, 2- hydroxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, n-lauryl acrylate, n-lauryl methacrylate, methyl methacrylate (MAM), butyl acrylate, acrylic acid, methacrylic acid, isobutyl acrylate, cyclohexyl acrylate, 2-butoxyethyl acrylate, cyclohexyl acrylate, N-vinyl pyrrolidone, and the like, with he preferred ones in the field of glass laminates being mono -functional monomers that are low in viscosity and provide a relatively higher glass transition temperature in the cured interlayer,
- one or more photo-initiators, - adhesion promoters, for example silane compounds
- additives, for example stabilizers.
Laminated glass is used in the automotive and the building industry. Its functions can be manifold, although typically the main objectives are sound insulation and safety and security performance. Glazing in the building industry has several functions, more or less dependent on its application:
- regulation of the incident light with respect to clarity and transparency, control of the heat transmission from infrared solar irradiation,
- physical integrity, protection against wind and heat, -heat insulation,
- acoustic insulation, - safety and/or security performances, to protect people against falling through glazing and against falling glass, to protect against burglary and vandalism,
- fire resistance
- bomb blast resistance - decoration.
Traditional film or resin laminated glass fulfils most of these functions, in particular film or resin laminated glass may have very good properties as to sound reduction and impact resistance.
As mentioned above, in laminate applications, multi-component formulations are pre- mixed or mixed in-situ and injected into a gap between glazing layers (lites) (preferably glass to glass, but can be glass to polymer, or polymer to polymer, etc.), and subsequently polymerized through irradiation (preferably UV-A type irradiation) to form a polymeric interlayer between the lites of glass (or polymer). The polymerized interlayer serves to adhere one lite to the other and also serves to dissipate energy under high shear (i.e. from ballistic impact), while also providing rigidity under low shear deformation ( e.g. window pressure cycling) of the laminate structure. Additionally, due to excellent adhesion to the lites, the interlayer prevents release of dangerously small and ballistic shards of glass (or polymer) upon impact of a projectile or other breakage of the glass.
For hurricane window applications, achieving an optimal balance of high shear energy dissipation to prevent interlayer penetration during ballistic impacts, in combination with sufficient low-shear rigidity to prevent flex-related pullout from the frame during pressure cycling has proven to be very difficult for large window sizes using the conventional radiation- curable (meth)acrylate chemistry. This dichotomous application need which requires flexibility to improve high shear energy dissipation, and yet requires rigidity to minimize flex under low- shear large-area pressure-induced deformation and to achieve sufficient toughness to prevent interlayer penetration is a difficult challenge. Thus, known radiation curable glass laminate interlayers, such as UVEKOL R -S, are not capable of meeting the performance requirements for large hurricane windows or certain corner window applications where relatively higher pressure cycles may occur. Competitive polymer ionomer-based materials such as Dupont SentryGlas® Plus are available that meet the performance needs, but via a less advantageous window manufacturing process and at a much higher cost. New formulations of curable formulations for laminate applications are therefore desired, and this invention is believed to meet those needs by providing a tough, polymeric interlayer that is sufficiently flexible to dissipate energy from ballistic impact while also providing sufficient rigidity to minimize laminate flex under large-area pressure deformations, and embodied in a technology and manufacturing process that provides the advantages of the liquid-fill in-situ polymerized laminate systems.
SUMMARY OF THE INVENTION
In one aspect, the present invention is directed to a laminate composition, comprising (1) one or more thiol-functional compounds; (2) one or more oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds; and (3) one or more monomeric compounds containing one or more carbon-carbon double bonds or triple bonds.
In another aspect, the present invention is directed to a method of producing a glass laminate, comprising the steps of (1) providing at least two juxtaposed panes of glass and/or polymer having a gap between them; (2) applying the above laminate composition into the gap; and (3) curing the composition.
In another aspect, the present invention is directed to a glass laminate comprising at least two juxtaposed panes of glass having a gap between them, the gap filled with the above composition in a cured state. In additional aspects, the present invention is also directed to methods of producing glass and/or polymer laminates using the above composition, glass and/or polymer laminates made from the method, and machines or articles of manufacture incorporating the above laminates.
