EP0190289A1 - Methode permettant d'appliquer une faible epaisseur de verre a un substrat resineux thermoplastique - Google Patents

Methode permettant d'appliquer une faible epaisseur de verre a un substrat resineux thermoplastique

Info

Publication number
EP0190289A1
EP0190289A1 EP85904055A EP85904055A EP0190289A1 EP 0190289 A1 EP0190289 A1 EP 0190289A1 EP 85904055 A EP85904055 A EP 85904055A EP 85904055 A EP85904055 A EP 85904055A EP 0190289 A1 EP0190289 A1 EP 0190289A1
Authority
EP
European Patent Office
Prior art keywords
glass
thin glass
further requires
adhesive
sheet
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.)
Withdrawn
Application number
EP85904055A
Other languages
German (de)
English (en)
Inventor
Fred Frank Holub
Daniel Robert Olson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0190289A1 publication Critical patent/EP0190289A1/fr
Withdrawn legal-status Critical Current

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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
    • B32B17/10009—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 number, the constitution or treatment of glass sheets
    • B32B17/10018—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 number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/1033—Laminated safety glass or glazing containing temporary protective coatings or layers
    • 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
    • B32B17/10697—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being cross-linked
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10706—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer being photo-polymerized
    • 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
    • B32B17/10743—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 acrylate (co)polymers or salts thereof
    • 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
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • 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
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • 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
    • B32B2369/00—Polycarbonates

