CN1878669A - 用于玻璃－塑料玻璃窗产品的耐擦伤低聚物基涂层 - Google Patents

用于玻璃－塑料玻璃窗产品的耐擦伤低聚物基涂层 Download PDF

Info

Publication number
CN1878669A
CN1878669A CNA2004800327535A CN200480032753A CN1878669A CN 1878669 A CN1878669 A CN 1878669A CN A2004800327535 A CNA2004800327535 A CN A2004800327535A CN 200480032753 A CN200480032753 A CN 200480032753A CN 1878669 A CN1878669 A CN 1878669A
Authority
CN
China
Prior art keywords
lamination
component
oligomer
polymer
polymer film
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.)
Pending
Application number
CNA2004800327535A
Other languages
English (en)
Inventor
J·C·安德森
R·巴索蒂
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 CN1878669A publication Critical patent/CN1878669A/zh
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/1033—Laminated safety glass or glazing containing temporary protective coatings or layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—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
    • B32B17/10761—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 vinyl acetal
    • 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
    • B32B17/10779—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 polyester
    • 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
    • B32B17/10788—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 ethylene vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4261—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups prepared by oxyalkylation of polyesterpolyols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • 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
    • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
    • B32B2329/06—PVB, i.e. polyinylbutyral
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • 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
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1414—Ceramic, glass, glasslike, vitreous
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
    • 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.]
    • 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.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • 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.]
    • Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
    • Y10T428/31601—Quartz or glass
    • 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.]
    • Y10T428/31616—Next to polyester [e.g., alkyd]
    • 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.]
    • Y10T428/31627—Next to aldehyde or ketone condensation product
    • Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
    • 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
    • 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]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • 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
    • 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]
    • Y10T428/31942—Of aldehyde or ketone condensation product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明为包括耐擦伤透明涂层的玻璃叠层制品。本发明的叠层耐划伤，并在约40℃以上的温度下可容易修复和甚至自愈合。