These and other aspects will become apparent upon reading the following detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Use of UVEKOL R type radiation-curable materials for manufacturing laminated glass windows offers many advantages including a fast curing process that is not temperature dependent, a one-component product that requires no mixing, and solvent-free materials that facilitate easy disposal and clean-up. However, certain parameters of these systems are less advantageous. For example, viscoelastic properties, impact dissipation properties, and rigidity of the formed products are not always suitable for certain applications.
The inventors have unexpectedly found that the compositions of the present invention overcome these limitations. Specific advantages of thiol-ene component chemical systems disclosed in the present invention include tailored viscoelastic properties of the cured interlay er that may provide for a significantly higher level of energy absorption and dissipation by the interlayer under ballistic impact as well as tailored rigidity under low-shear deformation of the laminate. This chemistry demonstrates a step-change in performance relative to the existing UVEKOL®-type formulations. When properly formulated, the thiol-ene formulations of the present invention also provide advantages for reduced photodegradation, reduced handling hazards relative to the commercial (meth)acrylate formulations, improved cure times, resistance to oxygen inhibition, and capability for curing very thick segments.
The technical basis of this step-change in application performance is tailoring of the rheological characteristics of the cured interlayer, for example by manipulation of the temperature and width of the glass transition temperature of the polymer interlayer through morphological design. The morphological design is achieved by intelligent selection of thiol component as well as one or more types of "ene" components, wherein variables are optimized including: (1) reactivity ratios of the enes for radical copolymerization relative to homopolymerization relative to Michael addition relative to thiol-ene step-growth polymerization (2) structural features of the "ene" such as aromaticity, flexibility, molecular weight, ene functionality (i.e. (meth)acrylate, vinylether, alkene, urethane, polyester, polyether, etc.), linear, branched, dendritic, etc. (3) structural features of the thiol such as thiol functionality, molecular weight, flexibility, etc. (4) kinetic rate effects through quantity and type(s) of photoinitiator(s). Intelligent manipulation of these compositional and process-related variables in thiol-ene multicomponent systems permits formation of novel morphologies such as interpenetrating polymer networks, tough materials with a very narrow or specific temperature Tg, durable highly elastic networks, durable inelastic networks, etc. These morphologies and resulting polymer viscoelastic properties are due the nature of the components and to the different reactions that may occur during the polymerization of the mixture: (1) thiol-ene polymerization through Michael addition (2) thiol-ene polymerization through step-growth chain mechanism (3) homopolymerization of the ene components (4) copolymerization of the ene components (5) cross polymerization of thiol-ene segments with free-radical hompolymers or copolymers of the ene components through chain-transfer and other reactions, as well as to secondary interactions within the resulting polymer structure such as (6) hydrogen bonding (7) pi-stacking (8) ionic interactions (9) dipolar interactions, and the like.
As indicated above, the present invention is directed to a laminate composition, comprising: (1) one or more thiol-functional compounds, (2) one or more oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds (the "ene" component); and (3) one or more monomeric compounds containing or more carbon- carbon double bonds or triple bonds. Each of these components is discussed in more detail below.
The thiol-functional component of the invention may be any poly-thiol functional molecule, oligomer, or polymer. Thiol functionality of 3 or more thiol groups per molecule is preferred. More than one thiol functional compound may be used in any particular formulation of this invention. Examples of preferred thiols are shown in Table 1 and Figure 1.
Table 1. Examples of Thiol-Functional Compounds
Figure imgf000009_0001
Figure imgf000010_0001
trimethylolpropane tris(3-mercaptopropionate)
Figure imgf000010_0002
398.54g/mol; 132.85g/eq SH pentaerythritol tetrakis(3-mercaptopropionate) 488.64g/mol; 122.16g/eq SH
Figure imgf000010_0003
TMXDI tetra thiol 1041.38g/mol, 260.34g/eq SH
Figure imgf000010_0004
IPDI tetra thiol 1019.38g/mol; 254.8g/eq SH
Figure imgf000010_0005
Figure 1. Selected thiols of the invention. The amounts of the thiol-functional component of the invention preferably ranges from 0.5 to 75wt%, more preferably from 5 to 60 wt%, and most preferably from 20 to 50 wt%., all based on the total weight of the composition.