Definitions

  • This invention relates to a method for making resinous laminates or sheets having exceptional scratch, mar, and chemical solvent resistance. More particularly, this invention relates to a method for making resinous laminates or sheets having thin glass adhered to at least one external surface by a UV cured adhesive interlayer. Such laminates or sheets are characterized by exceptional scratch, mar, and chemical solvent resistance, by a lack of residual stresses at room temperature or the chosen temperature of UV cure, by excellent impact resistance, and by their light weight. Such laminates combine the excellent properties of both glass and resinous thermoplastic to produce a single item having the above properties.
  • thermoplastic resinous sheets or laminates having external thermoplastic surfaces are well known and commercially available materials.
  • Such laminates or sheets can be engineered to possess a wide variety of chemical and physical properties.
  • items manufactured from these laminates or sheets are more break resistant at a lighter weight than glass and ' thus are used as a substitute for glass, as for example, in the manufacture of taillights, protective shields for street lights, safety shields in inspection windows, windshields, windows, and the like.
  • glass remains far superior to such materials in the surface characteristics of mar and chemical solvent resistance.
  • thermoplastic laminae into a laminate with external laminae of glass.
  • Such laminates benefit from both the mar resistance and strength of glass as well as the toughness of thermoplastic.
  • U.K. Pat. No. 2015427 discloses an in situ UV cure of the adhesive interlayer in glass-thermoplastic laminates. Such laminates as disclosed contain a substantial portion of their bulk in glass, thereby depriving the laminates to some degree of qualities of light weight and toughness which purely resinous laminates possess.
  • U.S. Pat. No. 3,666,614 discloses a laminate having a central lamina of polycarbonate and external laminae of glass bonded through adhesive interlayers such as polyvinyl butyral and the like. As above, these laminates contain a substantial portion of their bulk as glass and therefore become proportionately heavier and less shock resistant. In another line of development, the poor surface characteristics of thermoplastic laminates and sheets have been improved by use of thin protective layers of various organic and inorganic coatings. These protective coatings have substantially improved the mar and chemical solvent resistance of many resinous materials, but further improvement is still necessary.
  • 4,200,681 which is assigned to the same assignee as the present invention, discloses a polycarbonate article having deposited on the surface thereof (i) an intermediate primer layer containing the photoreaction products of certain polyfunctional UV cured acrylic monomers; and (ii) a top layer of vapor deposited silicon dioxide.
  • This article while an improvement over the prior art, suffers from a degree of erratic adhesion and crack resistance in the vapor deposited silicon dioxide coat.
  • thermoplastic laminates and sheets which have relatively good or excellent surface characteristics of mar and chemical solvent
  • thermoplastic sheets or laminates which thermoplastic sheets or laminates have adhered to at least one surface thereof a thin sheet of glass bonded by a UV cured adhesive.
  • thin glass sheet is best applied to a thermoplastic substrate through the use of a method characterized by the in situ UV cure of an adhesive interlayer. More particularly, the steps involved in performing this method include applying a thin film of a solventless photocurable adhesive composition to a thermoplastic substrate; laying on to the uncured adhesive composition a sheet of thin glass having a thickness of from about 0.3 mil to about 20 mil; and irradiating the composite with UV radiation under suitable conditions to cure the photocurable adhesive composition thereby forming a photocured adhesive interlayer. The method may additionally include steps for handling the thin glass sheet during lay on.
  • thermoplastic resinous substrates which may be used include acetal homopolymers; acetal copolymers produced by polymerization of trioxane and ethylene oxide; epoxy resins; polycarbonates; polyetherimides; phenylene oxide based resins such as polyphenylene oxide and blends of polyphenylene oxide and styrene resins; polyaryl ethers; polyesters; polyethylenes; polyphenylene sulfides; polypropylene; polysulfones; ethylene polymers such as ethyl vinyl acetates; conductive plastics and ordered aromatic copolymers, etc.
  • These thermoplastic resinous materials can be formed into sheets.
  • the substrate is preferably a thermoplastic resinous polycarbonate, particularly an aromatic polycarbonate.
