WO1995026377A1 - Acrylate blends and laminates using acrylate blends - Google Patents
Acrylate blends and laminates using acrylate blends Download PDFInfo
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- WO1995026377A1 WO1995026377A1 PCT/US1995/001847 US9501847W WO9526377A1 WO 1995026377 A1 WO1995026377 A1 WO 1995026377A1 US 9501847 W US9501847 W US 9501847W WO 9526377 A1 WO9526377 A1 WO 9526377A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- B32B17/10688—Adjustment of the adherence to the glass layers
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
- Y10T428/31649—Ester, halide or nitrile of addition polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the invention relates to acrylate copolymer blends and in particular to ethylene methylacrylate copolymer/ethylene butylacrylate copolymer blends and their use as a layer or interlayer which is bonded to mineral (e.g., glass) or polymer substrates for the manufacture of bilayer or multiple layer laminates.
- these films are useful between two or more transparent layers made of glass or polymer materials for use as safety glass for automotive and architectural applications.
- the performance of the interlayer films is based on film characteristics such as tensile strength, elongation at break, softening point and glass adhesion strength and laminate properties such as luminous transmittance, boil test stability, humidity test stability, light stability and impact and penetration resistance. While conventional PVB interlayers perform well, they do suffer from several drawbacks.
- PVB moisture sensitivity
- special precautions have to be taken to keep the moisture content of the PVB film and ulitmately the haze of the laminated flat glass products to an optimum.
- These special precautions may include reducing storage times of the PVB film to a minimum, refrigeration of the PVB film prior to lamination, pre-drying of the PVB film and/or the use of dehumidifiers in the clean rooms used for preparing the laminates. This both increases the cost and the difficulty in manufacturing laminates made with a polyvinyl butyral interlayer. Even then when the edges of the laminated glass are exposed to moisture, haze will develop.
- PVB Another drawback of PVB is the need for a plasticizer in film for bonding the PVB to the glass.
- the plasticizer tends to migrate over time leading to changes in the properties of the laminate and in particular delamination will begin to occur at the edges of the laminated glass due to loss of the plasticizer.
- the other polymers and formulations which have been used or tried include those based on polyurethane (PU) , polyvinylchloride (PVC) , ethylene copolymers such as ethylenevinylacetate (EVA) , polymeric fat acid polyamide (PAM) , polyester resins such as polyethyleneterephtalate (PET) , silicone elastomers (SEL) , epoxy resins (ER) or polycarbonates such as elastomeric polycarbonates (PC and EPC) . While many of these polymers and formulations do not have as relatively significant a moisture absorption problem as PVB, they do lack the overall performance of the PVB films at comparable costs.
- An object of this invention is to produce a polymer film which has a tensile strength, moisture absorption, elongation at break, softening point and a glass adhesion strength which are comparible or superior to PVB, and which can be incorporated in laminated glass products such as windshield and architectural safety glass that have a luminous transmittance, boil test stability, humidity test stability, light stability and impact and penetration resistance comparible or superior to those made with PVB.
- a further object of this invention is to produce an ethylene acrylate copolymer blend and film which is useful as a component of optical laminates.
- a further object of this invention is to produce an ethylene acrylate copolymer blend and film which can be processed into an interlayer under conditions similar to those used for processing PVB.
- the present invention comprises a film formed from an acrylate blend.
- the preferred blend comprising components (a) and (b) , component (a) being an ethylene butyl acrylate copolymer (EBAC) which is less than about 95 percent percent by weight of a total weight of components (a) and (b) , wherein the EBAC has a content of acrylate groups from about 8 to about 36 percent by weight of the total weight of the EBAC; and component (b) being an ethylene methyl acrylate copolymer (EMAC) which is greater than about 5 percent by weight of the total weight of components (a) and (b) , wherein the EMAC has a content of acrylate groups from about 8 to about 42 percent by weight of the total weight of the EMAC.
- EBAC ethylene butyl acrylate copolymer
- EMAC ethylene methyl acrylate copolymer
- the invention further includes a process for manufacturing this film comprising the steps of mixing the melt of thermoplastic polymer resins to form an ethylene butyl acrylate/ethylene methyl acrylate blend and forming the ethylene butyl acrylate/ethylene methyl acrylate blend of thermoplastic resins into a film.