Description

用于玻璃-塑料玻璃窗产品的耐擦伤低聚物基涂层
本申请要求2003年9月2日提交的美国临时申请No.60/499949的权益。
                         发明背景
发明领域
本发明涉及具有耐划伤和擦伤的低聚物涂层的层压玻璃制品，和制备这种制品的方法。
现有技术描述
通常在例如汽车中使用底涂层/透明涂层体系作为罩面漆。这种体系被设计来保护汽车的油漆和罩面漆。用于汽车罩面漆的可修补耐擦伤涂层是已知的，并描述在例如美国专利No.5827910和美国专利No.6376596 B1中。
用于透明玻璃叠层的涂层是已知的。例如，聚硅氧烷可用作挡风玻璃叠层的聚对苯二甲酸乙二醇酯(PET)膜上的硬质涂层。但是，聚硅氧烷涂层可被锋利的物体永久划伤。随着时间推移，透明叠层的光学质量可由于划伤的积聚而大大降低。另外，聚硅氧烷涂层不能以大于2.8微米的厚度被施加到叠层上，否则会因涂层膜的常规处理形成破裂。
透明叠层的可修补涂层是已知的。例如，美国专利No.4784916、美国专利No.4671838和美国专利No.4652494中描述了可粘着地施加到挡风玻璃上作为双层涂层的预成型耐划伤、可自修补的聚氨酯片。
                         发明概述
在一个方面，本发明为一种玻璃叠层制品，包括：透明涂层/聚合物膜双层，其中透明涂层为由组分(1)和(2)的组合得到的耐划伤涂层组合物，其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
在另一方面，本发明为一种制造玻璃叠层制品的方法，包括步骤：混合两种组分(1)和(2)得到透明涂层组合物；(b)通过施加透明涂层组合物到聚合物膜上涂覆聚合物膜；(c)固化聚合物膜上的透明涂层组合物得到固化的涂层膜；和(d)层压固化的涂层膜到包括至少一层玻璃的叠层上得到玻璃叠层；其中透明涂层组合物为耐划伤的涂层组合物，其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
在又一方面，本发明为一种制造玻璃叠层制品的方法，包括步骤：混合两种组分(1)和(2)得到透明涂层组合物；(b)通过施加透明涂层组合物到聚合物膜上涂覆聚合物膜；(c)固化聚合物膜上的透明涂层组合物得到固化的涂层膜；和(d)施加粘合剂组合物的涂层到固化的涂层膜的第二侧上，和(e)通过使粘合剂涂覆的固化膜表面与包括至少一层玻璃的衬底的表面接触来施加固化膜到衬底上得到玻璃叠层；其中透明涂层组合物为耐划伤的涂层组合物，其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
                         发明详述
在一种实施方案中，本发明为包括耐擦伤透明涂层的玻璃叠层。本发明的玻璃叠层包括被层压到至少一层热塑性聚合物夹层的至少一个玻璃层。热塑性聚合物夹层可为任何在玻璃叠层制造中已知的并常规使用的聚合物材料。例如，热塑性聚合物可选自(i)聚氨酯(PU)，(ii)聚碳酸酯(PC)，(iii)聚乙烯醇缩丁醛(PVB)，(iv)聚酯，如聚对苯二甲酸乙二醇酯(PET)或(v)由乙烯与α，β-不饱和羧酸共聚得到的乙烯酸共聚物或它的衍生物。在本发明的实施中可使用各种常规夹层材料的组合。优选地，夹层材料选自PVB和乙烯酸共聚物或它的衍生物。适用于本发明实施的酸衍生物对于本领域那些技术人员是已知的，并包括酯、盐、酐、酰胺等。酸共聚物可被完全或部分地中和为盐(或部分盐)。完全或部分中和的酸共聚物通常称为离聚物。合适的共聚物可包括可为烯键式不饱和羧酸的酯的任选第三单体成分。可在商业上从例如E.I.DuPont de Nemours & Company以商标名例如Surlyn和Nucrel购买适用于本发明的实施的酸共聚物。
叠层还包括第二聚合物层，其被层压到未层压到玻璃的第二表面上的夹层上。第二聚合物层可为透明的任何东西，并可粘着地结合到夹层和透明涂层组合物上，如例如聚氨酯、PET和乙烯/酸共聚物。在本发明的实施中优选作为第二聚合物层的是PET。
透明涂层被涂覆到第二聚合物层上。可由(A)至少一种含羟基的低聚物与至少一种异氰酸酯低聚物的组合，或(B)至少一种含酐的低聚物与至少一种含环氧化物的化合物的组合形成透明涂层。用于本发明实施的合适低聚物尤其描述在WO9744402和美国专利No.5827910中，并可按其中所述得到。
可通过使多官能醇如季戊四醇、己二醇、三羟甲基丙烷、类似化合物或它们的混合物和环单体酐如六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐等反应，并进一步使这样得到的酸低聚物和单官能环氧化合物如环氧丁烷、环氧丙烷、类似化合物或它们的混合物反应得到合适的含羟基低聚物。适用于本发明实施的含羟基低聚物可具有在约300至约3000范围内的分子量。优选地，含羟基低聚物的分子量在约400至约2500的范围内。更优选分子量在约450至约2000的范围内，最优选在约500至约1500的范围内。
合适的异氰酸酯低聚物为例如：1，6-己二异氰酸酯的异氰脲酸酯三聚物；可从Bayer得到的DESMODUR3300；可从Rhodia得到的TolonateHDT；和异佛尔酮二胺的异氰脲酸酯三聚物，等等。
合适的酐低聚物为结构用通式：R-CO-O-CO-(R’-CO-O-CO)n-R限定的线型酐，其中R为具有2至50个碳原子的单取代烃基，R’为具有2至50个碳原子的二取代烃基，烃R和R’基含有或不含有醚键、尿烷键或酯键，n为1至500的整数。另外合适的为分子量小于约2000并包括(1)中心部分和(2)超过1个键合到每个中心部分的非环酐部分的酐。可通过使多官能醇如季戊四醇、己二醇、三羟甲基丙烷等和环单体酐如六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐等反应，并进一步使这样得到的酸低聚物和烯酮反应得到适合作为(b)型酐的酐。
合适的环氧低聚物为例如环己烷二羧酸的二环氧甘油酯如CibaGeigy的AralditeCY-184以及环脂族环氧化物如可从Union Carbide得到的ERL-4221，等。在另一实施方案中，本发明为制备叠层的方法，包括制备透明涂层组合物的步骤。本发明的透明涂层可通过混合至少一种低聚物组分(1)化合物和至少一种低聚物成分(2)化合物得到。优选如果组分(1)为含羟基低聚物，则组分(2)应为含异氰酸酯的低聚物，和如果组分(1)为含酐的低聚物，则组分(2)为含环氧化物的低聚物。例如，至少一种合适的含羟基低聚物可与至少一种合适的异氰酸酯低聚物组合。异氰酸酯和羟基低聚物可按能使存在的全部羟基官能团与异氰酸酯官能团反应的化学计量比混合，即在全部羟基官能团已反应后，存在稍微化学计量过量的异氰酸酯。但是，优选加入化学计量过量的羟基组分以便在全部异氰酸酯官能团反应后保留部分残余的羟基官能团。本文使用的摩尔当量为完全与1摩尔其它反应物如组分(2)反应所需要的反应物如组分(1)的摩尔数。当量比为本领域的普通技术人员通过用实际存在的反应物摩尔数除以完全反应所需的摩尔数可容易确定的比。羟基低聚物与异氰酸酯低聚物的当量比(HY∶ISO)大于0.60。优选该比例在约0.70至约1.50的范围内，更优选在约0.80至约1.40的范围内，最优选在约0.90至约1.35的范围内。在尤其优选的实施方案中，对于四羟基低聚物，羟基低聚物与异氰酸酯低聚物的当量比在约1.10至约1.35的范围内。令人惊奇地发现，较高的HY∶ISO比能在较低的温度下产生较快的划伤和裂痕愈合。优选按在全部酐反应后剩余过量环氧化物的化学计量比使酐低聚物与含环氧化物的低聚物混合。优选地，环氧低聚物与酐的当量比为至少0.70，并优选约0.70至约1.40。更优选环氧化物与酐的当量比为约0.90至约1.30，最优选约1.00至约1.25。