  • thermoplastic resinous polycarbonate particularly an aromatic polycarbonate.
  • These are homopolymers and copolymers and mixtures thereof that are prepared by reacting a dihydric phenol with a carbonate precursor.
  • Suitable dihydric phenols of the bisphenol type are available and disclosed in U.S. Pat. Nos. 2,999,835, 3,028,365 and 3,334,154 which are incorporated herein by reference.
  • Polymethacrylate resins are common as sheet or in laminates as external thermoplastic resinous ' laminae.
  • Suitable methacrylic resins herein embrace those polymers or resins resulting from the polymerization of one or more methacrylates such as, for instance, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, etc. Copolymers of acrylic and methacrylic monomers are also included within the term acrylic resin as it appears herein.
  • the polymerization of the monomeric acrylates and methacrylates to provide the polyacrylate resins useful in the practice of the invention may be accomplished by any of the well known polymerization techniques.
  • a preferred acrylic resin is poly(methylmethacrylate) .
  • Suitable thin glass is presently in production and may be obtained commercially.
  • Thin glass is made by a draw down process in various thicknesses ranging from about 3 mils to about 20 mils. Pilot plant processes have produced such glass in thicknesses down to 0.3 mils. Though the above method is currently used to produce thin glass and the above thicknesses are available on the market the scope of the invention is in no way intended to be restricted by them. Any thin glass having a thickness of from about 0.3 mil to about 20 mil is suitable.
  • Suitable UV cured adhesive interlayers are the photoreaction products of any commonly used solventless UV curable adhesive. It is a requirement that the cured adhesive be generally flexible and that the uncured adhesive have a sufficiently low viscosity so as to flow easily. From the physical limitations of the application, it is understood that the adhesive may not be cured in the presence of a solvent, that by-products such as water or gas may not be generated during the cure, and that the adhesive must be compatible with the underlying substrate. However, while those skilled in the art may imagine other solventless UV curable adhesives meeting the above requirements, the photosensitized acrylates, the photosensitized epoxies, and the photosensitized thiol-enes are preferred.
  • Suitable acrylates or methacrylates of the adhesive interlayer are homopolymers, copolymers, terpolymers, etc., of acrylic or methacrylic monomers, which may additionally contain cross-linking copolymers including (1) polyfunctional acrylic or methacrylic monomers with a polyvalent hydrocarbon ester group; and/or (2) polyfunctional acrylic or methacrylic modified polymeric monomers wherein unbranched or branched polymer chains are terminated with functional acrylic or methacrylic.end groups or mixtures thereof. Additionally, minor amounts of other aliphatically unsaturated organic monomers such as vinyl or allyl monomers may be present.
  • Suitable cross-linking polyfunctional acrylic or methacrylic monomers with polyvalent ester groups of class (1) above are represented by the general formula:
  • n is an integer having a value of 2,3,or 4; has less than 20 carbons and is selected from the group consisting of n valent aliphatic organic residue, n valent organic residue having a cycloaliphatic constituent, and n valent organic residue having an aromatic constituent; and R* is selected from the group consisting of a methyl radical or hydrogen.
  • a preferred diacrylate is 1,6 hexanediol diacrylate
  • a suitable triacrylate is pentaerythritol triacrylate
  • a suitable tetraacrylate is pentaerthritol tetraacr late.
  • Preferred polyfunctional acrylic or methacrylic monomers of Formula 1 are represented by the general formula:
  • Q is n valent organic residue selected from C . 1-1 81 a ⁇ phatics, . , 3 _- j2) cycloaliphatics, and g ⁇ g ⁇ aromatics;
  • R* is hydrogen or a methyl radical;
  • R is an alkylene and n is 2,3,or 4.
  • Radicals included by Q of Formula (2) are, for example, alkylene radicals, such as ethylene, hexa ethylene, etc.; arylene, such as phenylene, tolylene, xylylene,
  • radicals included by R are, for example, methylene, ethylene, propylene, etc.
  • Suitable polyfunctional acrylic or methacrylic modified polymeric monomers of class (2) above are branched or unbranched polyesters, polyethers, polyamines, polyimides, polyamides, polycarbonates, polyurethanes, epoxies, etc. having at least two terminal acrylic or methacrylic functional groups.
  • These modified polymeric monomers are represented by the general formula:
  • m is 1 to 100 or more.
  • Formula (3) contains a urethane linkage.
  • These modified polymeric monomers may be represented by the general formula: (7)