- the invention still further includes a laminate comprising at least a first layer which is typically transparent and at least one layer comprised of the film described above.
- the invention still further includes a laminate comprising an acrylate film laminated between two lamina wherein the film and the laminate have properties similar to PVB and laminates made with PVB, respectively.
- the present invention is a film which has particular utility in glass laminates.
- the film comprises a blend of two or more acrylates.
- these acrylates include ethylene butyl acrylate, ethylene methyl acrylate, isobutylacrylate, and ethylene propyl acrylate. These examples are; however, given by way of illustration and not by way of limitation.
- the film preferably, comprises a blend of two components. These being component (a) which is an ethylene butyl acrylate copolymer and component (b) which is an ethylene methyl acrylate copolymer.
- the ethylene butyl acrylate (EBAC) of component (a) has a content of acrylate groups from about 8 to about 36 percent, preferably from about 16 to about 26 percent by weight and more preferably from about 18 to about 22 percent by weight of the total weight of the ethylene butyl acrylate (EBAC) .
- the ethylene methyl acrylate of component (b) has a content of acrylate groups from about 8 to about 42 percent, preferably from about 20 to about 32 percent, and more preferably from about 22 to about 27 percent by weight of the total weight of the ethylene methyl acrylate (EMAC) .
- the melt flow rate of the ethylene butyl acrylate copoylmer (EBAC) used as component (a) of the film as measured by ASTM Test Method D-1238 is preferably from about 0.5 to about 20.0 grams/10 minutes, more preferably is from about 0.5 to about 10 grams/10 minutes, and most preferably is from about 0.5 to about 6.0 grams/10 minutes.
- the melt flow rate of the ethylene methyl acrylate copoylmer (EMAC) used as component (b) of the film as measured by ASTM Test Method D-1238 is preferably from about 0.5 to about 100.0 grams/10 minutes, more preferably is from about 0.5 to about 20 grams/10 minutes, and most preferably is from about 2.0 to about 6.0 grams/10 minutes.
- the amount of component (a) present in the film is less than about 95 percent by weight of the total weight of components (a) and (b) , and the amount of component (b) present in the film is greater than about 5 percent by weight of the total weight of components (a) and (b) .
- the amount of component (a) present in the film is from about 95 percent to about 1 percent by weight of the total weights of components (a) and (b)
- the amount of component (b) present in the film is from about 5 percent to about 99 percent by weight of the total weights of components (a) and (b) .
- the amount of component (a) is from about 95 percent to about 5 percent by weight of the total weight of components (a) and (b)
- the amount of component (b) present in the film is from about 5 percent to about 95 percent by weight of the total weight of components (a) and (b) .
- the amount of component (a) is from about 50 percent to about 5 percent by weight of the total weight of components (a) and (b)
- component (b) is from about 50 percent to about 95 percent by weight of the total weight of components (a) and (b)
- component (a) is from about 20 percent to about 5 percent by weight of the total weight of components (a) and (b)
- component (b) is from about 80 percent to about 95 percent by weight of the total weight of components (a) and (b) .
- the relative amounts of components (a) and (b) may be varied within the defined ranges in order to satisfy the needs of a particular application or process. Variation of the components further depends on other variables including for example the nature of the substrate or laminus (e.g., whether it is a polymer or a glass) . Changes in the relative amounts of (a) and (b) lead to changes in properties including for example transparency, haze, tensile modulus, softening point and penetration resistance.
- the film of the invention may employ one or more additives. All of the additives are designated in this specification as component (c) .
- the additives include for example cross-linking agents, coupling agents, nucleation agents, UV-light absorbers, IR-light absorbers, pigments and other additives depending on the type and application of the final laminated product.
- the amount of the additives as a group called component (c) present in the film may consist of from about 0.25 percent to about 15.0 percent by weight of the total weight of components (a) , (b) , and (c) , more preferably is from about 0.5 percent to about 10.0 percent by.weight of the total weight of components (a), (b) , and (c) , and most preferably is from about 1.0 percent to about 5.0 percent by weight of the total weight of components (a) , (b) , and (c) .
- the film comprises a coupling agent and a clarifying agent known as components (c) (i) and (c) (ii) , respectively; and more preferably the film further comprises a cross-linking agent known as component (c) (iii) .
