WO2022008489A1 - Laminated glass with anti-counterfeiting properties - Google Patents

Laminated glass with anti-counterfeiting properties Download PDF

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Publication number
WO2022008489A1
WO2022008489A1 PCT/EP2021/068612 EP2021068612W WO2022008489A1 WO 2022008489 A1 WO2022008489 A1 WO 2022008489A1 EP 2021068612 W EP2021068612 W EP 2021068612W WO 2022008489 A1 WO2022008489 A1 WO 2022008489A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
interlayer
wavelength
identification compound
identification
Prior art date
Application number
PCT/EP2021/068612
Other languages
French (fr)
Inventor
Ion LAZAR
Yosiaki ASANUMA
Leonard VOLPI
Robin ESCHRICH
Original Assignee
Kuraray Europe Gmbh
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
Priority claimed from JP2020117703A external-priority patent/JP2022015080A/en
Application filed by Kuraray Europe Gmbh filed Critical Kuraray Europe Gmbh
Priority to EP21739683.7A priority Critical patent/EP4178797A1/en
Publication of WO2022008489A1 publication Critical patent/WO2022008489A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
    • 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
    • B32B17/10036—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 two outer glass sheets
    • 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
    • B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
    • B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
    • B32B17/10275—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • 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
    • B32B17/10559—Shape of the cross-section
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    • 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
    • B32B17/10559—Shape of the cross-section
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    • 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
    • B32B17/10559—Shape of the cross-section
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    • B32B17/10596—Surface roughness created by melt fracture
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    • 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
    • B32B17/10605—Type of plasticiser
    • 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
    • B32B17/10614—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 comprising particles for purposes other than dyeing
    • B32B17/10633—Infrared radiation absorbing or reflecting agents
    • 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
    • B32B17/10651—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 comprising colorants, e.g. dyes or pigments
    • B32B17/10669—Luminescent agents
    • 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
    • B32B17/10678—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 comprising UV absorbers or stabilizers, e.g. antioxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • 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
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    • 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
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • 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
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    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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Abstract

The present invention relates to an interlayer for use in laminated glass with anti-counterfeiting properties.

Description

Laminated glass with anti-counterfeiting properties
The present invention relates to an interlayer for use in laminated glass with anti-counterfeiting properties.
Laminated glass, produced by combining two sheets of glass with an interlayer has been known for decades and is used for example in windscreens in cars and windows in residential buildings. Besides optical transparency, laminated glass should provide sufficient mechanical resistance against impact of an object hitting the laminated glass. The safety properties of laminated glass should not only prevent the object from penetrating the laminated glass but also prevent the glass sheet from disintegrating into potentially dangerous glass splinters.
Examples of polymers used in the manufacturing of the interlayers include ionomers like the SentryGlas® range or polyvinyl acetals like the Trosifol® PVB films.
However, it has been observed in recent years that laminates are offered on the market which claimed to be made with such genuine material but in fact contain counterfeit material or recycled genuine material, possibly in admixture with counterfeit material. Unfortunately, it is not straightforward to verify the genuiness of the interlayer material without destroying the laminated glass.
Therefore, it would be desirous to check the genuiness as well as possibly other information like the name of a manufacturer, the lot number or the grade/type of an interlayer contained in a laminated glass without destroying the laminated glass. Accordingly, it was an object of the present invention to provide an interlayer for laminated glazing comprising a film containing an ionomer and/or a polyvinyl acetal and optionally at least one plasticiser characterised in that the film is provided with at least one identification compound having its absorption maximum at a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm wherein the identification compound is provided in a pattern or shape adapted to bear information.
The term "having its absorption maximum at a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm" is intended to denote that the spectrum measured with the spectrophotometer Lambda 950 commercially available from Perkin Elmer in the range from 50 to 1500 nm has its absorption maximum either in the range of 50 to 350 nm or in the range of 800 to 1500 nm.
Preferably, the identification compound is provided in form of a barcode, a plurality of dots, one or more lines or a grid to the film. The identification compound can also be provided in form of a writing indicating the name of the interlayer film, the manufacturer, the manufacturing plant, the date of manufacture, the manufacturing line, the customer, and the lot number, and encrypted information.
