EP2035470A1 - Compositions de résine thermoplastique pour usage dans des stratifiés transparents - Google Patents

Compositions de résine thermoplastique pour usage dans des stratifiés transparents

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Publication number
EP2035470A1
EP2035470A1 EP06773705A EP06773705A EP2035470A1 EP 2035470 A1 EP2035470 A1 EP 2035470A1 EP 06773705 A EP06773705 A EP 06773705A EP 06773705 A EP06773705 A EP 06773705A EP 2035470 A1 EP2035470 A1 EP 2035470A1
Authority
EP
European Patent Office
Prior art keywords
tert
butyl
bis
hydroxy
laminate
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Withdrawn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
EP06773705A
Other languages
German (de)
English (en)
Inventor
Jerrel C. Anderson
Richard A. Hayes
Steven C. Pesek
John W. Paul
C. Anthony Smith
Stephen J. Bennison
Sam L. Samuels
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and 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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2035470A1 publication Critical patent/EP2035470A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Definitions

  • the present invention relates to transparent laminate articles. More specifically, the present invention relates to resin compositions suitable for use as an intermediate layer in transparent laminate articles.
  • Glass laminated products have contributed to society for almost a century. Beyond the well known, every day automotive safety glass used in windshields, glass laminates are used in most forms of the transportation industry. They are utilized as windows for trains, airplanes, ships, and nearly every other mode of transportation. Safety glass is characterized by high impact and penetration resistance and does not scatter glass shards and debris when shattered. Glass laminates find widespread use in architectural applications, as well.
  • Safety glass typically consists of a sandwich of two glass sheets or panels bonded together with an interlayer of a polymeric film or sheet which is placed between the two glass sheets.
  • One or both of the glass sheets may be replaced with optically clear rigid polymeric sheets such as, for example, sheets of polycarbonate materials.
  • Safety glass has further evolved to include multiple layers of glass and/or polymeric sheets bonded together with interlayers of polymeric films or sheets.
  • the newer products are designed to maintain their integrity when a glass laminate is subjected to high force winds and impacts of flying debris as occur in a hurricane or where there are repeated impacts on a window by a criminal attempting to break into a vehicle or structure.
  • glass laminated products have now reached the strength requirements for being incorporated as structural elements within buildings. An example of this is the glass staircases that are now being featured in many buildings.
  • the interlayer is typically made with a relatively thick polymer film or sheet that exhibits toughness and adheres to the glass in the event of a crack or crash.
  • polymeric interlayers have been developed to produce laminated products. In general, it is desirable that these polymeric interlayers possess acceptable levels of: optical clarity (haze of less than 4%), impact resistance, penetration resistance, ultraviolet light resistance, long term thermal stability, adhesion to glass and/or other rigid polymeric sheets, ultraviolet light transmittance, moisture absorption, moisture resistance, long term weatherability, among other characteristics.
  • Widely used interlayer materials include complex multi-component compositions comprising polymers such as: polyvinylbutyral (PVB); polyurethane (PU); polyvinylchloride (PVC); metallocene-catalyzed linear low density polyethylenes; ethylene vinyl acetate (EVA); ethylene acid copolymer ionomers; polymeric fatty acid polyamides; polyester resins such as poly(ethylene terephthalate); silicone elastomers; epoxy resins; elastomeric polycarbonates; and the like. Acid copolymers have become more widespread in their use for fabricating transparent laminates.
  • PVB polyvinylbutyral
  • PU polyurethane
  • PVC polyvinylchloride
  • EVA ethylene vinyl acetate
  • EVA ethylene acid copolymer ionomers
  • polymeric fatty acid polyamides polyester resins such as poly(ethylene terephthalate); silicone elastomers; epoxy resins; elastomeric polycarbon
  • U.S. Patent No. 3,344,014 discloses laminated glass products with an ethylene copolymer ionomer interlayer.
  • U.S. Patent No. 3,404,134 discloses a process of ionicaliy crosslinking certain copolymers which contain carboxylic acids.
  • U.S. Patent No. 4,663,228 and U.S. Patent No. 4,668,574 each discloses a transparent laminated article which includes a water insoluble ionomer resin film comprising the metal salt of an ionomer resin prepared from ethylene and methacrylic acid monomers.
  • U.S. Patent No. 5,344,513 discloses a method for manufacturing a laminated transparent substrate which includes an ethylene copolymer ionomer interlayer.
  • Patent No. 5,759,698 discloses laminated glass which includes an interlayer comprising an ionomer resin of ethylene- methacrylic acid copolymer with a metal ion which has been thermoset with an organic peroxide and a silane coupling agent.
  • U.S. Patent No. 5,763,062 discloses a transparent article comprising an extruded ionomer resin film or sheet having a carboxylic acid content of between about 17 and 40 weight percent, said ionomer resin being essentially free of amines.
  • 6,238,801 each discloses a glazing which includes a transparent layer of an ionomer resin with improved adhesion through the use of a metal chelate.
  • U.S. Patent No. 6,150,028 discloses glass laminates which include ionomer resin interlayers and glass with solar control characteristics.
  • U.S. Patent No. 6,187,845 discloses red shifted benzotriazole UV absorbers for use in adhesives for glass laminates.
  • U.S. Patent No. 6,191 ,199 discloses hydroxphenyl-s-triazine UV absorbers for use in adhesives for glass laminates.