优选应恰好在施加到聚合物膜前混合透明涂层组分(1)和(2)。优选在施加到聚合物膜前少于约60分钟内混合组分(1)和(2)。在施加透明涂层到聚合物膜后，在放入到加热的环境中固化透明涂层前，可使涂层在室温下静置一段时间，一般少于30分钟。可在至少约100℃，优选在120℃以上，最优选在约125℃以上但低于约150℃的温度下固化涂层。
按本文所述得到的固化涂覆聚合物膜为具有低浊度和良好清晰透明度的光学透明膜。
如本文所述，通过层压涂覆聚合物膜到合适材料可得到包括固化透明涂层的叠层。本文使用的层压方法可为本领域中已知的或常规的任何方法。但是，优选的层压方法可能取决于层压的具体细节，包括叠层的结构和/或用于构造叠层的材料。例如，可使用合适的材料并在组件中按所需的顺序放置它们来构造叠层组件。优选在本发明的实施中使用玻璃盖板盖住并保护透明涂层膜的暴露表面。在一些情况下，希望在袋中放置组件，又把袋放到真空室中，从袋和室中除去尽可能多的空气，然后还在真空下密封袋。不管是否真空装袋，然后都在设定在90-150℃的炉中加热叠层组件至少约20分钟。炉可为高压釜，其中组件受到约125℃以上的温度和约12个大气压以上的压力。确切时间可取决于使用的条件，但在冷却和减压高压釜前保持温度和压力在所需的水平至少约9分钟。
在优选的实施方案中，可通过用粘合剂组合物涂覆聚合物膜的未涂覆表面即意欲层压到玻璃表面上的表面，然后用玻璃表面接触粘合剂涂覆的聚合物膜表面，得到本发明的叠层。粘合剂可为湿活化粘合剂。在这种情况下，可在接触两个表面之前润湿玻璃表面和/或粘合剂涂覆的聚合物膜表面中的一个或两个。在一些情况下，可优选在使玻璃与粘合剂涂覆的聚合物膜表面接触前润湿玻璃表面。在其它情况下，可优选润湿粘合剂涂覆的膜表面。在另外一些情况下，可优选在使两个表面彼此接触前润湿两个表面。例如，可从E.I.DuPont deNemours and Company得到的Elvanol聚乙烯醇的水混合物可适用作本文的水活性粘合剂。
可使用其中不需要水活化的其它粘合剂。例如，在美国专利公开No.US2002/0061395 A1中描述了一种适用于本发明的粘合剂。在一种优选的实施方案中，可能需要不包括水和/或不需要用水活化的粘合剂以便避免由叠层吸收或捕集的水引起的问题。
在任何情况下，用于本发明的合适粘合剂都是已知的。例如，美国专利No.4973511中描述了合适的粘合剂。合适的粘合剂为透明的粘合剂，其可包括：在DuPont Technical Bulletin No.17的题为“PolyesterAdhesives”中描述的聚酯粘合剂，尤其是其中的粘合剂No.46960、46971和46690；聚酰胺粘合剂，如例如“Versalon”1140(General Mills)；和/或在叠层安全玻璃的构造中通常使用的乙烯基树脂基粘合剂。
在另一实施方案中，本发明为包括用本发明的耐擦伤涂层涂覆的聚合物膜的叠层，其中聚合物膜被粘合性地直接粘结到玻璃上，在玻璃和涂覆的聚合物膜之间没有热塑性夹层插入层。例如，在一些应用中需要从叠层结构中排除PVB，并粘合性地粘结涂覆的PET膜到玻璃上。
本发明的叠层具有优异的耐久性、耐冲击性、韧性和夹层耐切割、划伤、裂痕性等。通过施加热到叠层的透明涂层上可容易地修复被划伤的本发明叠层。通过加热划伤的叠层到至少约30℃的温度保持至少约15分钟可除去(愈合)在本发明的涂覆叠层上产生的划伤。优选地，叠层表面被加热到至少约35℃的温度达至少约30分钟，更优选到40℃达至少约30分钟。甚至更优选地，划伤的叠层被加热到至少约60℃的温度达至少约45分钟。最优选地，可通过加热叠层表面到至少约70℃的温度达至少约60分钟来愈合划伤的叠层。
本发明的叠层可在汽车中用作挡风玻璃和/或侧挡风玻璃(sidelite)和/或玻璃天窗。本发明的叠层还尤其用于建筑应用，例如在建筑物中。本发明的叠层易清洗，并耐剥落和射弹的透过。
实施例
实施例仅用于说明目的，不用来限制本发明的范围。
实施例1
通过混合71.1wt％的成分1和28.9wt％的成分2制备涂层配方(A)。成分1由：56.87wt％的四羟基低聚物(按美国专利No.6376596的方法1所述得到)；0.68wt％的在丙二醇单甲醚乙酸酯中的10％BYK301，可从Byk Chemie得到；2.8wt％的1％二月桂酸二丁基锡在甲基乙基酮中的混合物；和10.75wt％的乙酸丁酯组成。成分2为TolonateHDT LV，其为可从Rhodia得到的1，6-己二异氰酸酯的异氰脲酸酯三聚物。重量百分比基于成分1和成分2组合的总重量。
实施例2
通过混合72.04wt％的成分1和27.96wt％的成分2制备涂层配方(B)。成分1由：28.73wt％的四羟基低聚物(按美国专利No.6376596B1的方法1所述得到)；29.09wt％的二羟基低聚物(按美国专利No.6376596B1的方法2所述得到)；0.68wt％的在丙二醇单甲醚乙酸酯中的10％BYK 301，可从Byk Chemie得到；2.77wt％的1％二月桂酸二丁基锡在甲基乙基酮中的混合物；和10.77wt％的乙酸丁酯组成。成分2为TolonateHDT LV，其为可从Rhodia得到的1，6-己二异氰酸酯的异氰脲酸酯三聚物。重量百分比基于成分1和成分2组合的总重量。成分1和成分2在施加到衬底表面上前才被混合。
实施例3
通过混合65.79wt％的成分1和34.21wt％的成分2制备涂层配方(D)。成分1由：26.17wt％的具有侧基的酐树脂(按美国专利No.5827910的实施例1A所述得到)；24.53wt％的直链酐(按美国专利No.5827910的实施例1B所述得到)；1.23wt％的在丙二醇单甲醚乙酸酯中的10％BYK 301，可从Byk Chemie得到；1.23wt％的25％氯化四丁基膦在丙二醇单甲醚乙酸酯中的混合物；1.45wt％的25％Niax A-99(可从Union Carbide得到的叔胺)在甲基乙基酮中的混合物；和7.86wt％的乙酸丁酯组成。成分2为可从Ciba-Geigy以AralditeCY-184得到的1，2-环己烷二羧酸的二环氧甘油酯。重量百分比基于成分1和成分2组合的总重量。成分1和成分2在施加到衬底表面上前才被混合。
实施例4-8
将实施例1-3的涂层组合物A、B和D各自涂覆到4密耳聚对苯二甲酸乙二醇酯膜上，膜表面已预先被火焰处理以提高粘合性。涂覆后将涂覆的膜样品在室温下保持5-10分钟，然后在140℃下焙烧30分钟以固化涂层。涂层厚度按表1所述变化。按照下面描述的方法测试划伤性能、耐磨性、涂层粘合性和浸入到沸水中对涂层粘合性和浊度的影响。测试结果描述在下面的表1-4中。