In one embodiment of the invention, the information is applied to the interlayer film by at least one medium selected from the group consisting of letters, symbols, one-dimensional codes, two- dimensional codes, three-dimensional codes, color codes and RF tags. Examples of the one-dimensional code include those defined in JI S X0500-2. Examples of the two-dimensional code include those defined in JIS X0500-2. By three-dimensional code is meant a three-dimensionally readable code. Also preferably, a compound is used which is an ink that reflects or absorbs infrared rays, an ink which reflects ultraviolet rays or absorbs ultraviolet rays, or an ink which absorbs ultraviolet rays or infrared rays and emits the electromagnetic wave of a wavelength different from the absorbed electromagnetic wave.
The interlayer film for laminated glass may have the identification compound in its entirety or in a part thereof.
The identification compound as used herein can be any compound which is absorbing light having a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm. In some embodiments of the invention the compounds then emits light with a different wavelength. This light can then be detected with detection devices for those wavelengths, e.g. portable handheld spectroscopes. Such detection devices are known in the art.
Preferably, the identification compound does not impact the optical properties of the film, i.e. it does not absorb light in the spectrum visible to the human eye, i.e. the identification compound does not adsorb light in the wavelength of 400 to 700 nm.
In case the identification compound is not detected in the correct pattern or shape on the interlayer in the manufactured laminated glazing, it is verified that the material is not genuine.
Moreover, it has been noticed in the industry that genuine interlayer polymer material is recycled and, optionally in admixture with non-genuine material, reused for lamination. In that case, the identification compound might still be detected in the polymer material. However, the shape or pattern the identification compound is presented in will inevitably be changed in the melting and re-extruding process. This feature sets the instant invention apart from the anti-counterfeiting solutions of the prior art, where the mere presence of the identification compound might still be detected after recycling and the material might wrongly be deemed genuine.
The at least one identification can be dispersed or dissolved in the polymer material of the film. In that case, the identification compound can be (co-)extruded in a small area of the film, e.g. forming a one or more lines in the machine direction of the films. In that case, the identification compound needs to be soluble or at least dispersible in the polymer matrix used for manufacturing the film.
In another embodiment, the at least one identification compound is printed or coated onto at least one surface of the film. In that case, the identification compound can be provided in the form of more distinguished patterns.
Fig. 1 shows examples of possible shapes or patterns to be printed or coated onto the film.
Examples of suitable identification compounds are typically, but not limited to, materials that emit visible light upon excitation by light in the UV or IR range. Such materials could be, but are not limited to, fluorescent carbon based materials, doped metal sulfides, doped metal oxides, rare earth doped oxides, metal oxy- sulfides of lanthanides, mixed oxides capable of fluorescing, fluorescent dyes or phosphors, up-converting phosphors, phosphorescent materials, photochromic materials, metal nanoparticles and luminescent metal complexes.
The fluorescent carbon based materials include fluorescent carbon dots, photo luminescent carbon nanostructures or graphene quantum dots. As metal nanoparticles and/or quantum dots gold nanoparticles or different cadmium compounds, such as CdS, CdSe, CdTe, CdZnS, are used. These are also commercially available as core-shell configurations, such as CdSe/CdS/CdZnS, ZnCdSe/CdZnS, and ZnCdS/CdZnS.
Compounds which emit light in the visible spectrum after absorbing and being excited by IR radiation, are commonly called IR up- converters. Examples of this group for the use in the present invention can be chosen from, but are not limited to, doped oxyhalides, oxysulfides, oxychlorides and/or oxyfluorides of transition-metal ions, lanthanide ions and/or actinoid ions, such as Ti2+ ' Cr3+ ' Ni2+, Mo3+, Re4+, Os4+, Pr3+, Gd+3 ' Dy+3, Ho3+, Er+3, Tm2+, U4+ and / or U3+ . They are typically doped with, for example, Li, Na, K, Mg, Ge, Ga, Al, Pb, Cd, Ba. Preferred examples include doped ytterbium oxychloride/fluoride, erbium oxychloride/fluoride, erbium sulfide, thulium oxysulfide, gadolinium oxysulfide or oxychloride/fluoride compounds, such as NaYF4 :Er,Yb; YF3 :Er,Yb; YF3 :Tm,Yb, Y2O3:Yb,Er, NdrYAG and Li, NaYF4:Er.