  • U.S. Patent No. 6,268,415 discloses stabilized adhesive compositions which contain certain benzotriazole UV absorbers.
  • U.S. Patent No. 6,432,522 discloses optically transparent glazing which includes interlayers comprising ethylene methacrylic acid copolymers that incorporate 15 to 17 weight percent of the acids and that are partially neutralized with sodium.
  • 2002/0155302 discloses a method for preparing a transparent laminated article which includes an interlayer comprising a copolymer of an olefin with 13 to 21 weight percent of methacrylic or acrylic acid monomers partially neutralized with an alkali cation.
  • U.S. Patent Application No. 2003/0044579 discloses a method for preparing a transparent laminated article which includes an interlayer comprising a copolymer of an olefin with 13 to 22 weight percent of methacrylic or acrylic acid monomers partially neutralized with an alkali cation.
  • WO 99/58334 discloses transparent laminates which comprise a polymer of ethylene and methacrylic acid or acrylic acid containing about 14 to 24 weight percent of the acid and having about 10 to 80 percent of the acid neutralized with a metallic ion.
  • WO 00/64670 discloses transparent laminates which comprise a polymer of ethylene and methacrylic acid or acrylic acid containing about 14 to 24 weight percent of the acid and having about 10 to 80 percent of the acid neutralized with a metallic ion.
  • WO 01/60604 discloses a laminated glazing that includes an infra-red reflecting film bonded between a ply of ionomer resin and a ply of a polymer material.
  • Intl. Patent Appln. Publn. No. WO 2004/011755 discloses transparent laminates which comprise a polymer of ethylene and methacrylic acid or acrylic acid containing about 14 to 28 weight percent of the acid and having about 20 to 60 percent of the acid neutralized with a metallic ion.
  • Another area of improvement for these copolyethylene ionomeric interlayers would be enhanced adhesion to the glass or rigid material in a laminate.
  • the recommended cooling rate for laminates comprising conventional acid copolymer ionoplast resins is at least 5°F per minute (2.78°C/min) or greater.
  • a laminate prepared using conventional conditions and a conventional ionoplast resin as interlayer material be cooled from an autoclave temperature of 275°F (135 0 C) to a temperature of 104 0 F (40 0 C) in less than about 35 minutes.
  • this is not a trivial process condition because manufacturing processes are typically carried out under less than ideal conditions.
  • an improved resin composition for the purpose of increasing adhesion to rigid substrates, particularly adhesion to glass. It can be even more desirable to have such a resin provide a laminate with at least the same, or preferably improved impact resistance and toughness. Further, it can be desirable to prepare such a resin wherein an interlayer sheet produced from the resin has improved toughness relative to conventional interlayers. Moreover, it can be desirable to have all of these properties in a laminate that provides good optical clarity when designed for uses where optical clarity is a requirement.
  • the present invention is an ionoplast resin composition
  • an ionoplast resin composition comprising or consisting essentially of an ethylene acid copolymer and optionally, an effective amount of at least one additive
  • the ethylene acid copolymer comprises or consists essentially of residues derived from ethylene and from about 20 to about 30 wt% of residues derived from carboxylic acids selected from the group consisting of ⁇ , ⁇ -unsaturated acids having from 3 to 8 carbons, and from about 10% to about 90 % of the carboxylic acid residues are neutralized
  • the ethylene acid copolymer has a melt index of about 60 g/10 min or less prior to neutralization
  • the least one additive is selected from the group consisting of hindered amine light stabilizers (HALS), ultraviolet (UV) light absorbers, and thermal stabilizers.
  • HALS hindered amine light stabilizers
  • UV ultraviolet
  • the present invention is a shaped article comprising the resin composition of the present invention.
  • the present invention is a multilayer film or sheet comprising at least one layer comprising the resin composition of the present invention.
  • the present invention is a transparent interlayer obtained from the resin composition of the invention.
  • the present invention is a laminate article comprising at least one transparent interlayer of the invention.
  • the present invention is a process for preparing a transparent laminate article having a haze of about 3% or less, comprising the steps of: (a) extruding at a temperature of from about 175 0 C to about 250 0 C, an interlayer sheet of the invention; (b) fabricating a laminate from the interlayer by (1) setting up the interlayer and at least one other laminate layer to form a pre-laminate assembly and (2) heating the pre-laminate assembly to a temperature of at least about 12O 0 C and applying pressure or vacuum to the assembly for a period of time and (3) cooling the laminate to obtain the transparent laminate.
  • (meth)acrylic as used herein, alone or in combined form, such as “(meth)acrylate”, refers to acrylic and/or methacrylic, for example, acrylic acid and/or methacrylic acid, or alkyl acrylate and/or alkyl methacrylate.
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such.
  • ranges set forth herein include their endpoints unless expressly stated otherwise. Further, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed.
  • the present invention is an improved ionoplast resin composition, particularly suitable for use in the manufacture of transparent laminates.
  • An ionoplast resin composition of the present invention comprises or consists essentially of an ethylene acid copolymer and optionally, an effective amount of at least one additive, wherein (i) the ethylene acid copolymer comprises or consists essentially of units derived from ethylene and from about 20 wt% to about 30 wt% of units derived from ⁇ , ⁇ -unsaturated carboxylic acids having from 3 to 8 carbons and (ii) the at least one additive is selected from the group consisting of hindered amine light stabilizers (HALS), ultraviolet (UV) light absorbers, and thermal stabilizers.