- the amount of the coupling agent (c) (i) present in the film consists of from about 0.10 percent to about 6.0 percent by weight of the total weight of components (a) , (b) and (c)
- the amount of clarifying agent (c) (ii) present in the film consists of from about 0.05 percent to about 3.0 percent by weight of the total weight of components (a) , (b) and (c)
- the amount of cross-linking agent present in the film consists of up to about 5.0 percent by weight of the total weight of components (a) , (b) and (c) .
- the amount of the coupling agent (c) (i) present in the film consists of from about 0.10 percent to about 4.0 percent by weight of the total weight of component (a) , (b) and (c)
- the amount of clarifying agent (c) (ii) present in the film consists of from about 0.15 percent to about 3.0 percent by weight of the total weight of components (a) , (b) and (c)
- the amount of cross-linking agent present in the film consists of up to about 4.0 percent by weight of the total weight of components (a) , (b) and (c) .
- the amount of the coupling agent (c) (i) present in the film consists of from about 0.20 percent to about 2.0 percent by weight of the total weight of component (a) , (b) and (c)
- the amount of clarifying agent (c) (ii) present in the film consists of from about 0.50 percent to about 2.0 percent by weight of the total weight of components (a) , (b) and (c)
- the amount of cross-linking agent present in the film consists of up to about 3.5 percent by weight of the total weight of components (a) , (b) and (c) .
- the amount of the coupling agent (c) (i) present in the film consists of from about 0.20 percent to about 1.0 percent by weight of the total weight of component (a) , (b) and (c)
- the amount of clarifying agent (c) (ii) present in the film consists of from about 0.50 percent to about 1.5 percent by weight of the total weight of components (a) , (b) and (c)
- the amount of cross-linking agent present in the film consists of from about 0.30 percent to about 2.5 percent by weight of the total weight of components (a) , (b) and (c) .
- Cross-linking agents may be used to increase the softening point of the film.
- the preferred cross-linking agent is an organic peroxide, and is chosen from peroxides with appropriate kinetics of degradation to be stable enough during mixing of the formulation. This includes peroxide compounds preferably having at least a 10 hour half-life at decomposition temperatures greater than 70 °C, and more preferably only includes compounds having at least a 10 hour half-life at decomposition temperatures greater than 100 °C.
- the half-life of the organic peroxides is defined as the time in which half the chemical decomposes at the given temperature.
- cross-linking agents examples include 2,5-dimethylhexane-2,5-dihydroperoxide; 2,5- dimethyl-2,5-di(t-butylperoxy)hexane-3; di-t-butyl peroxide; t-butylcumyl peroxide; 2,5-dimethyl-2,5-di(t- butylperoxy)hexane; dicumyl peroxide; a,a'-bis(t- butylperoxyisopropyl)benzene; n-butyl-4,4'-bis(t- butylperoxy)valerate; 2,2-bis(t-butylperoxy)butane; 1,1- bis(t-butylperoxy)cyclohexane; 1,1-bis(t-butylperoxy) - 3,3,5-trimethyl cyclohexane; t-butylperoxy benzoate; benzoyl peroxide; or combinations
- cross-linking may also be accomplished by electron beam treatment of the film to increase the softening point.
- the electron beam intensity is preferably in the range of from about 2 to about 20 MRads for a time sufficient to increase the softening point to between about 110 to about 125 °C.
- Coupling agents may be used to increase the bondability of the film to a lamina without pre-treatment of the surface of the lamina with primers.
- the preferred coupling agents are silane coupling agents.
- silane coupling agents which may be used include for example chloropropylmethoxysilane; vinyltrichlorosilane; vinyltriethoxysilane; vinyl-propyl trimethoxysilane; (3,4-ethoxycyclohexyl)ethyl-trimethoxysilane; glicidoxypropyl trimethoxysilane; vinyl-triacetoxysilane; aminopropyl triethoxysilane or combinations of these.
- the examples of coupling agents are given by way of illustration and not by way of limitation.
- the more preferred coupling agent is vinyltriethoxysilane.
- Clarifying agents may be used to increase the transparency and decrease the haze of the film.
- the clarifying agents are nucleating agents which decrease the haze and increase the transparency of the film by decreasing the amount of crystallinity, and controlling the size and uniformity of the crystals in the film.
- the processing conditions (e.g., cooling rate) of the film can also affect the amount, size and uniformity of crystals in the film.