Phosphors, which absorb light in the UV-spectrum and emit light with visible wave length can originate from a wide range of oxides, silicates, phosphates, halosilicates, borates, aluminates, gallates, halides, oxyhalides, sulfides. Examples include oxides, such as CaO:Eu, CaO:Eu,Na, CaO:Sm, CaO:Tb, ThO2 :Eu, ThO2 :Pr, ThO2 :Tb, Y2O3:Er, Y2O3:Eu, Y2O3:Ho, Y2O3:Tb,
La2O3:Eu, CaTiO3:Eu, CaTiO3:Pr, Srln2O4 :Pr,Al, SrY2O4:Eu, SrTiO3 :Pr,Al, SrTiO3:Pr, Y(P,V)O4:Eu, Y2O3:Eu, Y2O3:Tb, Y2O3:Ce,Tb, Y2O2S:EU, (Y,Gd)O3:Eu, YVO4:Dy; silicates, such as CasB2SiOio:Eu,
Ba2SoO4 :Ce,Li,Mn, CaMgSi2O6 :Eu, CaMgSi2C>6:Eu/Mn, Ca2MgSi207:Eu/Mn, BaSrMgSi207;Eu, Ba2Li2Si2O7)Sn, Ba2Li2Si2O7)Sn5Mn, MgSrBaSi207)Eu, Sr3MgSi2O8 :Eu,Mn, LiCeBa4Si4O14 :Mn, LiCeSrBa3Si40i4Mn; phosphates, such as YPO4:Ce,Tb, YPO4:Eu, LaPO4:Eu, Na3Ce(PO4)2 :Tb; halosilicates, such as LaSiO3ChCe5Tb; borates, such as YBO3:Eu, LaBO3:Eu, SrO.3B2O3 :Sm, MgYBO4:Eu, CaYBO4:Eu, CaLaBO4:Eu, LaALB2O6 :Eu, YA15B4O:EU, YA15B4O12 :Ce,Tb, LaAl3B40i2 :Eu, SrB8O,3:Sm, CaYB0. 8O3 . 7 :Eu, (Y5Gd)BC>3 Tb, (Y,Gd)BO3 :Eu; aluminates, such as YAIO3 :Eu, YAIO3 :Sm, YAlO3Tb, LaAlO3:Eu, LaAlO3 :Sm, Y4Al2O9:EU, Y3AI5O12:Eu, CaAl2O4:Tb, CaYAlO4:Eu, MgCeA109:Tb, Y3Al5O12Mn; miscellaneous oxides, such as LiInO2:Eu, LiInO2:Sm, LiLaO2:Eu, NaYO2 :Eu, CaTiO3:Pr, Mg2TiO4:Mn, YVO4:Eu, LaVO4:Eu, YAsO4:Eu, LaAsO4:Eu, MgsGe2On F2:Mn, CaY2ZrP6:Eu; halides and oxyhalides, such as CaF2 :Ce/Tb, K2SiF6Mn, YOBrrEu, YOChEu, YOF:Eu, YOF:Eu, LaOF:Eu, LaOChEu, (ErCls)o.2s(BaCl2)o.75, LaOBr:Tb, LaOBr:Tm ; CaS- type sulfides, such as CaS:Pr,Pb,Cl, CaS:Tb, CaS:Tb,Cl as well as miscellaneous sulfides and oxysulfides, such as Y2O2S:Eu and GdO2S:Tb.
In one embodiment of the present invention, the identification compound is a ultraviolet absorber like benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malo acid esters and formamidines. These ultraviolet absorbers may be used alone or in combination of two 2 or more.
Examples of benzophenones include, but are not limited to, (2- hydroxy-4-octyloxyphenyl)phenylmethanone, bis (2-hydroxy-4- methoxy)methanone, and the like.