实施例9-14
使用装在RESOURCE I实验室涂覆器设备上的#B0线缠绕棒将实施例1-2的涂层组合物A和B各自涂覆到4密耳聚对苯二甲酸乙二醇酯膜上，膜表面已预先被火焰处理以提高粘合性。涂覆后将涂覆的膜样品在室温下保持10分钟，然后在热风炉中在100℃、120℃或140℃下焙烧30分钟以固化涂层。“A”组合物的涂覆厚度为28-36微米，“B”组合物的涂覆厚度为32-37微米。
实施例15-通用层压过程
按如下构造玻璃叠层组件：玻璃/PVB/PET/透明涂层/盖板。盖板可为任何硬质材料，但通常是浮法玻璃。尽管在盖板上可使用任何表面图案，但对于光学应用，需要光滑表面。可按照常规技术层压多层构造。按照下面的步骤将本文描述的组件真空装袋。将叠层构造放在塑料袋中，然后将塑料袋放到真空室中，抽空真空室以除去空气，在还是真空的同时热密封。将真空装袋的构造放在高压釜中，并经受约17个大气压的压力和约125℃至约150℃的温度30分钟。对室减压并冷却。从袋中取出叠层并除去盖板。
实施例16-21
在140℃的高压釜温度下，利用实施例15的层压步骤在高压釜中将实施例9-14的固化涂覆膜层压到玻璃上。使用玻璃盖板，在使用前用含350ppm MgSO4的水洗涤盖板以防止盖板和透明涂层之间的粘附。得到的叠层在光学上是平滑的，并且盖板容易除去。
划伤性能
使用装备有与0.003英寸球面头以90°夹角搭接的金刚石触针的502型Taber Shear/Scratch Tester测定每个测试样品的划伤性能。触针与被测试涂覆膜的表面成90°角定位在试验装置的臂上。涂覆膜样品水平位于试验装置的盘上，涂覆面向上以接受触针。通过沿臂滑动重物到标记位置将给定重量施加到臂上。降低带触针的臂与涂覆膜接触，并以0.5英寸/秒的速度旋转附有涂覆膜的盘。然后检查触针路径的任何划伤，并测量任何可见划伤的宽度。在触针臂上使用不同的重物重复这种过程。在记录可见度程度和实际划伤宽度后，在保持在70℃的炉中加热样品30分钟以确定对划伤可见度和宽度的影响。实施例4-8的结果示于表1。
表1
  实施例   厚度(微米)  状态1   划伤宽度a(mm)   划伤宽度b(mm)   划伤宽度c(mm)   划伤宽度d(mm)   划伤宽度e(mm)
  4   30-40  AS   NV2   0.033   0.050   0.058   0.098
  4  AH   NV   NV   0.048   0.054   0.093
  5   10-15  AS   0.035   0.047   0.058   0.068   0.099
  5  AH   NV   NV   0.043   0.054   0.071
  6   30-40  AS   0.029   0.046   0.058   0.067   0.104
  6  AH   NV   NV   NV   NV   NV
  7   20  AS   NV   0.040   0.051   0.065   0.096
  7  AH   NV   NV   NV   0.053   0.077
  8   30-40  AS   NV   0.031   0.049   0.063   0.124
  8  AH   NV   NV   NV   NV   NV
1AS＝划伤态；AH＝在70℃下加热30分钟后。
2NV＝划伤不可见
a触针重量20克。
b触针重量30克。
c触针重量40克。
d触针重量50克。
e触针重量100克。
耐磨性
使用ANSI Z-26.1，Test Number 34定义的Taber Abrasion试验评价耐磨性。在这个试验中，在500克重物下用CS-10F磨蚀机轮磨蚀样品表面100转。测量磨蚀区中透明样品的浊度增加，并表示为Taber浊度％。在涂覆面上磨蚀透明涂覆的样品，并测量Taber浊度，然后加热并在保持在70℃的炉中保持30分钟。从炉中取出后再次测定Taber浊度，以确定加热是否消除了磨痕。结果记录在表2中。
表2
实施例 涂层厚度(微米)   Taber浊度a(％)
  初始   加热后
  4   30-40   25.8   13.6
  5   10-15   38.2   24.6
  6   30-40   36.2   20.8
  7   20   24.2   13.1
  8   30-40   23.1   11.7
a100转/500克
光学性质
为了测定膜的光学性质，将膜样品浸入在沸水中2小时和6小时，并按照ASTM D 1003-61(1977年重新批准)的方法测定Gardner浊度值。该膜具有良好的清晰透明度和低浊度。结果记录在表3中。
表3
实施例   Gardner浊度(％)
  初始   加热2小时后   加热6小时后
  4   1.1   3.8   12.5
  6   0.6   5.5   4.0
  8   1.0   8.1   12.4
涂层粘合性
使用对不锈钢的剥离强度为40盎司/英寸的PERMACELTM带按照ASTM D3359-87Tape Test测定涂层粘合性。在浸入到沸水中2小时和6小时的前和后测量粘合性。粘合性试验的结果提供在表4中。
表4
实施例   涂层粘合性(保留的涂层％)
  初始  浸入沸水中2小时后   浸入沸水中6小时后
  4   100  100   100
  6   100  100   100
  8   100  100   100
实施例22-27
通过以各种比例混合成分1和成分2制备涂层配方，使得羟基与异氰酸酯的当量比按表5中所示变化。成分1由：56.87wt％的四羟基低聚物；0.68wt％的在丙二醇单甲醚乙酸酯中的10％BYK 301，可从Byk Chemie得到；2.8wt％的1％二月桂酸二丁基锡在甲基乙基酮中的混合物；和10.75wt％的乙酸丁酯组成。成分2为TolonateHDT LV，其为可从Rhodia得到的1，6-己二异氰酸酯的异氰脲酸酯三聚物。重量百分比基于成分1和成分2组合的总重量。
                         表5
  实施例   成分1   成分2   当量比
  22   12.30   5.00   0.95
  23   14.15   5.00   1.09
  24   16.00   5.00   1.24
  25   12.90   5.00   0.95
  26   14.85   5.00   1.09
  27   16.80   5.00   1.24
实施例28-33
通过将7密耳厚的上述涂层组合物涂覆到PET膜上得到PET透明涂覆膜。按照实施例15的步骤制备叠层，并在热压处理后评价光学性质和性能。叠层没有变色，保持透明和不浑浊，完全符合盖板产生光学平表面，并能没有粘附趋势地从盖板容易地脱离的结果。结果列在表6中。
                         表6
  实施例   透明度(％)   浊度(％)   清晰度(％)   20°光泽   YID色
  C11   92.8   0.09   100   101.3   0.30