  • HALS hindered amine light stabilizers
  • UV ultraviolet
  • the ethylene acid copolymer comprises or consists essentially of units derived from ethylene and from about 20.5 to about 30 wt% of units derived from ⁇ , ⁇ -unsaturated carboxylic acids having from 3 to 8 carbons. More preferably, the ethylene acid copolymer comprises or consists essentially of units derived from ethylene and from about 21 to about 25 wt% of units derived from ⁇ , ⁇ -unsaturated carboxylic acids having from 3 to 8 carbons. Even more preferably, the ethylene acid copolymer comprises or consists essentially of units derived from ethylene and from about 21 to about 23 wt% of units derived from ⁇ , ⁇ -unsaturated carboxylic acids having from 3 to 8 carbons.
  • control of the final acid level in a copolymer of the present invention is not exact, and therefore the range of acid in a final product can vary within about + 1 wt% of the disclosed ranges without departing from the intended scope of the present invention.
  • various acid levels can be preferred. For example, in some cases an acid level of about 20 wt% (that is 20+1 wt%) can be preferred, in other cases it can be preferred to have an acid level of about 20.5 + 1 wt%, about 21 ⁇ 1 wt%, or about 22 ⁇ 1 wt%.
  • Suitable carboxylic acid monomers whose residues may be comprised in the ethylene acid copolymer of the present invention includes, but not limited to, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, monomethyl maleic acid, and mixtures thereof.
  • the ethylene acid copolymers of the present invention may optionally further comprise residues of other unsaturated comonomers.
  • Such unsaturated comonomers may be selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, octyl acrylate, octyl methacrylate, undecyl acrylate, undecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, iso
  • Acrylic acid and methacrylic acid are preferred acid comonomers.
  • the ethylene acid copolymers of the present invention may be polymerized as disclosed, for example, in US Patent Nos. 3,404,134; 5,028,674; 6,500,888 and 6,518,365.
  • the ethylene acid copolymers of the present invention are at least partially neutralized, and exist as partial salts comprising metal ions.
  • the metal ions may be monovalent, divalent, trivalent, multivalent, or mixtures of ions having the same or different valencies.
  • Exemplary monovalent metal ions include, but are not limited to, sodium, potassium, lithium, silver, mercury, copper, and mixtures thereof.
  • Exemplary divalent metal ions include, but are not limited to, beryllium, magnesium, calcium, strontium, barium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel, zinc, and mixtures thereof.
  • Exemplary trivalent metal ions include, but are not limited to, aluminum, scandium, iron, yttrium, and mixtures thereof.
  • Exemplary multivalent metal ions include, but are not limited to, titanium, zirconium, hafnium, vanadium, tantalum, tungsten, chromium, cerium, iron, and mixtures thereof.
  • the ethylene acid copolymers of the present invention have from about 10% to about 90% of the carboxylic acid groups neutralized.
  • the ethylene acid copolymers of the present invention are from about 15% to about 45% neutralized, and more preferably from about 20% to about 35% neutralized. Even more preferably, the copolymers are from about 25% to about 35% neutralized.
  • the ethylene acid copolymers of the present invention may be neutralized as disclosed, for example, in U.S.
  • the ionoplast resin composition of the present invention when used to prepare a laminate of the present invention, exhibits improved toughness relative to what would be expected of a laminate comprising a higher acid content in the interlayer as described herein. Without being held to theory, it is believed that improved toughness in the present invention is obtained by preparing an ethylene acid copolymer base resin with a lower melt index (Ml) before it is neutralized.
  • a base resin of the present invention preferably has a Ml of less than 60 grams/10 min as determined at 190 0 C, and more preferably less than 55 grams/10 min.
  • the Ml is less than 50 grams/10 min. Even more preferably the Ml is less than 35 grams/10 min. After neutralization, the Ml can be less than 2.5 grams/10 min, and possibly less than 1.5 g/10 min.
  • the compositions of the invention also include one or more additives selected from the group consisting of hindered amine light stabilizers (HALS), ultraviolet (UV) light absorbers, and thermal stabilizers. Any HALS known or presently unknown within the art may be utilized in the present invention.
  • HALS are disclosed to be secondary, tertiary, acetylated, N-hydrocarbyloxy substituted, hydroxy substituted, N- hydrocarbyloxy substituted, or other substituted cyclic amines which further incorporate steric hindrance, generally derived from aliphatic substitution on the carbon atoms adjacent to the amine function.
  • Exemplary HALS that may be comprised in the composition of the present invention include, but not limited to, 1,5,8,12-tetrakis[4,6-bis(N-butyl-N- 1 ,2,2,6,6-pentamethyl-4-piperidylamino)-1 ,3,5-triazin-2-yl]-1 ,5,8,12- tetraazadodecane, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 - octyloxy ⁇ 2,2,6,6-tetramethyl-4-piperidyl)sebacate, poly[[6-[(1 ,1 ,3,3- tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4- piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidylimino]], poly[
  • 2,2,6,6-tetramethylpiperidinyl)sebacate 2-(2-hydroxyethylamino)-4,6- bis ⁇ N-[1-(cyclohexyloxy)-2,2,6,6-tetramethylpi peridin-4 ⁇ yl]-butylamino-s- triazine, oligomer of N- ⁇ [2-(N-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]- s-triazin-4-yl ⁇ -N,N '-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1 ,6- hexanediamine terminated with 2,4-bis(dibutylamino)-s-triazin-6-yl,
  • compositions of the present invention may comprise from about 0.01 to about 10.0 wt% of the HALS and preferably, from about 0.01 to about 5.0 wt%. More preferably, the compositions of the present invention comprise from about 0.01 to about 1.0 wt% of the HALS. Most preferably, the compositions of the present invention comprise from about 0.01 to about 0.5 wt% of the HALS.