The ene components of the invention may be any unsaturated compound capable of undergoing free-radical homopolymerization, copolymerization, or polymerization with a thiol through Michael addition and/or free-radical step-growth reactions including vinyl ethers, vinyl esters, allyl esters, allyl ethers, allyl amines, vinyl amines, vinyl amides, esters and amides of (meth)acrylic acid, esters of maleic and fumaric acids, maleimides, et al. One preferred class of enes is (meth)acrylate functional compounds including (meth)acrylated monomers, oligomers, and polymers.
The ene component of the formulations of the invention(s) may be comprised of one or more enes of similar or dissimilar types. Preferred embodiments of the ene components of the present invention(s) include aliphatic urethane (meth)acrylates (ex. EBECRYL®® 230, EBECRYL® 244, EBECRYL® 264, EBECRYL® 265, EBECRYL® 270, EBECRYL® 284, EBECRYL® 290, EBECRYL® 4830, EBECRYL® 4833, EBECRYL® 8800, EBECRYL® 8804, EBECRYL® 8807, EBECRYL® 8411 , EBECRYL® 8402, EBECRYL® 8405, EBECRYL® 8301, available from Cytec Industries, West Paterson, NJ.), and thio-carbamate analogues of those materials. The ene component of the formulation may also contain one or more oligomeric, polymeric, or monomeric enes that do not readily homopolymerize through free-radical chemical processes such as vinyl ethers, N-vinylamides, et al. Norbornenes are also a preferred type of ene in the invention.
Enes may be reacted with other enes and/or with thiols to produce poly-enes of various useful structures. For example, cycloaddition reactions can be utilized to prepare norbornenes through, for example, [4+2] cycloaddition of cyclopentadiene to (meth)acrylates. Similarly, enes with thio-ether functionality may be prepared through Michael addition of poly-thiols with a stoichiometric excess of di or poly-enes such as (meth)acrylates, vinyl acrylate, et al. Selected enes of the invention are listed in Table 2 and Figure 2. Table 2. Examples of Ene Compounds
Figure imgf000012_0001
Figure imgf000013_0001
In general, the molecular weight of the ene component is preferably 500 g/mol to 20,000 g/mol, and the viscosity is preferably 1000 cP to 106 cP (at 25°C). The amounts of the ene component of the invention preferably ranges from 15 to 95 wt%, more preferably from 25 to 75 wt%, and most preferably from 35 to 60 wt%., based on the total weight of the composition. Viscosity being a prime factor in the practical utility of the compositions of the invention, preferred embodiments of the invention also include diluting monomers to control formulation viscosity. These diluting monomers comprise low molecular weight ethylenically unsaturated compounds with molecular weight lower than about 500g/mole and viscosity lower than about 50OcP at 25°C, and may include for example: vinyl ethers, vinyl esters, allyl esters, allyl ethers, allyl amines, vinyl amines, vinyl amides, esters and amides of (meth)acrylic acid, esters of maleic and fumaric acids, maleimides, and the like. Preferred diluting monomers include, for example: HDODA, BDODA, PETA, TMPTA, di-TMPTA, TRPGDA, NPGDA, DPGDA, IBOA, ODA-N, EBECRYL® 1040, EBECRYL® 1039, OTA-480, DPHA, acrylate of Cardura E-IOP, et al. as well as the corresponding methacrylates. (Meth)acrylic acid is also a preferred diluting monomer of the invention and may functions as an ene and/or as an adhesion promoter. In general, the molecular weight of the diluting monomeric component is preferably 500 g/mol or less, and the viscosity is preferably 1000 cP or less (at 25°C). The amounts of the diluting monomeric component of the invention ranges from 5 to 90 wt%, more preferably from 20 to 70 wt%, and most preferably from 35 to 55 wt%., based on the total weight of the composition.