- the preferred clarifying agents are organic nucleators. Examples of organic nucleators which may be used include for example polyol acetals.
- the more preferred clarifying agents are polyol acetals sold under the tradenames Millad 3940 and manufactured by Milliken Chemicals of Spartanburg, South Carolina, and Mark 2180 manufactured by Witco Corporation, New York, New York.
- UV and IR light absorbers may be used to provide the film and the laminated product with particular absorption and reflection characteristics, and pigments and other optical effect additives may be used to provide the film with special colors (e.g., shade band, etc) and other optical effects.
- the film produced from these acrylate blends preferably has a tensile strength at break greater than about 13.0 N/mm 2 , more preferably greater than about 14.0 N/mm 2 , and most preferably greater than about 16.0 N/mm 2 .
- the elongation at break is greater than about 400 percent, more preferably greater than about 500 percent, and most preferably greater than about 700 percent.
- the water content upon storage at 50 percent relative humidity at 50 °C for 14 days is less than about 0.20 percent by weight, more preferably less than about 0.15 percent by weight, and most preferably less than about 0.10 percent.
- the tear strength is greater than about 24.0 N/mm, more preferably greater than about 27.0 N/mm, and most preferably greater than about 30.0 N/mm.
- the softening point is greater than about 80 °C, more preferably greater than 105 °C, and most preferably greater than about 115 °C.
- the process for manufacturing the film of the invention comprises the steps of mixing and heating the thermoplastic polymer resins to form an acrylate blend or in the preferred embodiment an ethylene butyl acrylate/ethylene methyl acrylate blend, wherein the ethylene butyl acrylate/ethylene methyl acrylate blend of thermoplastic polymer resins comprises components (a) and (b) and optionally (c) as described above; and forming the ethylene butyl acrylate/ethylene methyl acrylate blend of thermoplastic resins into a film.
- the processing of a film from Components (a) , (b) and optionally (c) can be accomplished by mixing the components along with the application of heat.
- the mixing of the components and the application of heat can take place in any order including the mixing of the components before, during, or after the application of heat.
- the processing temperatures required for mixing the blend and forming the film are affected by many factors including pressure, time at temperature, whether the heat is applied before, during or after mixing, and the degree of mixing.
- the blend can be formed into pellets or other shapes known to those skilled in the art for further processing or can be directly formed into the desired film.
- the preferred method of processing comprises forming pellets or other shaped pieces by heating and mixing the components (a) , (b) and optionally (c) simultaneously.
- the pellets or other shaped pieces may be formed into a film by for example extrusion, casting or blow-extrusion or other means for producing film known to those skilled in the art. Extrusion is the preferable method of forming the film, and if extrusion is used the extruder is preferably equipped with a flat or ring die.
- the film is preferably formed at temperatures from about 160 °C to about 240 °C, more preferably at temperatures from about 170 °C to about 230 °C, and most preferably from about 180 °C to about 220°C .
- the formed film may be used as an interlayer in a laminate.
- the' laminate can be formed comprising at least two layers separated by at least one interlayer, wherein the interlayer is a film formed from components (a) , (b) and optionally (c) described above.
- the lamina or sheets used to form the laminate can be flat or bent.
- the lamina or sheets can be glass, glass-ceramic or polymers. Examples of polymers which may be used include polymethyl methacrylate and polycarbonate. These examples of polymers are given as an illustration and not as a limitation.
- the preferred glass would be a soda-lime-silicate glass which is commonly used in the flat glass industry.
- the interlayer is the film described above as a ethylene butyl acrylate/ethylene methyl acrylate blend with or without additives.
- the laminate comprises at least one lamina laminated to a polymer interlayer, however, when the laminate comprises at least two lamina the laminate is formed comprising x number of sheets separated by x-1 number of layers of polymer interlayer wherein x is at least two.
- the sheets can be of any thickness, however, for the process of lamination it is preferred that the sheets are from about 0.25 to about 12.7 mm thick, more preferably from about 1.25 to about 5 mm thick, and most preferably from about 1.5 to about 3.5 mm thick.
- the sheets and the interlayer can be laminated together by processes known to those skilled in the art. An example of process used to mature the laminate is the use of an autoclave which is given by way of illustration and not by way of limitation.
- Laminates made using this film are made from an acrylate blend and two lamina, wherein the film is laminated between the two lamina, and wherein the laminate has the following properties.