  • Any UV light absorbers known or yet to be known within the art may find utility in the present invention.
  • the general classes of UV absorbers including benzotriazoles, hydroxybenzophenones, hydroxyphenyl triazines, esters of substituted and unsubstituted benzoic acids, are within the definition of UV light stabilizers of the present invention.
  • Exemplary UV absorbers that may be contained in the present compositions include, but not limited to, 2,4-dihydroxybenzophenone,2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-
  • compositions of the present invention may contain from about 0.01 to about 10.0 wt% of UV light absorbers, or preferably, from about 0.01 to about 5.0 wt%. More preferably, the compositions of the present invention contain from about 0.01 to about 1.0 wt% of UV light absorbers. Most preferably, the compositions of the present invention contain from about 0.01 to about 0.5 wt% of UV light absorbers.
  • thermal stabilizers may also be contained in the present composition.
  • any known or yet to be known thermal stabilizers may find utility in the present composition.
  • Commonly known classes of thermal stabilizers include phenolic antioxidants, alkylated monophenols, alkylthiomethylphenols, hydroquinones, alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, O-, N- and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, aminic antioxidants, aryl amines, diaryl amines, polyaryl amines, acylaminophenols, oxamides, metal deactivators, phosphites, phosphonites, benzylphosphonates, ascorbic acid (vitamin C), compounds which destroy peroxide, hydroxylamines, nitrones, thiosynergists, benzofuran
  • thermal stabilizers of the present invention include, but not limited to, 2,6-di-tert-butyl-4- methylphenol, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-4,6-dimethylphenol,
  • EP-A-0589839 and EP-A-0591102 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert- butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]- benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2- hydroxyethoxylphenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4- ethoxyphenyl)benzofuran-2-one, 3 ⁇ (4-acetoxy-3,5-dimethylphenyl)-5,7-di ⁇ tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7 ⁇ di- tert-butylbenzofuran-2-
  • compositions of the present invention may include from about 0.01 to about 10.0 wt% of thermal stabilizers, or preferably from about 0.01 to about 5.0 wt%. More preferably, the compositions of the present invention contain from about 0.01 to about 1.0 wt% of thermal stabilizers. Most preferably, the compositions of the present invention contain from about 0.01 to about 0.3 wt% of thermal stabilizers.
  • the ionoplast resin composition of the present invention may further comprise other additives such as plasticizers, colorants, processing aides, flow enhancing additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, antiblocking agents such as silica, and the like.
  • additives such as plasticizers, colorants, processing aides, flow enhancing additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, antiblocking agents such as silica, and the like.
  • plasticizers which may be added to improve processing, final mechanical properties, or to reduce rattle or rustle of the films and sheets of the present invention, include, but not limited to, stearic acid, oleic acid, soybean oil, epoxidized soybean oil, corn oil, caster oil, linseed oil, epoxidized linseed oil, mineral oil, alkyl phosphate esters, Tween® 20 plasticizers, Tween® 40 plasticizers, Tween® 60 plasticizers, Tween® 80 plasticizers, Tween® 85 plasticizers, sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, citrate esters, such as trimethyl citrate, triethyl citrate, (Citroflex® 2 plasticizer, produced by Morflex, Inc.
  • ionomers of the present invention may also comprise an agent to prevent blocking.
  • an agent to prevent blocking may also comprise an agent to prevent blocking.
  • anti-block agents or processing aids is optional in the practice of the present invention, but preferred.
  • Conventional anti-blocking agents can be used, and one of ordinary skill in the art can determine whether such agents are desirable and at what level they should be used.
  • the present invention is sheet or film obtained from the ionoplast resin of the present invention.
  • a sheet or film of the present invention can be obtained, for example, by extruding the resin of the present invention using conventional or non-conventional means. Extrusion can be used to provide sheets of thickness ranging from about 0.38 to about 2.60 mm, or about 10 to about 200 mils, for example.
  • other conventional methods can be used, such as casting or blowing a film from the molten resin.
  • extrusion of an interlayer sheet is preferred.
  • Extrusion of an interlayer of the present invention can be carried out at a temperature in the range of from about 175°C to about 250 0 C.
  • An interlayer sheet of the present invention can be extruded without a surface pattern, but it is preferred that an interlayer of the present invention have a surface pattern to facilitate the process of removing air or gaseous vapors from the interfacial spaces of the laminate as it is fabricated.
  • the surface pattern can be applied either by known melt fracture techniques, or by use of an embossing tool, or by other conventional or non-conventional means.
  • the optical clarity of an interlayer comprising a surface pattern is poor relative to the transparent laminate that is eventually obtained from the interlayer.
  • the present invention is a laminate prepared from a sheet comprising a resin of the present invention.
  • a resin of the present invention In the glass laminating art, it is known that increased adhesion to glass can result in a laminate with diminished impact resistance.
  • the resins of the present invention have improved adhesion but also have improved impact resistance. Without being held to any theory, it is believed that this property results from the lower melt index of the improved resins relative to the conventional resins.