Examples of benzotriazoles include 2-(2H-benzotriazole-2-yl)-4- methylphenol, 2-(5-chloro-2H-benzotriazole-2-yl)-6-(1,1- dimethylethyl)-4-methylphenol (tinuvin 326), 2-(2H-benzotriazol- 2-yl)4,6-bis(1,1-dimethylpropyl)phenol (tinuvin 328), 2-(2H- benzotriazol-2-yl)-4-(1,1, 3,3-tetramethylbutyl)phenol, 2-(2H- benzotriazol-2-yl)-4,6-bis(1-methyl-l-phenylethyl)phenol, 2,2'- methylene bis[6-(2H-benzotriazol-2-yl)4-t-octylphenol], and 2- (5-octylthio-2H-benzotriazol-2-yl)-6-tert
As an example of an ultraviolet absorber of triazines, 2,4,6- tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Examples of ultraviolet absorbers of benzoates include, but are not limited to, 3,5-(1,1-dimethylethyl)-2,4-bis(1,1- dimethylethyl)phenylbenzoate, (2,4-di-butylphenyl)3,5-di- oxybutyl-4-hydroxybenzoate, and the like.
Examples of ultraviolet absorbers of salicylates include, but are not limited to, salicylic acid, octyl salicylate, ethylhexyl salicylate, and the like.
Examples of ultraviolet absorbers for cyanoacrylates include, but are not limited to, ethyl-2-cyano-3,3-diphenylacrylate, (2- propyl)-2-cyano-3,3-diphenylacrylate, and the like.
Examples of the ultraviolet absorber of oxalic acid anilides include, but are not limited to, N-(2-ethylphenyl)-N'-(2- ethoxyphenyl)oxalic acid dianilide and the like.
When the identification compound is an ultraviolet absorber, the content thereof is not particularly limited, but is preferably 0.001 to 2.5% by mass, more preferably 0.01 to 1.0% by mass, and particularly preferably 0.05 to 0.5% by mass, based on the total mass of the resin composition constituting the layer. In addition, when the medium contains an ultraviolet absorber as a label compound, the content thereof is not particularly limited.
Examples of infrared absorbers useful in the present invention include indium oxide compounds such as tin doped indium oxide (ITO), aluminum doped tin oxide, antimony doped acid tin oxide (ATO), gallium doped zinc oxide, aluminum doped zinc oxide, tin doped zinc oxide, silicon doped zinc oxide, niobium doped titanium oxide, sodium doped tungsten oxide, particles containing a metal oxide such as cesium doped tungsten oxide (CWO), and lanthanum hexaboride, and particles comprising an inorganic infrared absorber. Further, examples thereof include a phthalocyanine compound, a naphthalocyanine compound, and an anthracyanine compound, which include metal ions such as copper, vanadium, and zinc.
When the identification compound used in the present invention is an infrared absorber, the content thereof is not particularly limited, but is preferably 0.001 to 2.5% by mass, more preferably 0.01 to 1.0% by mass, and particularly preferably 0.05 to 0.5% by mass, based on the total mass of the resin composition constituting the layer. In addition, when the medium contains an infrared absorber as a label compound, the content thereof is not particularly limited.
Examples of useful fluorescent agents as identification compounds include tris (2-phenylpyridinate)iridium (III), tris(2,2'- bipyridinate)iridium (III) hexafluoride phosphate trisalt, and tris(3,4,7,8-tetramethyl-1,10-phenanthrolinate)iridium (III), trisalts of hexafluoride, tris(2,2'-biquinolinate)iridium (III) hexafluoride, tris(4,7-diphenyl-l,10- phenanthrolinato)iridium (III) hexafluoride, tris(4,4'-diphenyl-, 2'-bipyridinate)iridium (III) hexafluoride,Tris(2,9-dimethyl-4,7- diphenyl-1,10-phenanthrolinato)iridium (III) hexafluoride trisalt, tris(4,4'-dimethyl-2,2'-bipyridinate)iridium (III), tri(4,4'-diphenyl-2,2'-bipyridinate) hexafluoride phosphate, tenium(II) hexafluoride dihydrochloride, tris(4,7-diphenyl-l,10- phenanthrolinato)ruthenium (II) hexafluoride dihydrochloride, tris(3,4,7,8-tetramethyl-1,10-phenanthrolinato) ruthenium (II) hexafluoride dihydrochloride,Tris(4,4'-dimethyl-2,2'- bipyridinate)ruthenium (II) hexafluoride di-salt, tris(4,4'- dimethyl-2, 2'-bipyridinate) ruthenium (II) perchlorate dichloride; tris(2,2'-biquino linato) ruthenium (II) hexafluoride phosphate dihydrochloride; tris(2,2'-bipyridinate) ruthenium (II) perchlorate dichlorate, tris(2,2'-bipyridinate) ruthenium (II) hexafluoride phosphate dichloride, and tris(2,9-dimethyl-4,7- diphenyl-1,10)-phenanthrolinate ruthenium (II) perchlorate, tris(acetylacetona-te)terbium (III), tris(trifluoroacetylacetonate)mono(4,7)-diphenyl-1,10- phenanthrolinate)terbium (III), tris(trifluoroacetylacetonate)mono(1,10- phenanthrolinate)terbium (III), tris(acetylacetonate)mono(4,7- diphenyl-1,10-phenanthrolinate)terbium (III), tris(acetylacetonate)mono(1,10-phenanthrolinate)terbium (III), tris(hexafluoroacetyl)mono(1,10-phenanthrolinate)terbium (III), tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6- octadionato)mono(1,10-phenanthrolinate)terbium (II), tris(trifluoroacetylacetonate)mono(4,4'-dimethyl-2,2'- bipyridinate).