- the laminate preferably has a luminous transmittance which is greater than about 82.0 percent, more preferably greater than about 85.0 percent, and most preferably greater than about 87.0 percent.
- the laminate's haze is less than about 1.0 percent, more preferably less than about 0.5 percent, and most preferably less than about 0.35 percent.
- the peel strength is greater than about 15 N/cm, more preferably greater than about 20 N/cm, and most preferably greater than about 30 N/cm.
- the laminate can further pass the standard German penetration test DIN 52338.
- Ethylene Butyl Acrylate/Ethylene Methyl Acrylate blends were produced by mixing the melts of these two thermoplastic resins (some blends further included a certain package of additives) .
- Blends using an additive package comprised 100 parts by weight acrylate blend along with 0.3 parts by weight of vinyltriethoxysilane as a coupling agent, 1 part by weight of dicumyl peroxide as a crosslinking agent sold under the tradename of Luprasol 101 from Elf tochem Company, Philadelphia, Pennsylvania, and 1 part by weight of a polyol acetal as a clarifying agent sold under the tradename Millad 3940 and manufactured by Milliken Chemicals of Spartanburg, South Carolina.
- the extruded pellets were processed into films using a cast film line consisting of a single screw extruder Model No. 20IN20 made by Davis Standard of Pawcatuck,
- the screw of the extruder had a diameter of 50.8 mm and a relative barrel length of 24 diameters.
- the extruder was equiped with a flat extrusion die having an orifice which was 45.72 cm wide. Films of two thicknesses 0.18 mm and 0.36 mm were produced from each blend. Table I describes the blends produced. An experimental design program was used to reduce the number of samples necessary to cover the full range of possible combinations of the EMAC and EBAC blends.
- the barrel of the extruder was divided into six heating zones progressively increasing the temperature of the blend up to the die.
- the barrel temperature was maintained in each of zones 1-6 at 180, 190, 200, 200, 200 and 210 °C, respectively.
- the temperature of the extrusion die was maintained at approximately 200 °C.
- the pressure to which the blend was subjected was measured for both the 0.18 and 0.36 mm thick films.
- the pressure at the end of the screw was 1390 and 1260 psi, respectively, and in the die was 815 and 770 psi, respectively.
- the speed of the screw was maintained at between 10-14 rp for 0.18 mm thick films and 16-21 rpm for 0.36 mm thick films.
- Example 2 Each film was extruded and cooled using a three roll casting roll stock and was wound on to 7.6 cm cores. Fifteen samples were cut for testing from each film produced. At each of five sampling locations which were 20 linear feet apart, samples were obtained at three points across the film (from each of the edges and from the middle) .
- Example 2
- the test for water content after storage was performed by measuring the change in weight of the sample before and after exposing a sample of film to 50% relative humidity at 20 °C for 14 days. The softening point was measured on a DSC using a heating at a rate of 2.5 °C per minute. The elongation on break and tensile strength was determined by using ASTM D-638 testing method. The test for tear strength was performed using ASTM D-882 testing method. The transmission and the haze were measured after laminating 0.4 mm film between two layers of 3 mm thick sheets of clear, soda-lime-silicate glass. The transmission was measured using ANSI Standard Z26.1T2. The haze was measured using German Standard DIN R43-A.3/4.
- the results of the films made from 100% EBAC resin show that EBAC films containing 8-16 percent by weight of butyl acrylate groups have a relatively low transparency and high haze.
- the results indicate that as the amount of acrylate groups in the film increase from 16 to 26 percent by weight this leads to a significant improvement in the optical properties of the EBAC film with the best optical properties being found when the amount of acrylate in the film is between 18 and 22 percent by weight. While the transparency and haze of these films improve, the improvement is not enough to consider using these films as a substitute for PVB or EVA as a glass interlayer.
- the results further show that EBAC films have excellent mechanical properties which appear to be superior to PVB, EVA and EMAC films.
- the brittleness at low temperatures is independent of the molecular weight (melt flow rate) and acrylate content, however, the tensile strength, elongation on break and tear resistance are optimal when the melt flow rate of the EBAC is between 0.5 and 6.0 grams/10 minutes and these properties decrease when the melt flow rate of the EBAC exceeds 6.0 grams/10 minutes.