  • Adhesion to glass of the presently claimed resins is typically greater than 200 J/m 2 for laminates obtained using the presently claimed resins, and yet the resins exhibit impact toughness of greater than about 300 kJ/m 2 .
  • the DCB adhesive strength is within the range of from about 200 to about 1200 J/m 2 .
  • Peel strength of laminates of the presently claimed invention is preferably greater than about 3 or about 6 lbs/inch.
  • Toughness of the laminate can be determined by measuring the impact toughness, particularly the impact penetration.
  • the laminates of the present invention generally provide greater penetration resistance than conventional laminates.
  • lnterlayers of the present invention can be laminated to glass or other transparent materials according to known or non-conventional methods.
  • an interlayer of the present invention can be assembled with at least one other laminate structural layer, such as glass, and laminated to the glass in an autoclave at a temperature above the softening point of the interlayer.
  • the autoclave temperature can be at least about 120°C.
  • the autoclave temperature is at least about 125 0 C, and more preferably at least about 13O 0 C.
  • the present invention is a lamination process wherein a high acid resin can be laminated at a temperature of less than 12O 0 C, preferably less than 110 0 C, to obtain a laminate wherein the adhesion of the laminate is at least as high as that in a laminate obtained from a conventional ethylene copolymer ionomer having less than about 20 wt% acid, and which requires lamination temperatures at or above 12O 0 C.
  • a high acid resin can be laminated at a temperature of less than 12O 0 C, preferably less than 110 0 C, to obtain a laminate wherein the adhesion of the laminate is at least as high as that in a laminate obtained from a conventional ethylene copolymer ionomer having less than about 20 wt% acid, and which requires lamination temperatures at or above 12O 0 C.
  • alternate lamination processes such as for example press-heating, pulse heating, or pass-through oven heating.
  • An interlayer suitable for use herein preferably comprises a surface pattern prior to lamination that facilitates removal of air or trapped vapors and gasses that may otherwise be trapped in the interface between the layers of the laminate. Vacuum or pressure can be applied to the laminate assembly to promote adhesion to glass and/or force out trapped gasses.
  • the lamination can be carried out at atmospheric pressure by application of heat and roll pressure from a nip roll, for example, or other mechanical pressure to the laminate assembly as it is heated.
  • a nip roll for example, or other mechanical pressure to the laminate assembly as it is heated.
  • One of ordinary skill in the art of lamination will know how to carry out the lamination to obtain a laminate of the present invention by using the teachings of this application together with those known and practiced in the conventional art.
  • the laminate thus obtained can be cooled to ambient temperatures at a cooling rate of at least about 5°F/min (2.78°C/min).
  • Laminates of the present invention can be constructed using multiple layers of interlayer of the present invention, or they can comprise interlayers or film layers of different chemical composition.
  • the interlayers of the present invention can be laminated together with other conventional interlayer materials such as, for example: conventional ionomeric interlayers can be laminated with the interlayers of the present invention, as can interlayers comprising EVA copolymers; polyurethanes; polyvinyl chloride polymers; or PVB.
  • Laminates of the present invention can comprise adhesive layers to enhance adhesion between the polymeric layers and/or between polymer layers and glass. Conventional adhesives can be useful in the practice of the present invention as optional components. Typically, however, an interlayer of the present invention does not require an adhesive to promote adhesion to glass.
  • a laminate of the present invention having about 3% haze or less can be obtained by a process comprising a cooling step wherein the laminate is cooled at a rate of less than about 2.75°C/min.
  • the cooling rate of a laminate of the present invention can be slowed to less than about 2°C/min and a laminate having about 3% haze or less can be obtained, and even more surprising, the cooling rate can be slowed to less than 1°C/min to obtain a laminate having about 3% haze or less.
  • Laminates of the present invention are useful in applications such as: windows in buildings; windshields and sidelites in automobiles, planes, trains and the like; structural support units such as stairs, floors, walls, partitions; other architectural units such as ceilings.
  • Laminates of the present invention can comprise at least one rigid structural layer that is adhered to at least one interlayer obtained from the improved resin composition of the present invention.
  • Preferred are laminates comprising at least one interlayer of the present invention with at least one layer of glass as a rigid structural layer.
  • Laminates of the present invention are particularly useful in applications where safety glass is desirable or required.
  • Haze was determined according to ASTM D1003, and is defined as the percentage of transmitted light that deviates from the incident by more than 2.5 degrees. Haze/Clarity measurements were obtained using a
  • Melt Flow Index was determined at 19O 0 C according to ISO 1133 and ASTM D1238.
  • Interlayer Toughness was determined according to ASTM 1822. This is a tensile impact method that determined the energy to rupture a polymer sheet at high rates of strain that are similar to the rates encountered during impact loading of a glass-interlayer laminate. Laminate Toughness was determined using a pendulum impact test. An impact test was performed on glass laminates to ascertain the impact energy required to penetrate the laminate (defined as the penetration energy). As a general guideline, a pendulum impactor defined by the Society of Automotive Engineers (SAE) Recommended Practice - J2568 'Intrusion Resistance of Safety Glazing System for Road Vehicles' (generally believed by those in the industry to be reproducible and accurate) was used.
  • SAE Society of Automotive Engineers
  • the impactor mass was increased to 31.8-kg from 9.5-kg to allow smaller impact drop heights to be used.
  • the pendulum was suspended on 6 cables (4-mm diameter) from a height of approximately 5.6 meters.