It is also anticipated that hybrid and/or dual-cure formulations may be utilized wherein one or more cationically (glycidyl ethers, cycloaliphatic epoxides, etc.), or anionically polymerizable compounds, or compounds that can be polymerized via free-radical and cationic reactions (e.g. vinyl ethers, styryloxy's, propenylethers, et al.) may be advantageously included in the mixture with the thiol or thiol-ene components.
The formulations of the invention optionally may contain a compound that initiates the chemical reactions upon exposure to radiation (visible, UV, infrared, or electron beam), or that initiates the reaction upon exposure to heat. A preferred embodiment of the invention comprises thiol-ene formulations containing free-radical generating cleavage and hydrogen-abstraction type photoinitiators such as Additol TPO (Cytec Industries Inc.); Additol BCPK (Cytec Industries Inc.); Additol BDK (Cytec Industries Inc.); Additol HDMAP (Cytec Industries Inc.); Additol ITX (Cytec Industries Inc.); Additol CPK (Cytec Industries Inc.); Additol BP (Cytec Industries Inc.); and the like. In formulations of the inventions containing cationically polymerizable ene or epoxy components, a photo-acid generating initiator may optionally included, selected from, for example, sulphonium salts, iodoium salts, and other compounds known or reasonably expected to initiate a cationic polymerization. Optionally, one or more photo-base generators which produce Lewis base upon irradiation may be used, particularly in anionically polymerizable hybrid formulations of the invention.
The formulations of the inventions may also contain stabilizers to prevent premature reaction of the formulation. These stabilizers may be antioxidants, free-radical scavengers, UV- absorbers, and/or other known stabilizers including for example compounds selected from: hydroquinone type compounds, phenolics, nitrosoamines, thiazines, thioesters, phosphites, antimony compounds, hindered amine light stabilizers (HALS), and the like, including for example: hydroquinone (HQ); 4-methoxyphenol (MEHQ); 2,6-di-t-butyl-4-methylphenol (BHT); 2-methyl-1,4-benzenediol (THQ); phenothiazine (PTZ), tris(N-nitroso-N- phenylhydroxyamine) aluminum salt (NPAL, Albemarle Corp.); CYAN OX® 425 (Cytec
Industries Inc.); CYANOX® 1741(Cytec Industries Inc.); CYANOX® 1790(Cytec Industries Inc.); CYANOX® 2246(Cytec Industries Inc.); CYANOX® 711 (Cytec Industries Inc.); CYANOX® 1212 (Cytec Industries Inc.); CYANOX® LTDP(Cytec Industries Inc.); CYANOX® STDP(Cytec Industries Inc.); CYANOX® 2777(Cytec Industries Inc.); CYANOX® XS4(Cytec Industries Inc.); CYASORB® UV-2337(Cytec Industries Inc.); CYASORB® UV-5411 (Cytec Industries Inc.); CYASORB® UV-594; CYASORB® UV-9(Cytec Industries Inc.); CYASORB® UV-24(Cytec Industries Inc.); CYASORB® UV-531(Cytec Industries Inc.); CYASORB® UV- 2126(Cytec Industries Inc.).
Optionally, for formulations of the invention that contain cationically polymerizable components, an acid-scavenging stabilizer may be included to prevent premature cationic polymerization or oligomerization of the formulation. While use of a shelf-stable fully formulated thiol-ene component resin mixture is preferred, a possible embodiment may include a multi-component system that must be mixed by the end-user just prior to use.
The composition of the invention(s) optionally may contain additives to increase adhesion of the cured interlayer to the glass or polymer lites. These additives may be selected from a range of compound types may include for example, free-radically or cationically polymerizable compounds with secondary functionality selected from one or more of the following types: silane, siloxane, phosphonate, phosphate, sulfonate, amine, thio-ether, urethane, urea, thiocarbamate, thiourea, carboxylic acid. Other additives, such as colorants, flow-aides, dispersing aides, foam-control agents, surfactants, antioxidants, light stabilizers, and others known in the field including inert fillers such as silica, alumnia, titanium dioxide, pigments, dyes, clays, acrylic polymers, and similar materials may optionally be included in the compositions of the invention.