- the results show that films made from 100% EMAC resin with acrylate content of 8 to 42 percent by weight are more transparent and have a lower haze than EBAC films.
- the optimal optical properties of EMAC occur when the acrylate content of the film is between 22 to 27 percent by weight.
- Film samples produced according to Example 1 from EMAC, EBAC and combinations of EMAC and EBAC were used to manufacture a number of samples of laminates. These samples were produced using Saint Gobains "pilot technology" to simulate the manufacturing technology.
- a piece of film was cut to obtain a sample which is 50 x 50 cm. This sample was then put onto the surface of the bottom glass sheet and pressed onto the glass sheet using a rubber roll. Another glass sheet was placed on top of the film obtaining a "sandwich” structure which is then clamped. This "sandwich” was then placed in an autoclave and heated to a temperature of between 110-115 °C while drawing a vacuum of 3-5 x 10 "2 mm of Hg. This melts the film surfaces while eliminating air between the layers. The "sandwich” structure was held in the autoclave under these conditions for 3 hours during which time a safety glass laminate was produced.
- the glass/film (interlayer)/glass laminates were peel tested, boil tested, humidity tested, light stability tested and penetration tested, and compared with the properties of polyvinyl butyral film (PVB) sold under the registered trademark Saflex SR 41 manufactured by Monsanto of St. Louis, Missouri, and ethylene-vinyl acetate film (EVA) sold under the tradename EVA Poly BD 300 manufactured by Elf Atochem, Philadelphia, Pennsylvania which are used worldwide as interlayers in safety glass manufacturing.
- PVB polyvinyl butyral film
- EVA ethylene-vinyl acetate film
- the humidity test was performed by exposing the laminate to 100% relative humidity at 50 °C for 14 days and then examining the laminate visually for any signs of haze.
- the peel test was performed by peeling the film from the glass.
- the boil test stability was determined by boiling a sample of the laminate in water for 2 hours at 100 °C and then visually examining the sample for haze.
- the light stability test was performed by aging a sample of the laminate with a UV-Bulb #5 using an intensity of 0.5 watts/m 2 for 100 hours and then examining the laminate for any visual changes.
- the pentration test was performed using the German Standard DIN 52338 which is similar to the U.S. ball drop standard.
- a 50 x 50 cm sample of the laminate is cut from a safety glass sheet.
- the laminate was placed on a solid metered concrete substrate.
- a ball of 2,260 grams is used.
- the laminate passes if no penetration occurs while it is considered a failure if the ball is able to penetrate the laminate.
- the tests start with the smallest height of drop of the ball of 1.5 m, then if positive results are obtained, the test is repeated by increasing to the height of 2.0 m and dropping the ball on a similar new specimen, and if no failure the test is repeated increasing the height of the drop to 2.5 m. If positive results are achieved at the last height the safety glass is considered to have passed the penetration test.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9507334A BR9507334A (en) | 1994-03-29 | 1995-02-14 | Mixtures of acrylate and laminates using mixtures of acrylate |
MXPA/A/1996/004479A MXPA96004479A (en) | 1994-03-29 | 1995-02-14 | Acrylate mixtures and laminated materials queusan mixes of acryl |
AU18763/95A AU1876395A (en) | 1994-03-29 | 1995-02-14 | Acrylate blends and laminates using acrylate blends |
JP7525154A JP3057646B2 (en) | 1994-03-29 | 1995-02-14 | Acrylate compound and laminate using the acrylate compound |
DE69501400T DE69501400T2 (en) | 1994-03-29 | 1995-02-14 | ACRYLATE MIXTURES AND COMPOSITES THAT USE THIS |
EP95910994A EP0754201B1 (en) | 1994-03-29 | 1995-02-14 | Acrylate blends and laminates using acrylate blends |