  • the six-point cable suspension provides for an accuracy of +/- 5-mm of the desired impact point.
  • the impactor is fabricated from steel into a 75-mm diameter hemispherical impacting end that was casehardened to prevent damage from repetitive impacts and glass shards. Samples were mounted into a rigid steel support structure allowing for impact perpendicular to the glass surface and preventing the edges of the samples from visibly moving in plane.
  • the 30-cm square laminates were sandwiched between two steel frames with mating neoprene rubber gaskets peripherally holding the outer 22-mm of the laminate. Sufficient clamping was utilized to minimize any slippage of the sample within the supporting frame. Impacts were performed at a variety of impact energies on multiple sets of samples. The penetration energy was then calculated from the results based on a traditional 'stair-case' methodology used widely in the industry. Laminates from the above impacted set were then submerged into a container of water at room temperature to check for the resiliency and hydrolytic stability of the retention of glass to the interlayer under potentially adverse environmental conditions. The higher percent acid containing interlayers show greater retention of glass fragments after breakage than the lower acid counterparts.
  • Laminates were peeled at either a 90-degree or a 180-degree angle using an INSTRUMENTORS, Inc., Model SP-102B-3M90 SLIP/PEEL Tester. The laminates were peeled at a rate of 25.4 mm (1 inch) per minute. Peel strength data shown in Table 1 were acquired on laminates made from interlayer sheets that were hot press molded. Peel strength data shown in Table 3 were acquired on laminates made from extruded interlayer sheets. Glass laminates were prepared by the following method. Sheets of annealed glass 300 mm square by 3-mm thickness were washed with a solution of trisodium phosphate (5 g/liter) in deionized water and then rinsed thoroughly with deionized water and dried.
  • Trisodium phosphate 5 g/liter
  • the prelaminate assembly was then placed into an air autoclave and the pressure and temperature was increased from ambient to 135°C and 200 psi in a period of 15 minutes. This temperature and pressure was then held for a sufficient period of time to allow the laminate assembly to heat properly (in this case 30 minutes). Next the temperature was decreased to 4O 0 C within a 20-minute period, 60-minute period or 120-minute period whereby the pressure was then dropped back to ambient and the laminated unit was removed. After autoclaving the laminates were cleaned thoroughly and the haze measured. The determined values are reported in Table 1 below. Several sheets of an interlayer obtained from resin having 21 wt% of methacrylic acid were laminated to glass at either 105 0 C or 135°C in an autoclave. The sheets had moisture content as indicated in Table 2, and the laminates were tested for 180° peel strength. Table 1
  • a glass/interlayer/glass laminate For architectural uses in coastal areas, a glass/interlayer/glass laminate must pass a simulated hurricane impact and cycling test which measures resistance of the laminate to debris impact and wind pressure cycling. A currently acceptable test is performed in accordance to the
  • the test consists of two impacts on the laminate (one in the center of the laminate sample followed by a second impact in a corner of the laminate).
  • the impacts are done by launching a 9-pound (4.1 kilograms) board nominally 2 inches (5 cm) by 4 inches (10 cm) and 8 feet (2.43 meters) long at 50 feet/second (15.2 meters/second) from an air pressure cannon. If the laminate survives the above impact sequence, it is subjected to an air pressure cycling test. In this test, the laminate is securely fastened to a chamber. In the positive pressure test, the laminate with the impact side outward is fastened to the chamber and a vacuum is applied to the chamber and then varied to correspond with the cycling sequences set forth in the following Table A.
  • the pressure cycling schedule as shown in Table A below, is specified as fraction of a maximum pressure P. Each cycle of the first 3500 cycles and subsequent cycles is completed in about 1-3 seconds. On completion of the positive pressure test sequence, the laminate is reversed with the impact side facing inward to the chamber for the negative pressure portion of the test and a vacuum is applied corresponding to the following cycling sequence. The values are expressed as negative values (-).
  • a laminate passes the impact and cycling test when there are no tears or openings over 5 inches (12.7 cm) in length and not greater than 1/16 inch (0.16 cm) in width.
  • Glass laminates used in the hurricane impact tests are prepared in the following manner: All laminates used a 90 mil (2.3 mm) thick interlayer of an ionomer resin (Type 'A') composed of 81% ethylene, 19% methacrylic acid, 37% neutralized with sodium ion and having a final melt index around 2.6 or (Type 'B') composed of 78.5% ethylene, 21.5% methacrylic acid, 32% neutralized with sodium ion and having a final melt index around 0.9.
  • the interlayer was sandwiched between two layers of glass as described below.
  • the ionomer resin interlayer has a StorageYoung's Modulus of about 361 MPa.
  • All laminates are prepared by placing the interlayer between the glass panels. Each of the glass panels is washed with deionized water.
  • the laminates are placed in an air autoclave at 220 PSIG (1.6 MPa) pressure at 135 0 C for 30 minutes.
  • the laminates for the impact testing are 30 inches (77.2 cm) high by 48 inches (121.9 cm) wide.
  • Laminates were then glued into an aluminum frame glazed with a silicone sealant (Dow Corning type 995). This frame was then mounted into a steel supporting frame to conduct the impact test in such a way to minimize movement of the overall glazing.
  • the laminates tested and displayed in Table 6 were impact tested to measure the impact 'toughness' against the timber missile at increased velocities.
  • the laminates of Table 7 were first tested according to the Florida impact and the then subjected to the air pressure cycling test sequence.