When the identification compound used in the present invention is a fluorescent agent, the content thereof is not particularly limited. It is preferably from 0.001 to 2.5% by mass, more preferably from 0.01 to 1.0% by mass, and particularly preferably from 0.05 to 0.5% by mass, based on the total mass of the resin composition constituting the layer.
A wide array of metal complexes could also be used as emitters for anti-counterfeit purposes. These include rare earth metal complexes derived from scandium, yttrium and lanthanides, transition metal complexes, such as zinc-, gold-, palladium-, rhodium-, iridium-, silver-, platinum-, ruthenium-, europium-, indium-, samarium-, as well as boron complexes with a wide range of ligands, and their derivatives, such as bis(8- hydroxyquinolato)zinc, (2,2'-bipyridine)dichloropalladium (II), (2,2'-bipyridine)dichloroplatinum (II), chlorobis(2-phenylpyridine)rhodium (III), 8-hydroxyquinoline aluminium salt, lithium tetra(8-hydroxyquinolinato)boron, tris(dibenzoylmethane) mono(5-aminophenanthroline)europium (III), trichlorotris(pyridine)iridium (III). Organic dyes can also be used in pure or encapsulated form. Encapsulation hinders the migration after the taggant substance is applied onto or into the film. Preferably these materials withstand the temperatures commonly used in the lamination process, typically up to 140°C during autoclaving. Such organic dyes should also be light stable, if used for outdoor applications. This is especially true for non-encapsulated dyes. Examples for these dyes include, but are not limited to, stilbenes and triazine derivates, coumarins, rhodamines, uranin, ethylene and thiophene derivates with Benzoxazole compounds, Thinopal™ (made by Ciba), hydroxyanthraquinone, Blankophor® (manufactured by Bayer), Leucophor® (manufactured by Clariant) and Photine® (manufactured by Hickson and Welch).
The taggant materials can be encapsulated to hinder migration and increasing longterm stability, by increasing thermal stability and hindering degradation caused by radiation. Common matrix materials include, but are not limited to, methylmethacrylate, polystyrene, polypropylene, polyethylene, silicon dioxide, titanium dioxide, iron oxide or rare-earth oxides.
Readily available for purchase solutions are for example, but not limited to, Securalic® systems by Merck, Microtaggant® systems by MICROTRACE or SECUTAG® by 3S Simons Security Systems GmbH.
Such non-soluble materials are known to people skilled in the art and can be used without limitation and in different mixtures, as long as the material is not visible to the naked eye when used in a glass laminate. This can be achieved, by an intrinsic transparency, small enough particle size or low enough used concentration of the security compound. Most preferably, the identification compound is a mixture of quantum dots made of the CdS family, such as CdSe/CdS/CdZnS, ZnCdSe/CdZnS, and ZnCdS/CdZnS, used as produced or embedded in a silica matrix.