  • the major constituent of the UV curable acrylic composition in the instant invention are acrylic and methacrylic monomers. Suitable such monomers are represented by the general formula:
  • R is defined above, and R is a monovalent aliphatic organic radical.
  • R may be a lower ( 1 -C 2Q ) alkyl acrylic ester or mixtures thereof, e.g. methyl acrylate, ethyl acrylate, methyl methylacrylate, ethyl methacrylate. Included within R are also epoxide, carboxyl, hydroxyl, etc. ester groups if no crosslinking is present.
  • Suitable acrylic and methacrylic monomers are those monomers wherein the ester group contains a urethane linkage. These monomers are represented by the general formula:
  • R is selected from c ⁇ -8 ) alkylene, for example methylene, ethylene, propylene
  • R is selected from ., - g ⁇ aliphatic radicals and Cl.b,- n io o .) aromatic radicals, for example alkyl radicals, such as methyl, ethyl, propyl, butyl, etc. and aryl radicals, such as phenyl, xylyl, tolyl, etc.
  • Particularly useful and preferred acrylates of Formula (9) are N-n-butyl-acryloxyethyl carbonate, 2-acryloxyethyl N-phenyl carbonate, 2-methacryloxypropyl N-phenyl carbonate, 2-acryloyloxypropyl N-phenyl carbonate, etc.
  • UV radiation photosensitizers for the acrylics are well known.
  • Some non-limiting examples of these UV radiation photosensitizers include ketones, such as benzophenone, acetophenone, benzil, benzyl methyl ketone; benzoins and substitute benzoins such as benzoin methyl ether, alpha-hydroxymethyl benzoin isopropyl ether; halogen containing compounds such as alpha-bromoacetophenone, p-bromoacetophenone, alpha-chloromethylnaphthalene; sulfur compounds such as aromatic disulfides; and other photosensitizers such as azides, thioketones, or mixture or synergistic.
  • ketones such as benzophenone, acetophenone, benzil, benzyl methyl ketone
  • benzoins and substitute benzoins such as benzoin methyl ether, alpha-hydroxymethyl benzoin isopropyl ether
  • diary1 perioxides the diary1 perioxides; the hydroperoxides; the peracids and peresters; and azo compounds; or any other known free radical initiator, such as di-t-butyl peroxide, benzoyl peroxide,
  • the photosensitized epoxy resins of the present invention are homopolymers, copolymers, terpolymers, etc. of the photopolymerization products of monofunctional epoxy monomers with polyfunctional epoxy monomer cross linking agents.
  • the functional epoxy groups are usually present on the monomer as a glycidyl epoxy group, a cycloaliphatic epoxy group, a vinyl epoxy group, an internal epoxy group, or a methyl glycidyl epoxy group.
  • Preferred functional epoxy groups are the glycidyl epoxy group, the cycloaliphatic epoxy group, and the vinyl epoxy group.
  • Suitable polyfunctional epoxy monomer cross linking agents are polyfunctional epoxy organic molecules or epoxy terminated branched or unbranched polymer chains.
  • the epoxy terminated polymer chains are, for example, epichlorohydrin - BPA resins, glycidyl ether terminated diol-diisocyanante'resins, polyethylene oxide diglycidyl ether, polypropyleneoxide diglycidyl ether, bisepoxy dicylcopentyl succinate, cresol-novolac epoxy resins, etc.
  • the polyfunctional epoxy organic molecules are, for example: cycloaliphatic epoxides, such as vinyl cyclohexene dioxide, bis(3,4-epoxy-6- methylcyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, etc; aliphatic polyepoxides, such as the diglycidyl ethers or diglycidyl esters resulting from the reaction of for example ethylene glycol, propylene glycol, 1,6 hexanedicarboxylic acid, etc.
  • cycloaliphatic epoxides such as vinyl cyclohexene dioxide, bis(3,4-epoxy-6- methylcyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, etc
  • aliphatic polyepoxides such as the dig
  • any epoxide adhesive interlayer composition of the present invention are the monofunctional epoxies.
  • These monofunctional epoxies may have any of the above named epoxide functional groups attached to either an aliphatic or aromatic hydrocarbon radical.
  • the monofunctional epoxies are alpha-olefin oxides of the general formula:
  • R 8 is methyl or hydrogen and R9 may be hydrogen, a c g_4g ⁇ aromatic organic radical, but is preferably a ,. 3Q . aliphatic organic radical.
  • Preferred monofunctional epoxide monomers of Formula (10) are, for example,
  • UV sensitizers may be known, • suitable UV sensitizers for use with the epoxies are disclosed in U.S. Pat. Nos. 4,319,974, 4,407,759, 4,250,311, 4,264,703, 4,310,469 assigned to the same assignee as the present invention. These disclosures are incorporated herein by reference.
  • the thiol-ene resins can be cured by the use of such photoinitiators as, for example, benzophenone, acetaphenone, dibutyl ketone, etc.