  C22   89.8   0.61   99.7   153.7   1.60
28a 91.9 1.08 99.7 99.3 1.47
  29b   91.6   0.73   99.6   104.3   1.45
  30c   91.9   0.57   99.8   103.6   1.52
  31d   91.9   0.79   99.6   103.1   1.46
  32e   91.7   0.59   99.7   105.8   1.56
  33f   91.9   1.29   99.7   103.0   1.41
190密耳玻璃，不是本发明的实施例
27密耳PET膜，不是本发明的实施例
a由实施例22的膜得到的叠层
b由实施例23的膜得到的叠层
c由实施例24的膜得到的叠层
d由实施例25的膜得到的叠层
e由实施例26的膜得到的叠层
f由实施例27的膜得到的叠层
                         表7
  实施例   触针负荷(g)   在该温度下加热1小时后的划伤可见度：
  25℃   40℃   50℃   60℃   70℃
  C1   50   V1   V   V   V   V
  C1   100   V   V   V   V   V
  C2   50   V   V   V   V   V
  C2   100   V   V   V   V   V
  2g   50   V   V   V   V   NV
  28   100   V   V   V   V   NV
  29   50   V   V   V   V   NV
  29   100   V   V   V   V   NV
  30   50   V   V   V   NV   NV
  30   100   V   V   V   V   NV
  31   50   V   NV   NV   NV   NV
  31   100   V   NV   NV   NV   NV
  32   50   V   NV   NV   NV   NV
  32   100   V   NV   NV   NV   NV
  33   50   NV   NV   NV   NV   NV
  33   100   V   V4   BV3，4   BV4   BV4
1V＝对肉眼可见
2NV＝对肉眼不可见
3BV＝对肉眼勉强可见
4触针穿透到PET膜表面
实施例34-35
使用下面表8a中描述的涂层组合物，按实施例15中所述制备两个叠层。然后使用ASTM G26-90方法A对叠层进行XENOTEST1200CPS测试。将样品暴露于1515MJ/m2UV辐射(300-400nm)总共5260小时的时间。测量曝光叠层的GardnerHaze(ASTM 1003-61)、20°光泽和通过ASTM带粘合试验(ASTM 3359-97)测量涂层粘合性。结果示于表8b中。还目视检查了样品的发黄度和清晰透明度。
表8a
  涂层组合物   实施例34   实施例35
  成分1(羟基低聚物)   30.0g   30.0g
  成分2(异氰酸酯)   11.64g   9.90g
  当量比成分1/成分2   0.95   1.12
样品没有显示出任何视觉颜色变化，透明度被认为良好。由于XENOTEST喷水循环而出现一些起雾。
表8b
实施例 浊度(％)   20°光泽   带粘合性
  对照   暴露   交叉影线   无划痕   x-划痕
  34   1.6   108   96.3   30   100   100
  35   2.2   124   124   100   100   100
实施例36
涂覆透明的7密耳火焰处理的PET膜，一面上用ELVANOLPVA配方的水溶液涂覆以作为水活化粘合剂，另一面上用实施例34(B1)中描述的低聚物透明涂层涂覆以作为耐划伤的可愈合涂层。通过润湿玻璃和/或在粘合剂涂覆面上的膜然后使用橡胶辊或“刮刀”挤压润湿的膜以除去所有多余的水来将膜粘结到玻璃上。然后使玻璃和膜粘结结构在室温下干燥直到粘合剂是干的，即直到水分扩散透过PET膜和粘合剂层“凝固”，并且膜被牢固地粘着到玻璃上。
实施例37
7密耳的透明CRONARPET膜，两面都经火焰处理，使用#28线-缠绕的涂覆棒在一面上用包含ELVANOL型51-05粉末的15％水溶液涂覆。在用实施例34(B1)描述的透明涂层配方涂覆相对面前使涂层在室温下干燥。使用#28线缠绕的涂覆棒施加涂覆配方。使涂层在室温下闪蒸去溶剂，然后在施加透明涂覆的PET膜到玻璃上(参见“玻璃施加方法”，下面的实施例39)前使其在室温下凝固24小时。
实施例38
7密耳的透明CRONARPET膜，两面都经火焰处理，使用#28线-缠绕的涂覆棒在一面上用包含ELVANOL型51-05粉末的15％水溶液涂覆。在用实施例35(B2)描述的透明涂层配方涂覆相对面前使涂层在室温下干燥。使用#28线缠绕的涂覆棒施加涂覆配方。使涂层在室温下闪蒸去溶剂，然后在施加透明涂覆的PET膜到玻璃上(参见“玻璃施加方法”，下面的实施例40)前使其在室温下凝固24小时。
玻璃施加方法
实施例39
通过(1)用水雾喷洒玻璃表面，(2)放置涂覆膜到湿玻璃上，ELVANOL涂覆面朝向玻璃，和(3)使用橡胶刃“刮刀”挤压膜到玻璃上，利用多次通过以从界面除去全部多余的水，将实施例37的涂覆膜附着到90密耳厚的退火浮法玻璃上。在测试耐划伤性和光学性质前，使涂覆膜/玻璃结构干燥几天。干燥的结构非常透明和无色，膜充分粘结到玻璃上。
实施例40
按照实施例39的方法将实施例38的涂覆膜附着到90密耳厚的退火浮法玻璃上。
表9
  实施例   浊度(％)   透射率(％)   透明度(％)   YID
  C31   2.2*   90.8   98.4   0.55
  39   0.9   92.0   98.6   0.52
  40   0.6   92.1   98.8   0.70
1未涂覆的PET/PVA/玻璃，不是本发明的实施例
*用刮刀磨蚀未涂覆的PET膜，得到较高的浊度读数，即没有透明涂层保护不受划伤。
对实施例39和40的膜/玻璃结构进行Taber划伤试验，如上所述，使用50和100克的划伤负荷。使用显微镜测量划伤样品的划痕宽度，用肉眼测量可见度。然后使它们在室温下静置过夜，然后再次检查划伤。结果提供在表10中：
表10
  可见度   宽度
  实施例   负荷(g)   划伤态   18小时后(室温)   划伤态   18时后(室温)
  C3   50   V   V   0.050   0.052
  100   V   V   0.079   0.078
  39   50   V   NV   0.070   NV
  100   V   NV   0.085   0.019
  40   50   V   NV   0.069   NV
  100   V   V   0.076   0.042
*实施例40的涂层比39涂层软，触针渗透穿过它到下面的PET表面内-这使划伤永久可见，即使在室温下静置时发生一定的透明涂层愈合。