In order to completely erase all information during recycling of a used genuine film, the identification compound may have a decomposition temperature defined as the onset temperature of thermogravimetric analysis in accordance with ISO 11358-1 of equal to or more than 80°C and equal to or less than 180 °C, preferably equal to or more than 90°C and equal to or less than 160 °C, more preferably equal to or more than 100°C and less than 140 °C. Thus, it will survive the autoclaving step during the laminate production process, but will not survive the extrusion conditions during the recycling step. Naturally, this embodiment can only be used when the identification compound is printed or coated onto or injected into the film after initial extrusion.
In a preferred embodiment, at least two identification compounds are provided which absorb light at different wavelengths.
The identification compounds can be applied via techniques that are commonly known in the printing industry such as offset printing, rotogravure printing, roll-to-roll printing, flexography, spray printing and screen-printing, followed usually by a drying step.
Additionally the taggant can be injected under the surface of the film, using needles or syringes.
As discussed later, the identification compounds may be provided to different layers of the interlayer film. If the interlayer film consists of different layers, they may be provided with the same or different identification compounds. In one embodiment of the present invention, information read from one side of the intermediate film and information read from the other side are not identical. This embodiment encompasses an embodiment in which information read from one surface of an intermediate film is different from information read from the other surface, and an actual form in which information can be read from one surface of the intermediate film, but no information can be read from the other surface. In this embodiment, for example, information read from an indoor side or an inner side of a vehicle and information read from an outdoor side or an outer side of a vehicle can be designed so as to be different from each other, or information can be read only from an indoor side or an inner side of a vehicle. It is more preferable from the viewpoint that a constructor or an owner or the like of a building which is easily accessible to an indoor side, or a vehicle owner or the like of a vehicle which is easily accessible to an inner side of a vehicle can obtain information different from other third persons, and that the interlayer film for laminated glass of the present invention is an authentic article, and that a third person cannot easily obtain information on an indoor side or an inner side of a vehicle. Such embodiments include, for example, embodiments of an intermediate membrane in which information imparted by a medium comprising a label compound that absorbs light having a wavelength of less than 380nm and emits light having a wavelength of 380 to 780nm is non-uniformly disposed in the thickness direction of the interlayer film for laminated glass, and wherein the label compound contains an ultraviolet absorber that absorbs light of a wavelength absorbed by the label compound over the entire surface direction of at least one layer of the interlayer film for laminated glass (preferably at least one layer outdoors or outside the medium of the interlayer film for laminated glass) In one embodiment of the present invention, in the surface direction of the intermediate film, the area occupied by the medium relative to the area of the intermediate film is preferably 0.0001% or more, more preferably 0.0005% or more, particularly preferably 0.001% or more, and is preferably 99% or less, more preferably 30% or less, more preferably 10% or less, more preferably 1% or less, still more preferably 0.5% or less.
In an especially preferred embodiment, the film according to the present invention contains a ionomer.
As used hereunder, the term "copolymer" refers to a polymer comprising copolymerized units or residues resulting from the copolymerization of two or more comonomers. In this connection, the copolymer may be described in terms of its component comonomer or the amount of its component comonomer, for example, "a copolymer comprising ethylene and 9% by weight acrylic acid" or similar description.
The term "acid copolymer" means an α-olefin, a copolymerized unit of an a, b-ethylenically unsaturated carboxylic acid, and optionally another one such as an α, β-ethylenically unsaturated carboxylic acid ester or it means a polymer containing copolymerized units of a plurality of comonomers.
The term "ionomer" means a polymer produced by partial or complete neutralization of an acid copolymer as described above. More specifically, ionomers include ionic groups that are metal ion carboxylates, such as alkali metal carboxylates, alkaline earth metal carboxylates, transition metal carboxylates, and mixtures of such carboxylates. Such polymers are generally produced by partially or fully neutralizing the carboxylic acid groups of the precursor or parent polymer which are acid copolymers as defined herein, for example by reaction with a base. Examples of alkali metal ionomers used herein include sodium ionomers (ie sodium neutralized ionomers), such as copolymers of ethylene and methacrylic acid, where all or all of the carboxylic acid groups of the copolymerized methacrylic acid units or a part is in the form of sodium carboxylates.
The ionomer interlayer sheet is 18 to 30 % by weight, preferably 20 to 25 % by weight, based on the total weight of the alpha- olefin copolymerized unit having 2 to 10 carbon atoms and the precursor acid copolymer, or containing an ionomer that is an ion neutralized derivative of a precursor acid copolymer containing from about 21 to about 24 % by weight of a copolymerized unit of an α, β-ethylenically unsaturated carboxylic acid having 3 to 8 carbons.