The amounts of these additional ingredients preferably ranges from 0.005 to 25 wt%, more preferably from 0.01 to 10 wt%, and most preferably from 0.025 to 5 wt%. The compositions of the present invention are prepared using methods known in the art.
For example, in the Examples described below, glass laminates are made by sandwiching two panes (lites) of heat treated or annealed glass wherein the lites are separated around the perimeter by a spacer tape with thickness of 0.76 mm to 3mm, and then filling the interstitial volume with the compositions of the invention by pumping the resin into the cavity with the sandwiched lites standing at an angle of at least 60°. After filling with the proper volume of liquid, the filled sandwich is slowly returned to horizontal, allowing the liquid to flow throughout the entire cavity. When the liquid reaches the filling opening, the opening is sealed with hot melt material. Any entrapped air is then removed with a small syringe. The polymer interlayer is then formed through exposure of the sandwiched resin composition to irradiation under a bank of fluorescent UV-A bulbs for 20 minutes.
Polymerization, or cure, of the formulations of the invention may be accomplished by exposure of the resin mixture to electromagnetic radiation in the ultraviolet, visible, or infrared spectral regions. Polymerization may also be conducted thermally alone, or in combination with electromagnetic irradiation. Optionally the formulations of the invention may be cured via electron-beam irradiation. While the most preferred method of cure is irradiation by UV-A fluorescent bulbs, preferred methods also include exposure to solar radiation (e.g. sunshine), LED lamps, or emissions from doped or undoped mercury arc lamps (medium pressure, high pressure), microwave lamps (Fusion D, H, V, excimer bulbs), and other gas plasma sources.
The laminates of the invention are preferably constructed to be translucent to the curing radiation from either face of the laminate. Optionally, the laminates may be opaque on both faces, in which case the cure may be accomplished thermally, by electron beam, or by exposure of the laminate edge to irradiation.
Products that may be made from the composition of the invention include laminate structures wherein two or more glass and/or polymeric substrates are adhered together in a layered arrangement such that the polymerized compositions of this invention form one or more polymeric interlayer(s) interspaced between adjacent glass or polymeric substrates. For example, two glass panes could form a sandwich of the composition of the invention. Alternatively, two polymeric panes could be used to form such a sandwich, or a combination of glass and polymeric panes. Construction of the products of the invention may be conducted via standard UVEKOL® S type manufacturing processes or other processes known in the art. In a given product, the substrate layers may be colored or colorless, translucent, opaque, reflective, painted, decorated, or printed. Optionally the polymeric interlayer(s) may be colored or colorless, translucent or opaque.
The present invention also includes machines or articles of manufacture incorporating the above laminates. The composition of the invention is particularly useful in the production of glass laminates for hurricane glass, bullet resistant glazing and/or polymer laminates for window or structural applications, acoustical dampening laminates for window applications, and safety glass for automotive or architectural applications. Particular applications of the composition of the invention is in producing windows designed for protection against ballistic impact of bullets or other projectiles, and windows designed for protection against overpressures generated by detonation of bombs and other explosive devices.
EXAMPLES
The following examples are intended to illustrate, but in no way limit the scope of the present invention. All parts and percentages are by weight, and temperatures are in degrees Celsius unless explicitly stated otherwise. COMPOSITION 1
Composition 1 includes tetrathiol/triallylether components in a 1:1 equivalent ratio plus 30% by wt. di/tri methacrylate as follows:
Figure imgf000018_0001
Composition 1 is prepared by admixture of 31.6g trimethylolpropane diallylether with 1Og trimethylolpropane trimethacrylate, 2Og 1,6-hexanedioldimethacrylate, Ig [3- (methacryloyloxy)propyl] trimethoxysilane, and 36.1g of pentaerythritol tetrakis(3- mercaptopripionate) under low-shear mixing conditions at for 1 hour at 25°C. To this homogeneous mixture is added Ig NPAL (Albemarle Corp.) and 0.3g Additol CPK (Cytec Industries, Inc.) followed by further mixing at 25°C until homogeneous.