KR1019960705298A KR970701752A (en) | 1994-03-29 | 1995-02-14 | Acrylate blends and laminates using acrylate blends |
CA002183578A CA2183578C (en) | 1994-03-29 | 1995-02-14 | Acrylate blends and laminates using acrylate blends |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/219,317 US6596400B1 (en) | 1994-03-29 | 1994-03-29 | Acrylate blends and laminates using acrylate blends |
US08/219,317 | 1994-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995026377A1 true WO1995026377A1 (en) | 1995-10-05 |
Family
ID=22818793
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/001847 WO1995026377A1 (en) | 1994-03-29 | 1995-02-14 | Acrylate blends and laminates using acrylate blends |
Country Status (13)
Country | Link |
---|---|
US (2) | US6596400B1 (en) |
EP (1) | EP0754201B1 (en) |
JP (1) | JP3057646B2 (en) |
KR (1) | KR970701752A (en) |
AT (1) | ATE161862T1 (en) |
AU (1) | AU1876395A (en) |
BR (1) | BR9507334A (en) |
CA (1) | CA2183578C (en) |
DE (1) | DE69501400T2 (en) |
ES (1) | ES2113737T3 (en) |
TW (1) | TW304970B (en) |
WO (1) | WO1995026377A1 (en) |
ZA (1) | ZA951477B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0747210A2 (en) * | 1995-06-08 | 1996-12-11 | Sekisui Chemical Co., Ltd. | A laminated glass and an interlayer film for the same |
WO1997038049A1 (en) * | 1996-04-04 | 1997-10-16 | The Procter & Gamble Company | Blends of and methods of blending olefin/ester copolymers having improved environmental stress cracking or environmental fatigue resistance, products made therefrom, methods of molding said products |
US6559230B2 (en) | 2000-09-29 | 2003-05-06 | Dupont Dow Elastomers L.L.C. | Thermosetting ethylene/alpha-olefin composition and safety glass interlayer film made from the composition |
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US20060223942A1 (en) * | 2003-05-21 | 2006-10-05 | Basell Poliolefine Italia S.R.L. | Stretch wrap films |
EP1629038A2 (en) * | 2003-05-21 | 2006-03-01 | Basell Poliolefine Italia S.r.l. | Polyethylene films for packaging |
US20060108322A1 (en) * | 2004-11-19 | 2006-05-25 | Wei Wu | Lift-off material |
US7957524B2 (en) * | 2006-03-02 | 2011-06-07 | Zagg Incorporated | Protective covering for an electronic device |
JP2007279554A (en) * | 2006-04-11 | 2007-10-25 | Three M Innovative Properties Co | Film for preventing scattering of protective glass of liquid crystal display |
US20090179356A1 (en) * | 2008-01-14 | 2009-07-16 | Ama, Inc. | Low Haze Thermoplastic Films, Methods and Manufacturing System For Forming the Same |
US11134580B2 (en) | 2010-07-08 | 2021-09-28 | Zagg Inc | Protective cover for portable electronic device and associated systems and methods |
JP5778441B2 (en) * | 2011-02-22 | 2015-09-16 | 株式会社ブリヂストン | Solar cell sealing film and solar cell using the same |
WO2012178168A2 (en) | 2011-06-23 | 2012-12-27 | Zagg Intellectual Property Holding Co., Inc. | Accessory and support for electronic devices, systems including the same and methods |
US20130139476A1 (en) * | 2011-12-06 | 2013-06-06 | Jeffrey Smith | Acrylic formation process for marine enclosure fabrication |
CN110482969A (en) * | 2019-09-30 | 2019-11-22 | 西京学院 | A kind of permeable concrete and preparation method thereof |
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EP0145213A2 (en) * | 1983-11-16 | 1985-06-19 | Stc Plc | Oil resistant flame retardant compositions |
EP0244982A2 (en) * | 1986-04-25 | 1987-11-11 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Film compositions |
EP0287403A2 (en) * | 1987-04-16 | 1988-10-19 | W.R. Grace & Co.-Conn. | Oriented polymeric films and process ofr enhanced orientation of polymeric films |
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US4351931A (en) * | 1961-06-26 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Polyethylene copolymers |
GB1089907A (en) | 1963-09-27 | 1967-11-08 | Union Carbide Corp | Plasticized ethylene-acrylic acid copolymers |
DE1596821A1 (en) * | 1965-12-27 | 1969-10-30 | Gulf Research Development Co | Glass laminate and method of making the same |