  • Polymer A is poly(ethylene-co-methacrylic acid) with 15 wt% of methacrylic acid, 59% neutralized with sodium, and a Ml of 0.9.
  • Polymer B is poly(ethylene-co-methacrylic acid) with 21.4 wt% of methacrylic acid, 29% neutralized with sodium, and a Ml of 0.9.
  • Polymer C is poly(ethylene-co-methacrylic acid) with 21.4 wt% of methacrylic acid, 32% neutralized with zinc, and a Ml of 1.3.
  • Polymer D is poly(ethylene-co- methacrylic acid) with 19 wt% of methacrylic acid, 37% neutralized with sodium, and a Ml of 2.0.
  • Polymer E is poly(ethylene-co-methacrylic acid) with 10 wt% of methacrylic acid, 55% neutralized with sodium, and a Ml of 1.3.
  • Polymer F is poly(ethylene-co-methacrylic acid) with 20 wt% of methacrylic acid, 35% neutralized with sodium, and a Ml of 2.6.
  • Chimassorb® 119 FL stabilizer is reported to be 1 ,5,8,12- tetrakis[4,6-bis(N-butyl-N-1 ,2,2,6,6-pentamethyl-4-piperidylamino)-1 l 3,5- triazin-2-yl]-1 ,5,8,12-tetraazadodecane, (CAS Number 106990-43-6).
  • Tinuvin® 770 stabilizer is reported to be bis(2,2,6,6-tetramethyl-4- piperidyl)sebacate, (CAS Number 52829-07-9).
  • Tinuvin® 123 stabilizer is reported to be bis(1-octyloxy-2,2,6,6 ⁇ tetramethyl ⁇ 4-piperidyl)sebacate, (CAS Number 129757-67-1).
  • Chimassorb® 944 FD stabilizer is reported to be poly[[6-[(1 ,1 ,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6- tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4- piperidylimino]], (CAS Number 71878-19-8).
  • Irganox® HP 2215 FF stabilizer is reported to be a 2:4:1 (by weight) blend of Irganox® 1010:lrgafos® 168:HP-136.
  • Irganox® 1010 stabilizer is reported to be pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), (CAS Number 6683-19-8).
  • Irgafos® 168 stabilizer is reported to be tris(2,4-di- tert-butylphenyl)phosphite, (CAS Number 31570-04-4).
  • HP-136® stabilizer is reported to be 5,7-di-tert-butyl-3-(3,4-di-methylphenyl)-3H- benzofuran-2-one, (CAS Number 181314-48-7).
  • Cyasorb® UV-5411 stabilizer is reported to be 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole.
  • Cyasorb® 3346 stabilizer is reported to be poly[(6-morpholino-s-triazine- 2,4-diyl) [2,2,6,6-tetramethyl-4-pipe ⁇ tyl)imino]-hexamethylene[(2,2,6,6- tetramethyl-4-piperidyl)imino]].
  • Tinuvin® 1577 stabilizer is reported to be 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, (CAS Number
  • Tinuvin® 328 stabilizer is reported to be 2-(2H- benzotriazol-2-yl)-4,6-di-tert-pentylphenol, (CAS Number 25973-55-1).
  • Tinuvin® 360 stabilizer is reported to be 2,2'-methylenebis[6-(2H- benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol], (CAS Number 103597-45-1).
  • Irganox® 3114 stabilizer is reported to be tris(3,5-di-tert- butyl-4-hydroxybenzyl)isocyanurate, (CAS Number 27676-62-6).
  • Tinuvin® 234 stabilizer was reported to be 2-(2H-benzotriazol-2-yl)-4,6-bis(1- methyl-1-phenylethyl)phenol, (CAS Number 70321-86-7).
  • Tinuvin® 326 stabilize was reported to be 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5- chloro-21-l-benzotriazole, (CAS Number 3896-11-5).
  • Cyasorb® UV-531 stabilizer was reported to be 2-hydroxy-4-n-octoxybenzophenone, (CAS Number 1843-05-6).
  • TinuvinTM, ChimassorbTM, IrganoxTM, IrgafosTM and HP-136 product lines are available from Ciba Specialty Chemicals of Basel, Switzerland, whose North American headquarters are in Tarrytown, NY.
  • CyasorbTM products are available from Cytec Industries, Inc. of West Paterson, NJ; they were formerly available from the American Cyanamid Co.
  • the extruder had a melt temperature of approximately 200 0 C and a rate of 2.5 pounds per hour.
  • the screw speed ranged from 47 to 70 RPM and the rear zone temperature ranged from 120 0 C to 170 0 C, depending on the composition.
  • the adapter pressure ranged from 400 psi to 800 psi and power consumption ranged from about 2.5 to 3 amps.
  • the typical extruder barrel temperature profile was as follows; Rear (Feed Hopper) Zone: 120 to 170 0 C
  • Front Zone 200 to 202°C Adapter: 200 to 201 0 C
  • a single strand was passed through a water bath and pelletized to form small pellets.
  • the pellets were purged with nitrogen overnight at room temperature and then sealed in a moisture barrier package.
  • Plaques (6 inch by 7 inch (152 mm X 178 mm) by 25 mil thick) were produced for comparative samples C1-5 and samples 1-15 through compression molding on a Carver Melt Press. The compression molding was conducted at a temperature of 190 0 C and a pressure of 20,000 psi. The plaques were cooled to room temperature over approximately 30 minutes. The plaques were then packaged in moisture barrier packaging, Laminates composed of a glass layer and a 25 mil thick interlayer from the plaques for comparative samples C1-5 and samples 1 , 4, 6, 10, 11 , and 13-15 produced above were produced in the following manner.