COMPOSITION 2
Composition 2 includes tetrathiol/tetra allylether urethane in a 1: 1 equivalent ratio plus 20% by wt. dimethacrylate as follows:
Figure imgf000018_0002
Composition 2 is prepared as follows. 16.34g TMXDI diisocyanate (CYTEC) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0.1 g dibutyltindilaurate and 0.2g methoxyphenol are added to the mixture and mixed until homogenous. 28.66g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated TMXDI-tetrallylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries, Inc.), and 32.7g pentaerythritol tetrakis(3-mercaptopripionate), and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
COMPOSITION 3
Composition 3 includes tetrathiol/tetraallyl ether urethane in a 1: 1 equivalent ratio plus 20% by wt dimethacrylate as follows:
Figure imgf000019_0001
Composition 3 is prepared as follows. 17.29g Desmodur W diisocyanate (Bayer) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0. Ig dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 28.2 Ig trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), and 32.2g pentaerythritol tetrakis(3-mercaptopripionate), and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
COMPOSITION 4 Composition 4 includes trithiol/tetraallylether urethane in a 1: 1 equivalent ratio plus 30% by wt. di/tetra methacrylate as follows:
Figure imgf000020_0001
Composition 4 is prepared as follows. 14.55g Desmodur W diisocyanate (Bayer) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0.1 g dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 23.75g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 1Og di-trimethyolpropane tetramethacrylate, and 29.4g trimethyolopropane tris(3- mercaptoproprionate), and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous. COMPOSITION 5
Composition 5 includes tetrathiol/tetraallylether urethane in a 1: 1 equivalent ratio plus 20% dimethacrylate plus 20% UA oligomer as follows:
Figure imgf000021_0001
Composition 5 is prepared as follows. 12.84g Desmodur W diisocyanate (Bayer) and 2Og 1 ,6-hexanedioldimethacrylate are added to a reaction flask and mixed at 25°C. 0. Ig dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 20.96g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 2Og EBECRYL® 230 (CYTEC), and 23.9g pentaerythritol tetrakis(3-mercaptopripionate), and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
COMPOSITION 6
Composition 6 includes tetrathiol urethane/triazine triallylether (1 :1 equivalents) plus 30% HDDDA, 20% EB230 as follows:
Figure imgf000022_0001
Composition 6 is prepared as follows. 28.14g trimethyolopropane tris(3- mercaptoproprionate) is added to a reaction flask. 0.05g dibutyltindilaurate and 0.2g 4- methoxyphenol are added and mixed at 25°C until homogenous. 7.86g isophorone diisocyanate (Bayer) is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated IPDI tetra thiol. 1 g NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 2Og EBECRYL® 230 (CYTEC), 30g 1,6- hexanedioldiacrylate, 11.7g 1,3,5-triallyl-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione, and Ig [3- (methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
COMPOSITION 7
Composition 7 includes tetrathiol urethane/triazine triallylether (1 :1 equivalents) plus 30% HDDMA, 15% EBECRYL® 230, 10% EBECRYL® 3720-TM40 as follows:
Figure imgf000023_0001
Composition 7 is prepared as follows. 25.17g trimethyolopropane tris(3- mercaptoproprionate) is added to a reaction flask. 0.05g dibutyltindilaurate and 0.2g 4- methoxyphenol are added and mixed at 25°C until homogenous. 7.03g isophorone diisocyanate (Bayer) is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated IPDI tetra thiol. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 15g EBECRYL® 230 (CYTEC), 30g 1,6- hexanedioldimethacrylate, 1Og EBECRYL® 3720-TM40 (CYTEC), 10.5g 1, 3,5 -triallyl- 1,3,5 - triazine-2,4,6-(1H, 3H, 5H)-trione, and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
COMPOSITION 8
Composition 8 includes tetrathiol/tetraallylether urethane (1: 1 equivalents) plus 25%
TCDDMDMA, 20% EBECRYL ® 230, and 10% methylmethacrylate.