  • Acrylic, epoxy, or thiol-ene adhesive interlayer compositions may be prepared from the above suitable acrylic monomers, the above preferred urethane ester acrylic monomers, the above epoxy monomers, or the above thiol-enes according to methods well known to the art. Each class of monomers are blended with an appropriate UV initiator and optional additives discussed below to form a generally homogenous composition.
  • the selection of particular monomers and ratios of monomers, photoinitiators, and additives lies within the skill of the art for meeting the criterion of low viscosity in the uncured composition, flexibility in the cured composition, and good adhesive properties.
  • the viscosity of the uncured composition should be low enough to allow for application of the thin glass to the substrate and the flexibility of the cured adhesive must be sufficient to retain impact strength and adhesion in the finished laminate.
  • non-crosslinking monomers should constitute the majority of any UV curable adhesive composition.
  • the adhesive interlayer compositions of the instant invention may also optionally contain various surface active agents, thixotropic agents, and UV light absorbers. All of these additives and the use thereof are well known in the art and do not require extensive discussions.
  • any compounds possessing the ability to function in such a manner i.e., as a surface active agent, UV light absorber, and the like, can be used so long as they do not deleteriously affect the photocuring of the primer compositions and do not adversely affect the non-opaque character of the coated polycarbonate article.
  • suitable ultraviolet light absorbing compounds may be added to the UV curable adhesive interlayer composition in an effective amount to. rotect a sensitive substrate from the degradative effects of ultraviolet light, provided they do not unduly interfere with or hinder the photocure of the adhesive interlayer composition.
  • the benzophenones and benzotriazoles may be used in controlled amounts, the latent ultraviolet light absorbers are preferred.
  • suitable latent ultraviolet light absorbing compounds are the salicylates, such as, p-octylphenyl salicylate, phenyl salicylate, t-butyl phenyl salicylate, and the like, and the monobenzoates, such as, resorcinol monobenzoate and the like.
  • the photocurable compositions are first compounded by adding together the monomer mixture, the UV photoinitiator, and optionally, any of the aforementioned additives.
  • the various components are thoroughly mixed to form a generally homogenous adhesive interlayer composition.
  • the composite of thin glass interposing UV curable adhesive composition and thermoplastic substrate is. laid up prior to or simultaneously with the UV cure of the adhesive composition.
  • a thin, uniform film of the adhesive composition is applied onto a substrate such as polycarbonate sheet by any of the known means such as dipping, spraying, roll-coating, and the like.
  • the adhesive layer composition is applied in an amount sufficient to provide a cured film or layer of from about 0.1 mils to about 20 mils in thickness.
  • Thin glass is laid on to the uncured adhesive composition by any suitable method.
  • a sufficiently low viscosity of the adhesive interlayer allows air bubbles, and excess adhesive to be easily removed.
  • such low viscosity of the adhesive interlayer composition provides for minimal stresses on the glass.
  • a large or especially thin sheet of the glass must be supported or otherwise specially handled during its application to the uncured adhesive interlayer. This may involve the optional use of a UV transparent supportive backing lightly adhered to the glass on the side opposite the uncured adhesive interlayer.
  • the uncured adhesive interlayer may be injected between a spaced arrangement of thin glass on a supportive backing and the thermoplastic resinous substrate.
  • a spaced arrangement of thin glass on a supportive backing and the thermoplastic resinous substrate.
  • thermoplastic resinous substrate The composite of thermoplastic resinous substrate, adhesive interlayer composition, and thin glass with optional supportive backing is subjected to UV radiation in such a way that the uncured adhesive interlayer is irradiated through the thin glass.
  • the uncured adhesive interlayer may also be irradiated through a suitable UV transparent resinous substrate, many such substrates are sensitive to UV radiation and others may not be transparent to the UV radiation.
  • Suitable UV irradiation can have a wavelength of from 2537 A. to 4000 A.
  • the lamp systems used to generate such radiation may be an ultraviolet lamp which may be any discharge lamp, as for example, xenon, metallic halide, metallic arc, low or high pressure mercury vapor discharge lamps etc., having generating pressure of from as low as a few milli-torr up to about 10 atmospheres, can be employed.