Claims (33)

1.一种玻璃叠层，包括：透明涂层/聚合物膜双层，其中该透明涂层为由组分(1)和(2)的组合得到的耐划伤涂层组合物，其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
2.权利要求1的叠层，其中所述组分(1)为至少一种含羟基的低聚物，组分(2)为至少一种异氰酸酯低聚物。
3.权利要求2的叠层，其中所述叠层包括至少一个被层压到至少一个热塑性聚合物层上的玻璃层。
4.权利要求3的叠层，其中所述透明涂层/聚合物双层的聚合物被层压到所述热塑性聚合物层上。
5.权利要求4的叠层，其中所述热塑性聚合物为PVB或乙烯共聚物。
6.权利要求5的叠层，其中所述热塑性聚合物为PVB。
7.权利要求6的叠层，其中所述双层组分的聚合物为PET。
8.权利要求7的叠层，其中所述至少一种含羟基低聚物为多官能醇与环单体酐然后进一步与环氧化物反应的反应产物。
9.权利要求8的叠层，其中所述多官能醇选自：季戊四醇、己二醇、三羟甲基丙烷、类似化合物或它们的混合物。
10.权利要求9的叠层，其中所述环氧化物选自：1，2-环氧丁烷；2，3-环氧丁烷；环氧丙烷；环氧乙烷；和类似化合物，或它们的混合物。
11.权利要求10的叠层，其中所述含羟基的低聚物为含四羟基的低聚物。
12.权利要求11的叠层，其中所述异氰酸酯低聚物为1，6-己二异氰酸酯的异氰脲酸酯三聚物。
13.权利要求1的叠层，其中所述透明涂层/聚合物膜双层在玻璃和双层之间没有中间热塑性聚合物层的情况下被粘着地结合到玻璃上。
14.权利要求13的叠层，其中所述组分(1)为至少一种含羟基的低聚物，组分(2)为至少一种异氰酸酯低聚物。
15.权利要求14的叠层，其中所述双层组分的聚合物为PET。
16.权利要求15的叠层，其中所述至少一种含羟基低聚物为多官能醇与环单体酐然后进一步与环氧化物反应的反应产物。
17.权利要求16的叠层，其中所述多官能醇选自：季戊四醇、己二醇、三羟甲基丙烷、类似化合物或它们的混合物。
18.权利要求17的叠层，其中所述环氧化物选自：1，2-环氧丁烷；2，3-环氧丁烷；环氧丙烷；环氧乙烷；和类似化合物，或它们的混合物。
19.权利要求18的叠层，其中所述含羟基的低聚物为含四羟基的低聚物。
20.权利要求19的叠层，其中所述羟基低聚物与异氰酸酯低聚物的当量比大于0.60。
21.权利要求20的叠层，其中所述当量比在约0.70至约1.50的范围内。
22.权利要求21的叠层，其中所述当量比在约0.80至约1.40的范围内。
23.权利要求22的叠层，其中所述当量比在约0.90至约1.35的范围内。
24.权利要求23的叠层，其中所述异氰酸酯低聚物为1，6-己二异氰酸酯的异氰脲酸酯三聚物。
25.一种制品，其在聚合物膜上包括透明涂层，其中该透明涂层为组分(1)和(2)以大于0.90的当量比混合的混合产物，其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
26.权利要求25的制品，其中所述聚合物膜为选自聚氨酯、乙烯/酸共聚物和PET的聚合物。
27.权利要求26的制品，其中所述聚合物膜为PET。
28.一种制品，其在聚合物膜上包括透明涂层，其中该透明涂层为组分(1)和(2)以约1.10至约1.35范围内的当量比混合的混合产物，其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物，其中组分(1)具有在约300至约3000范围内的分子量。
29.权利要求28的制品，其中所述组分(1)具有在约400至约2500范围内的分子量。
30.权利要求29的制品，其中所述组分(1)具有在约450至约2000范围内的分子量。
31.权利要求30的制品，其中所述组分(1)具有在约500至约1500范围内的分子量。
32.一种制造玻璃叠层制品的方法，包括步骤：(a)混合两种组分(1)和(2)得到透明涂层组合物；(b)通过施加透明涂层组合物到该聚合物膜至少两个表面的一个上涂覆聚合物膜；(c)固化聚合物膜表面上的透明涂层组合物得到固化的透明涂层/聚合物膜双层膜，其中该聚合物膜的至少一个表面被暴露；和(d)层压该固化双层膜的暴露聚合物表面到包括至少一个玻璃层的叠层上得到玻璃叠层；其中该透明涂层组合物为耐划伤的涂层组合物，并且其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
33.一种从透明叠层表面除去缺陷的方法，包括步骤：加热叠层的有缺陷表面到至少70℃，其中该表面包括通过以至少0.90的当量比(组分(1)：组分(2))混合两种组分(1)和(2)得到的透明涂层，并且其中组分(1)包括选自具有羟基官能团或酐官能团的低聚物化合物中的低聚物化合物，和其中组分(2)为异氰酸酯低聚物或具有环氧官能团的化合物。
CNA2004800327535A 2003-09-02 2004-08-27 用于玻璃－塑料玻璃窗产品的耐擦伤低聚物基涂层 Pending CN1878669A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US49994903P 2003-09-02 2003-09-02
US60/499,949 2003-09-02