US3488715A (en) | 1966-09-14 | 1970-01-06 | Dow Chemical Co | Laminated glass structures and method therefor |
US3494903A (en) | 1967-08-02 | 1970-02-10 | Gulf Research Development Co | Process for the recovery of ethylene polymers |
JPS55162451A (en) | 1979-05-31 | 1980-12-17 | Sekisui Chem Co Ltd | Interlayer composition for safety laminated glass |
US4358329A (en) | 1980-08-25 | 1982-11-09 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Safety laminate and process for production thereof |
US4600627A (en) * | 1984-04-24 | 1986-07-15 | Bridgstone Corporation | Sandwich glasses |
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JP3211261B2 (en) | 1991-06-07 | 2001-09-25 | 株式会社ブリヂストン | Laminated glass |
JP3423308B2 (en) * | 1991-09-24 | 2003-07-07 | シェブロン ケミカル カンパニー エルエルシー | Copolymer of ethylene and alkyl acrylate, method for producing the same, and highly transparent film |
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AU672250B2 (en) | 1992-12-17 | 1996-09-26 | Sekisui Chemical Co., Ltd. | An interlayer film and laminated glass using the same |
-
1994
- 1994-03-29 US US08/219,317 patent/US6596400B1/en not_active Expired - Fee Related
-
1995
- 1995-02-14 DE DE69501400T patent/DE69501400T2/en not_active Expired - Fee Related
- 1995-02-14 CA CA002183578A patent/CA2183578C/en not_active Expired - Fee Related
- 1995-02-14 AU AU18763/95A patent/AU1876395A/en not_active Abandoned
- 1995-02-14 WO PCT/US1995/001847 patent/WO1995026377A1/en active IP Right Grant
- 1995-02-14 AT AT95910994T patent/ATE161862T1/en not_active IP Right Cessation
- 1995-02-14 EP EP95910994A patent/EP0754201B1/en not_active Expired - Lifetime
- 1995-02-14 KR KR1019960705298A patent/KR970701752A/en active IP Right Grant
- 1995-02-14 BR BR9507334A patent/BR9507334A/en not_active IP Right Cessation
- 1995-02-14 JP JP7525154A patent/JP3057646B2/en not_active Expired - Fee Related
- 1995-02-14 ES ES95910994T patent/ES2113737T3/en not_active Expired - Lifetime
- 1995-02-22 ZA ZA951477A patent/ZA951477B/en unknown
- 1995-03-28 TW TW084103010A patent/TW304970B/zh active
- 1995-05-12 US US08/440,366 patent/US6590037B1/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0145213A2 (en) * | 1983-11-16 | 1985-06-19 | Stc Plc | Oil resistant flame retardant compositions |
EP0244982A2 (en) * | 1986-04-25 | 1987-11-11 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Film compositions |
EP0287403A2 (en) * | 1987-04-16 | 1988-10-19 | W.R. Grace & Co.-Conn. | Oriented polymeric films and process ofr enhanced orientation of polymeric films |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0747210A2 (en) * | 1995-06-08 | 1996-12-11 | Sekisui Chemical Co., Ltd. | A laminated glass and an interlayer film for the same |
EP0747210A3 (en) * | 1995-06-08 | 1997-09-24 | Sekisui Chemical Co Ltd | A laminated glass and an interlayer film for the same |
WO1997038049A1 (en) * | 1996-04-04 | 1997-10-16 | The Procter & Gamble Company | Blends of and methods of blending olefin/ester copolymers having improved environmental stress cracking or environmental fatigue resistance, products made therefrom, methods of molding said products |
US6559230B2 (en) | 2000-09-29 | 2003-05-06 | Dupont Dow Elastomers L.L.C. | Thermosetting ethylene/alpha-olefin composition and safety glass interlayer film made from the composition |
Also Published As
Publication number | Publication date |
---|---|
JP3057646B2 (en) | 2000-07-04 |
EP0754201B1 (en) | 1998-01-07 |
BR9507334A (en) | 1997-09-16 |
AU1876395A (en) | 1995-10-17 |
JPH09507694A (en) | 1997-08-05 |
US6596400B1 (en) | 2003-07-22 |
ATE161862T1 (en) | 1998-01-15 |
MX9604479A (en) | 1997-07-31 |
CA2183578C (en) | 2000-05-09 |
ES2113737T3 (en) | 1998-05-01 |
EP0754201A1 (en) | 1997-01-22 |
DE69501400D1 (en) | 1998-02-12 |
US6590037B1 (en) | 2003-07-08 |
CA2183578A1 (en) | 1995-10-05 |
TW304970B (en) | 1997-05-11 |
KR970701752A (en) | 1997-04-12 |
DE69501400T2 (en) | 1998-07-16 |
ZA951477B (en) | 1995-12-07 |
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