  • an ultraviolet lamp which may be any discharge lamp, as for example, xenon, metallic halide, metallic arc, low or high pressure mercury vapor discharge lamps etc., having generating pressure of from as low as a few milli-torr up to about 10 atmospheres, can be employed.
  • a lightly adhered supportive backing prevents the fragile glass from breaking or shattering during lay on and is subsequently removable from the surface of the thin glass following cure of the adhesive interlayer.
  • the supportive backing must be easily removable following cure by either mechanical or chemical means, flexible to facilitate the application of the glass to the uncured adhesive interlayer, and transparent to UV radiation to permit the UV cure of the adhesive interlayer through the thin glass.
  • the supportive backing may be a sheet which is inherently tacky or has an organic adhesive coat on at least one side such as a contact adhesive sheet or it may be a backing applied to the thin sheet glass as a liquid and subsequently hardened by either polymerization, crosslinking, evaporation of a solvent, or any combination thereof to a highly viscous of.flexible but solid state.
  • Suitable supportive backings are sheets of polymeric materials, cellophane, glass, and others. Suitable organic adhesive coats applied to such sheets when necessary to provide tackiness are the siloxanes, epoxies and the acrylics. These and other suitable adhesives for such use are disclosed in the Handbook of Adhesives, 2nd Edition, Van Nostrand Reinhold Company, New York, N.Y., 1962, which is incorporated herein by reference. Suitable supportive backings for application to the thin glass as a liquid may be any UV transparent organic substance which will adhere to the giass and dry, polymerize, or crosslink to a highly viscous or $ flexible but solid state thereby providing support to the glass during subsequent processing.
  • Example 1 Hydroxyethyl acrylate (47 g, 0.4 moles), butyl isocyanate (40 g, ' 0.4 moles), dibutyltin dilaurate (0.01 g) and ⁇ -butyl catechol (0.1 g) were combined 0 and stirred at 75°C for 7 hours to give
  • HEABI N-n-butyl-acryloxyethyl carbamate
  • Example 2 A UV-curable adhesive interlayer composition was 5 made by combining 10 pbw of HEABI from Example 1 with 0.1 pbw of diethyoxyacetophenone.
  • Example 3 A layer of thin glass manufactured by Corning Glass of Elmira, N.Y. was bonded to a LEXAN resin 0 polycarbonate sheet by 1) placing a 6" x 6" piece of 2 mil thin glass on a glass plate, 2) placing a portion of UV-curable composition from Example 2 on the thin glass, 3) placing a 4" x 4" x 1/4" LEXAN sheet panel on the curable composition, 4) squeezing out and $ removing excess UV-curable composition so that no bubbles remain, and 5) curing in a Model 1202AN PPG UV Processor at a belt speed of 20'min in a nitrogen flow of 20 standard cubic ft/min by placing the sample with the glass facing up. Excess glass was trimmed from the edges. 5
  • Example 4 A layer of thin glass manufactured by Corning Glass of Elmira, N.Y. was bonded to a LEXAN resin 0 polycarbonate sheet by 1) placing a 6" x 6" piece of 2 mil thin glass on a glass plate,
  • the surface protected polycarbonate sheet from Example 3 was tested for adhesion by scribing the glass with.a 1 mm Gitter4.000prufgerat Crosshatch adhesion cutter, applying Mystik 6432 tape to the 10 crosshatched area, and rapidly pulling the tape away from the scribed area. The glass was not removed by the tape.
  • Example 5 The sample from Example 3 was tested for impact 15 resistance by impacting the side away from the glass (reverse impact) in a Gardner Falling Dart Tester set at 320 in-lbs. Although the glass cracked, it remained bonded to the polycarbonate. The polycarbonate was ductile and had no cracks in this 20. test.
  • Example 6 The sample from Example 3 was tested for abrasion resistance using 1000 cycles of abrasing on a Model 174 Taber Abraser equipped with CS-10F wheels and 500 25 gm weights. The difference in haze after Taber abrasing, measured using a Gardner Model UX10 Hazemeter, was found to be 1.2%. The glass surface was not subject to scratching by sharp objects.
  • Example 7 30 The procedure of Example 3 was repeated to make a surface protected polycarbonate sheet except 10 pbw of HEABI from Example 2 containing 0.5 pbw of resorcinol monobenzoate was used.
  • Example 8 35 The procedure of Example 7 was repeated to make a surface protected polycarbonate sheet except 10 pbw of HEABI from Example 2 containing 1 pbw of resorcinol monobenzoate was used as the adhesive interlayer.
  • a UV-curable adhesive composition was made by combining 10 pbw of HEABI from Example 1 with 0.2 pbw benzophenone and 0.2 pbw methyldiethanol amine.
  • Example 10 A 10 mil sheet of thin glass manufactured by Corning Glass of Elmira, N.Y. was bonded to a LEXAN resin polycarbonate sheet by the steps of 1) adhering to the thin glass from a solvent spray a 1-2 mil layer of a UV transparent polymer, sold under the name Krylon by Borden, Inc.