Figure imgf000024_0001
Composition 8 is prepared as follows. 8.97g TMXDI diisocyanate (Cytec Industries, Inc.) and 1Og methylmethacrylate are added to a reaction flask and mixed at 25°C. 0.02g dibutyltindilaurate and O.lg 4-methoxyphenol are added to the mixture and mixed until homogenous. 15.73g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated TMXDI-tetrallylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), and 18g pentaerythritol tetrakis(3-mercaptopripionate), 25g tricyclodecane- dimethanoldimethacrylate, 2Og EBECRYL® 230 (Cytec) and 1 g [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous. COMPOSITION 9
Composition 9 includes tetrathiol/hexylallylether urethane (1: 1 equivalents) plus 20% TMPTMA, 20% EHA, 5% MAA, and 10% EBECRYL® 230.
Figure imgf000025_0001
Composition 9 is prepared as follows. 5.09g hexamethylene diisocyanate (Bayer) and 2Og ethylhexylacrylate are added to a reaction flask and mixed at 25°C. 0.02g dibutyltindilaurate and 0.1 g 4-methoxyphenol are added to the mixture and mixed until homogenous. 15.51 g pentaerythritol tetraallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designatedHDI hexa-allylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 22.1g pentaerythritol tetrakis(3-mercaptopripionate), 2Og trimethylolpropanetrimethacrylate, 1Og EBECRYL/ 230 (Cytec), 5g methacrylic acid, and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous. COMPOSITION 10
Composition 10 includes tetrathiol/tetraallylether urethane (1: 1 equivalents) plus 20% TMPTMA, 15% MMA, and 20% EBECRYL® 8302.
Figure imgf000026_0001
Composition 10 is prepared as follows. 6.72g Desmodur W diisocyanate (Bayer) and 15g methylmethacrylate are added to a reaction flask and mixed at 25°C. 0.05g dibutyltindilaurate and 0.2g 4-methoxyphenol are added to the mixture and mixed until homogenous. 10.98g trimethylolpropane diallylether is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated H12MDI-tetrallylether. Ig NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 2Og EBECRYL® 8302 (CYTEC), 2Og trimethylolpropane trimethacrylate, 25g pentaerythritol tetrakis(3-mercaptopripionate), and Ig [3-(methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
COMPOSITION 11
Composition 11 includes tetrathiol urethane/triallylamine (1 :1 equivalents) plus 20% DiTMPTMA, 15% MMA, and 20% EBECRYL® 8405.
Figure imgf000027_0001
Composition 11 is prepared as follows. 29.78g trimethyolopropane tris(3- mercaptoproprionate) is added to a reaction flask. 0.05g dibutyltindilaurate and 0.2g 4- methoxyphenol are added and mixed at 25°C until homogenous. 8.32g isophorone diisocyanate (Bayer) is then added dropwise to the stirring reaction mixture over 1 hour, after which the reaction mixture is heated to 60°C and held until all of the isocyanate has been consumed. The reaction mixture is cooled to 25°C, and is designated IPDI tetra thiol. 1.5g NPAL (Albemarle Corp.), 0.3g Additol CPK (Cytec Industries Inc.), 4.6g triallylamine, 2Og di-trimethylolpropane tetramethacrylate, 2Og EBECRYL® 8405 (CYTEC), 15g methylmethacrylate, and Ig [3- (methacryloyloxy)propyl] trimethoxysilane are added to the reaction flask and mixed until homogeneous.
While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents, and other publications cited herein are incorporated by reference in their entireties.

Claims

CLAIMSWHAT IS CLAIMED IS:
1. A laminate composition, comprising:
(1) one or more thiol-functional compounds;
(2) one or more oligomeric or polymeric compounds containing one or more carbon- carbon double bonds or triple bonds; and
(3) one or more monomeric compounds containing one or more carbon-carbon double bonds or triple bonds.