Publications (1)

Publication Number Publication Date
CN1878669A true CN1878669A (zh) 2006-12-13

Family

ID=34434827

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2004800327535A Pending CN1878669A (zh) 2003-09-02 2004-08-27 用于玻璃－塑料玻璃窗产品的耐擦伤低聚物基涂层

Country Status (8)

Country Link
US (4) US7294401B2 (zh)
EP (1) EP1660322A2 (zh)
JP (1) JP2007504024A (zh)
CN (1) CN1878669A (zh)
AU (1) AU2004280342A1 (zh)
CA (1) CA2537030A1 (zh)
MX (1) MXPA06002151A (zh)
WO (1) WO2005035241A2 (zh)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297407B2 (en) * 2004-09-20 2007-11-20 E. I. Du Pont De Nemours And Company Glass laminates for reduction of sound transmission
MX2007004353A (es) 2004-10-12 2007-10-19 3M Innovative Properties Co Peliculas protectoras y metodos relacionados.
US20080053516A1 (en) * 2006-08-30 2008-03-06 Richard Allen Hayes Solar cell modules comprising poly(allyl amine) and poly (vinyl amine)-primed polyester films
US20080128018A1 (en) * 2006-12-04 2008-06-05 Richard Allen Hayes Solar cells which include the use of certain poly(vinyl butyral)/film bilayer encapsulant layers with a low blocking tendency and a simplified process to produce thereof
US20080280076A1 (en) * 2007-05-11 2008-11-13 Richard Allen Hayes Decorative safety glass
US20080318063A1 (en) * 2007-06-22 2008-12-25 Anderson Jerrel C Glass laminates with improved weatherability
US20090087669A1 (en) * 2007-09-28 2009-04-02 Hayes Richard A Glass laminates comprising acoustic interlayers and solar control films
US20090155576A1 (en) * 2007-12-18 2009-06-18 E. I. Du Pont De Nemours And Company Glass-less glazing laminates
WO2009120824A1 (en) * 2008-03-26 2009-10-01 E. I. Du Pont De Nemours And Company High performance anti-spall laminate article
US7641965B1 (en) * 2008-06-30 2010-01-05 E.I. Du Pont De Nemours And Company Transparent light-weight safety glazings
US8298659B2 (en) * 2008-09-30 2012-10-30 E I Du Pont De Nemours And Company Polysiloxane coatings doped with aminosilanes
WO2010051525A1 (en) * 2008-10-31 2010-05-06 E. I. Du Pont De Nemours And Company High clarity laminated articles comprising an ionomer interlayer
US8399098B2 (en) * 2008-12-31 2013-03-19 E I Du Pont De Nemours And Company Laminates comprising ionomer interlayers with low haze and high moisture resistance
CN102341556A (zh) 2009-03-06 2012-02-01 纳幕尔杜邦公司 轻型玻璃层压板
US8760728B2 (en) * 2011-09-22 2014-06-24 Fuji Xerox Co., Ltd. Transparent plate for platen, document scanning apparatus, and image forming apparatus
WO2014059206A1 (en) 2012-10-12 2014-04-17 E. I. Du Pont De Nemours And Company Glass laminates with nanofilled ionomer interlayers
WO2014100309A1 (en) 2012-12-19 2014-06-26 E. I. Du Pont De Nemours And Company Cross-linkable acid copolymer composition and its use in glass laminates
US20160096350A1 (en) * 2014-10-02 2016-04-07 Solutia Inc. Multiple layer interlayer resisting defect formation
EP3368310A1 (en) * 2015-10-27 2018-09-05 Corning Incorporated Method of laminating ultra-thin glass to non-glass substrates
CN107698790B (zh) * 2016-08-05 2023-10-03 法国圣戈班玻璃公司 用于玻璃上的薄膜及其制造方法以及车窗
CN107323055A (zh) * 2017-07-28 2017-11-07 东莞市鼎力薄膜科技有限公司 用于汽车表面防护的tpu薄膜及其自修复涂层制备方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2251608B1 (zh) * 1973-11-16 1977-09-23 Saint Gobain
US4059469A (en) * 1974-02-01 1977-11-22 Libbey-Owens-Ford Company Glazing units, methods of making the same and adhesion promoters therefor
DE2629779C3 (de) * 1976-07-02 1985-04-04 Saint Gobain Verfahren zur Herstellung einer zweischichtigen Folie mit Selbstheileigenschaften unter Verwendung von Polyurethanen als Splitterschutzschicht eines Sicherheitsglases
FR2496089A1 (fr) * 1980-12-11 1982-06-18 Saint Gobain Vitrage Vitrage feuillete de securite
FR2548956B1 (fr) * 1983-07-11 1985-10-18 Saint Gobain Vitrage Feuille en matiere plastique transparente de haute qualite optique
US4652494A (en) * 1983-07-11 1987-03-24 Saint-Gobain Vitrage Bilayer laminate and preformed sheet for use therein
US4925794A (en) * 1985-01-02 1990-05-15 Fujisawa Pharmaceutical Co., Ltd. Hybrid plasmids and microorganisms containing them
US4871806A (en) 1987-11-16 1989-10-03 The Sherwin-Williams Company Reactive coatings comprising an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound
US4923757A (en) * 1987-12-16 1990-05-08 Ppg Industries, Inc. Bilayer windshield with an abrasion and solvent resistant polyurethane protective coating
FR2631628B1 (fr) * 1988-05-20 1992-04-30 Saint Gobain Vitrage Couche de polyurethane transparente resistant a la rayure et a l'abrasion ayant les proprietes d'absorbeur d'energie et d'anti-buee, procede de fabrication et vitrages qui l'utilisent
US4973511A (en) * 1988-12-01 1990-11-27 Monsanto Company Composite solar/safety film and laminated window assembly made therefrom
US5145744A (en) * 1990-11-26 1992-09-08 Monsanto Company Bilayer glazing panel
US5567529A (en) * 1991-11-27 1996-10-22 E. I. Du Pont De Nemours And Company Multilayered glass laminate having enhanced resistance to penetration by high velocity projectiles
JP3231151B2 (ja) * 1993-07-23 2001-11-19 サン−ゴバン ビトラージュ 複層フィルムの製造方法
FR2725399B1 (fr) * 1994-10-06 1996-11-08 Saint Gobain Vitrage Vitrage de securite
US5827910A (en) * 1994-12-21 1998-10-27 E. I. Du Pont De Nemours And Company Mar-resistant coating
TW380151B (en) 1996-05-17 2000-01-21 Du Pont Mar-resistant oligomeric-based coatings
US6376506B1 (en) * 1997-01-23 2002-04-23 Syntex (U.S.A.) Llc Sulfamide-metalloprotease inhibitors
WO1998038227A1 (en) * 1997-02-28 1998-09-03 E.I. Du Pont De Nemours And Company New ionomers based on copolymers of ethylene with both mono- and dicarboxylic acids and polyamide blends containing these ionomers
US6376596B1 (en) * 1997-05-14 2002-04-23 E. I. Du Pont De Nemours And Company Mar-resistant oligomeric-based coatings
PT1322467E (pt) * 2000-09-28 2008-02-15 Solutia Inc Laminado de vidro resistente à intrusão
US6877341B1 (en) * 2001-01-26 2005-04-12 The Trustees Of Columbia University In The City Of New York Method for controlled surface scratch removal and glass resurfacing