Landscapes

  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Une méthode pour protéger les substrats thermoplastiques contre l'abrasion et l'attaque par des solvants consistant à faire adhérer une feuille de verre mince, d'une épaisseur comprise entre environ 0.3 mils et environ 20 mils, à l'aide d'une composition adhésive photopolymérisable exempte de solvants, et à irradier ladite composition adhésive pour en réaliser la polymérisation.
EP85904055A 1984-08-13 1985-08-13 Methode permettant d'appliquer une faible epaisseur de verre a un substrat resineux thermoplastique Withdrawn EP0190289A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64033784A 1984-08-13 1984-08-13
US640337 1984-08-13

Publications (1)

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EP0190289A1 true EP0190289A1 (fr) 1986-08-13

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EP85904055A Withdrawn EP0190289A1 (fr) 1984-08-13 1985-08-13 Methode permettant d'appliquer une faible epaisseur de verre a un substrat resineux thermoplastique

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Country Link
EP (1) EP0190289A1 (fr)
JP (1) JPS61503016A (fr)
WO (1) WO1986001153A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP0429668B1 (fr) * 1989-06-16 1995-12-13 Dai Nippon Insatsu Kabushiki Kaisha Pellicule a enrobage souple
DE4427471A1 (de) * 1994-08-03 1996-02-08 Henkel Kgaa Einkomponentiger Reaktionsklebstoff
DE19501933A1 (de) * 1995-01-24 1996-07-25 Henkel Kgaa Aerob härtbarer Klebstoff

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DE1629350A1 (de) * 1966-02-16 1971-05-19 Deutsche Spiegelglas Ag Mit UEberzug versehene,kratzfeste,chemisch und mechanisch widerstandsfaehige Kunststoffscheibe
GB1191011A (en) * 1966-07-01 1970-05-06 Ford Motor Co Coating Process Involving Radiation Curing of Coating
GB1417974A (en) * 1971-12-10 1975-12-17 Lemoine H G Adhesive tape assembly and a method of use thereof
GB1461255A (en) * 1972-11-09 1977-01-13 Ici Ltd Laminating process
US4328277A (en) * 1974-04-26 1982-05-04 General Electric Company Impact resistant laminate
DE2606569A1 (de) * 1976-02-19 1977-08-25 Degussa Verfahren zur herstellung von beschussfesten verbund(glas)scheiben
JPS546005A (en) * 1977-06-15 1979-01-17 Tazumi Seikiyou Kk Multiilayer glass and method of joining same
JPS5740101A (en) * 1980-08-22 1982-03-05 Hitachi Ltd Device for converting rotational frequency into oil pressure
DE3225691A1 (de) * 1981-10-29 1983-05-11 General Electric Co., Schenectady, N.Y. Verfahren zur herstellung verbesserter sicherheitsglaslaminate
JPS58136672A (ja) * 1982-02-09 1983-08-13 Nippon Synthetic Chem Ind Co Ltd:The ポリカ−ボネ−ト成型物用の光硬化型接着剤組成物
JPS58138766A (ja) * 1982-02-10 1983-08-17 Nippon Synthetic Chem Ind Co Ltd:The ガラス用の光硬化型接着剤組成物
NZ205990A (en) * 1982-11-05 1987-04-30 Deltaglass Sa Radiation-curable, urethane acrylate-containing liquid adhesive composition and glass laminates

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Title
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Also Published As

Publication number Publication date
WO1986001153A1 (fr) 1986-02-27
JPS61503016A (ja) 1986-12-25

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