  • the 6 inch by 7 inch, (152 mm X 178 mm), 25 mil thick sheet produced as described above was placed onto a 12 inch by 12 inch, (305 mm X 305 mm), by 2.5 mm thick annealed float glass plate.
  • a thin Teflon® film was placed on top of the polymeric interlayer and a cover glass plate was placed on top of the thin Teflon® film.
  • the glass/interlayer/Teflon® film/glass assembly was then placed into a vacuum bag and heated to 90 - 100 0 C for 30 minutes to remove any air contained between the glass/interlayer assembly.
  • the glass/interlayer pre-press assembly was then subjected to autoclaving at 135 0 C for 30 minutes in an air autoclave to a pressure of 200 psig, (14.3 bar), as described above.
  • the air is then cooled while no more air is added to the autoclave. After 20 minutes of cooling when the air temperature is less than about 50 0 C, the excess pressure is vented, and the glass/interlayer laminate is removed from the autoclave.
  • These glass laminates were subjected to 90 degree peel strength adhesion testing with the results reported below within Tables 9 and 10.
  • the laminates were peeled at a 90-degree angle using an INSTRUMENTORS, Inc., Model SP-102B-3M90 SLIP/PEEL Tester. The laminates were peeled at rates of 1 inch and 2 inches per minute.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

La présente invention concerne une composition de résine polymère améliorée comprenant des unités issues de l'éthylène, d'environ 20 % en poids à environ 30 % en poids d'unités provenant d'un acide carboxylique α,β-insaturé ayant de 3 à 8 carbones, et de manière facultative, d'une quantité efficace d'au moins un additif choisi dans le groupe consistant en stabilisants vis-à-vis de la lumière de type amines encombrées, agents absorbant la lumière ultraviolette et stabilisants thermiques. Les résines de la présente invention sont particulièrement appropriées à la préparation de stratifiés transparents utiles comme éléments de vitrage qui fournissent une meilleure sécurité que les éléments de vitrage non stratifiés.
EP06773705A 2006-06-20 2006-06-20 Compositions de résine thermoplastique pour usage dans des stratifiés transparents Withdrawn EP2035470A1 (fr)

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ES2751084T3 (es) 2008-06-02 2020-03-30 Performance Mat Na Inc Módulo de células solares que tiene una capa encapsulante de baja turbidez
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DE102008051730A1 (de) 2008-10-15 2010-04-22 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Transparenter Gegenstand mit einem örtlich begrenzten, strukturierten, elektrisch beheizbaren, transparenten Bereich, Verfahren zu seiner Herstellung und seine Verwendung
DE102008051739A1 (de) 2008-10-15 2010-04-22 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Transparente, farbiges sichtbares Licht reflektierende Interferenzschicht, Verfahren zu ihrer Herstellung und ihre Verwendung
DE202008018521U1 (de) 2008-10-15 2015-02-09 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Transparente, farbiges Licht reflektierende Interferenzschicht
EP2342241B1 (fr) 2008-10-31 2016-08-03 E. I. du Pont de Nemours and Company Articles stratifiés à transparence élevé comportant une couche ionomère intermédiaire
DE102008064356A1 (de) 2008-12-20 2010-06-24 Saint-Gobain Glass Deutschland Gmbh Integrierter Glasaufbau, Verfahren zu seiner Herstellung und seine Verwendung
DE202008017611U1 (de) 2008-12-20 2010-04-22 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Scheibenförmiges, transparentes, elektrisch beheizbares Verbundmaterial
MX2011006996A (es) 2008-12-31 2011-08-08 Du Pont Laminados que comprenden capas ionomericas intermedias con baja opacidad y alta resistencia a la humedad.
DE102009025888B4 (de) 2009-05-29 2014-04-10 Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg Elektrisch großflächig beheizbarer, transparenter Gegenstand und seine Verwendung
DE202009018204U1 (de) 2009-10-26 2011-04-21 Saint-Gobain Glass France Integrierter Glasaufbau
AU2011282567B2 (en) 2010-07-30 2015-06-18 Performance Materials Na, Inc. Crosslinkable materials for safety laminates
US9435913B2 (en) 2010-08-20 2016-09-06 Sekisui Chemical Co., Ltd. Interlayer for laminated glass, and laminated glass
JP5789151B2 (ja) * 2011-07-28 2015-10-07 アキレス株式会社 合わせガラス用中間膜
US20150251384A1 (en) 2012-10-12 2015-09-10 E.I.Du Pont De Nemours And Company Glass laminates with nanofilled ionomer interlayers
WO2014100309A1 (fr) 2012-12-19 2014-06-26 E. I. Du Pont De Nemours And Company Composition de copolymère d'acide réticulable et son utilisation dans des verres feuilletés
US20150158986A1 (en) 2013-12-06 2015-06-11 E.I. Du Pont De Nemours And Company Polymeric interlayer sheets and light weight laminates produced therefrom
US9809009B2 (en) * 2014-12-08 2017-11-07 Solutia Inc. Multiple layer interlayer having improved optical and sound insulation properties
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CN113993909B (zh) * 2019-12-19 2022-10-04 株式会社可乐丽 离聚物树脂、树脂片和夹层玻璃

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