2. The laminate composition of claim 1 , wherein said thiol-functional compound is poly thiol-functional.
3. The laminate composition of claim 2, wherein said poly thiol functional compound contains 3 or more thiol groups per molecule.
4. The laminate composition of claim 1 , wherein said thiol-functional compound is selected from the group consisting of pentaerythritol tetrakis [3-mercaptopropionate], trimethylolpropane tris [3-mercaptopropionate], TMXDI terra thiol, IPDI tetra thiol, HDI terra thiol, hexanedithiol, ethyleneglycol di-2-mercaptoacetate, pentaerythritol tetrakis(2-mercaptoacetate), trimethyolopropane tris(2-mercaptoacetate), ethyleneglycol di-3-mercaptoproprionate, and combinations thereof.
5. The laminate composition of claim 1 , wherein said thiol-functional component comprises from 0.5 to 75wt%, more preferably from 5 to 60 wt%, and most preferably from 20 to 50 wt%., all based on the total weight of said laminate composition.
6. The laminate composition of claim 1 , wherein said oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds is selected from the group consisting of allyl ethers, acrylates, and methacrylates.
7. The laminate composition of claim 1 , wherein said oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds is selected from the group consisting of trimethylolpropane diallylether, pentaerythritol triallylether, TMXDI-tetrallylether, IPDI-tetrallylether, H12MDI tetraallylether, HDI hexaallylether, TATATO, triallyl amine, [3- (methacryloyloxy)propyl]trimethoxysilane, TMPTA, TMPTMA, HDDMA, DiTMPTMA, BADGE dimethacrylate, EBECRYL® 3720-TM40, and combinations thereof.
8. The laminate composition of claim 1, wherein said oligomeric or polymeric compounds containing one or more carbon-carbon double bonds or triple bonds comprise from 15 to 95 wt%, more preferably from 25 to 75 wt%, and most preferably from 35 to 60 wt%., based on the total weight of the composition.
9. The laminate composition of claim 1, wherein said one or more monomeric compounds containing one or more carbon-carbon double bonds or triple bonds is selected from the group consisting of vinyl ethers, vinyl esters, allyl esters, allyl ethers, allyl amines, vinyl amines, vinyl amides, esters and amides of (meth)acrylic acid, esters of maleic and fumaric acids, maleimides, HDODA, BDODA, PETA, TMPTA, di-TMPTA, TRPGDA, NPGDA, DPGDA, IBOA, ODA-N, EBECRYL® 1040, EBECRYL® 1039, OTA-480, DPHA, acrylate of Cardura E-IOP, and their corresponding methacrylates.
10. The laminate composition of claim 1, wherein said one or more monomeric compounds containing one or more carbon-carbon double bonds or triple bonds comprise from 5 to 90 wt%, more preferably from 20 to 70 wt%, and most preferably from 35 to 55 wt%., based on the total weight of the composition.
11. The laminate composition of claim 1, further comprising optional additional ingredients selected from the group consisting of one or more monomeric or oligomeric compounds containing epoxy or glycidylether groups, photoinitiators, thermal initiators, photoacid generators, photobase generators, stabilizers, pigments, dyes, coloring agents, surfactants, and combinations thereof.
12. A method of producing a laminate, comprising the steps of:
(1) providing at least two juxtaposed panes of glass and/or polymer having a gap between them; (2) applying a laminate composition according to any of claims 1 to 11 into said gap; and
(3) curing said composition.
13. The method of claim 12, wherein said curing step comprises ultraviolet, visible, infrared, electromagnetic irradiation, electron beam, or heating.
14. A laminate, comprising at least two juxtaposed panes of glass and/or polymer having a gap between them, said gap filled with the composition of claim 1 in a cured state.
15. A machine or article of manufacture incorporating the laminate of claim 14, and comprising a window, door, or curtainwall designed for use in hurricane conditions, for acoustical dampening, for protection against ballistic impact of bullets or other projectiles, for protection against overpressures generated by detonation of bombs and other explosive devices, for use in safety and security applications, and/or for use in fire resistant applications.
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