Also Published As

Publication number Publication date
CA2537030A1 (en) 2005-04-21
JP2007504024A (ja) 2007-03-01
US7294401B2 (en) 2007-11-13
EP1660322A2 (en) 2006-05-31
US7435481B2 (en) 2008-10-14
US20070154723A1 (en) 2007-07-05
US20070144654A1 (en) 2007-06-28
US20050077002A1 (en) 2005-04-14
MXPA06002151A (es) 2006-04-27
US20070160852A1 (en) 2007-07-12
WO2005035241A2 (en) 2005-04-21
WO2005035241A3 (en) 2005-06-23
AU2004280342A1 (en) 2005-04-21

Similar Documents

Publication Publication Date Title
CN1878669A (zh) 用于玻璃－塑料玻璃窗产品的耐擦伤低聚物基涂层
EP1944277B1 (en) Antifogging article
EP1845141B1 (en) Antifogging coating composition
CN1931942A (zh) 改良制品
CN103228447A (zh) 防雾性物品及其制造方法
JP5018218B2 (ja) 防曇性物品および該防曇性物品の製造方法
TWI770069B (zh) 積層聚酯膜
TW200934738A (en) Edge coated glass polarized lens
JP2013203042A (ja) 積層体
WO2015152049A1 (ja) 防曇性物品及びその製造方法
JP2014001106A (ja) 防曇性ガラス物品その製造方法および輸送機器用物品
WO2009151086A1 (ja) 防曇性組成物および防曇性組成物用キットならびに防曇性物品および該防曇性物品の製造方法
JP6443443B2 (ja) 防曇剤組成物並びに防曇性物品及びその製造方法
JP2014114430A (ja) 防曇膜形成材料、防曇膜形成用塗布液、防曇性物品、及びそれらの製法
JP2020040869A (ja) 合わせガラスの中間膜用樹脂組成物、合わせガラス用中間膜、合わせガラスの中間膜用フィルム材、合わせガラス、合わせガラスの製造方法、画像表示装置、耐衝撃部材用樹脂組成物、耐衝撃膜及び耐衝撃膜用フィルム材
EP3124228B1 (en) Antifouling sheet
JP2019077750A (ja) シリコーン吸着フィルム
JP2017215585A (ja) 樹脂基材のハードコート形成用組成物、ハードコートの形成方法およびそれを用いた物品
JP2017100435A (ja) 透明樹脂積層体
JP6460097B2 (ja) 防曇剤組成物並びに防曇性物品及びその製造方法
KR100698481B1 (ko) 엘씨디 백라이트용 반사판 및 그 제조방법
JP6842764B2 (ja) 保護フィルム
CN113692417A (zh) 聚氨酯合成
JP2020152590A (ja) 合わせガラスの中間膜用フィルム材、合わせガラス、及び合わせガラスを製造する方法
JP2020152764A (ja) 合わせガラスの中間膜用フィルム材、合わせガラス、及び合わせガラスを製造する方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20061213