Suitable α-olefin comonomers include ethylene, propylene, 1- butene, 1-pentene, 1-hexene, 1-heptene, 3 methyl-l-butene, 4- methyl-l-pentene, and the like of these olefins. Combinations of two or more are included, but are not limited to these. In one preferred ionomer, the α-olefin is ethylene.
Suitable a, b-ethylenically unsaturated carboxylic acid comonomers include acrylic acids, methacrylic acids, itaconic acids, maleic acids, maleic anhydrides, fumaric acids, monomethylmaleic acids and combinations of two or more of these acids Is included, but is not limited thereto. In one preferred ionomer, the a, b-ethylenically unsaturated carboxylic acid is selected from acrylic acids, methacrylic acids, and combinations of acrylic and methacrylic acids. In another preferred ionomer, the α, β-ethylenically unsaturated carboxylic acid is methacrylic acid.
The precursor acid copolymer may further comprise an unsaturated carboxylic acid or derivative thereof having copolymerized units of one or more other comonomers, such as 2 to 10 or preferably 3 to 8 carbons. Suitable acid derivatives include acid anhydrides, amides and esters. Esters are preferred. Specific examples of preferred esters of unsaturated carboxylic acids include methyl acrylates, methyl methacrylates, ethyl acrylates, ethyl methacrylates, propyl acrylates, propyl methacrylates, isopropyl acrylates, isopropyl methacrylates, butyl acrylates, Butyl methacrylates, isobutyl acrylates, isobutyl methacrylates, tert- butyl acrylates, tert-butyl methacrylates, octyl acrylates, octyl methacrylates, undecyl acrylates, undecyl methacrylates, octadecyl acrylates, octadecyl methacrylates, Dodecyl acrylates, dodecyl methacrylates, 2-ethylhexyl acrylates, -Ethylhexyl methacrylates, isobornyl acrylates, isobornyl methacrylates, lauryl acrylates, lauryl methacrylates, 2-hydroxyethyl acrylates, 2-hydroxyethyl methacrylates, glycidyl acrylates, glycidyl methacrylates, poly (ethylene Glycol) acrylates, poly (ethylene glycol) methacrylates, poly (ethylene glycol) methyl ether acrylates, poly (ethylene glycol) methyl ether methacrylates, poly (ethylene glycol) behenyl ether acrylates, poly (ethylene glycol) bases Henyl ether methacrylates, poly (ethylene glycol) 4-nonylphenyl ether acrylates, poly (ethylene Lenglycol) 4 nonylphenyl ether methacrylates, poly (ethylene glycol) phenyl ether acrylates, poly (ethylene glycol) phenyl ether methacrylates, dimethyl maleates, diethyl maleates, dibutyl maleates, dimethyl fumarate , Diethyl fumarates, dibutyl fumarate, dimethyl fumarate, vinyl acetates, vinyl propionates, and mixtures of two or more thereof. In one preferred ionomer, the other comonomer is selected from methyl acrylates, methyl methacrylates, butyl acrylates, butyl methacrylates, glycidyl methacrylates, vinyl acetates and combinations of two or more of these esters. However, in another preferred ionomer, the precursor acid copolymer does not incorporate other comonomers. The ionomer contains a cation as a counter ion for the carboxylate anion. Suitable cations include any positively charged species that is stable under the conditions under which the ionomer composition is synthesized, processed and used. In some preferred ionomers, the cations used are metal cations which may be monovalent, divalent, trivalent, multivalent or mixtures thereof. Useful monovalent metal cations include, but are not limited to, cations such as sodium, potassium, lithium, silver, mercury, copper, or mixtures thereof. Useful divalent metal cations include beryllium, magnesium, calcium, strontium, barium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel, zinc, and other cations and mixtures thereof. It is not limited to. Useful trivalent metal cations include, but are not limited to, cations such as aluminium, scandium, iron, yttrium, and mixtures thereof. Useful polyvalent metal cations include, but are not limited to, cations such as titanium, zirconium, hafnium, vanadium, tantalum, tungsten, chromium, cerium, iron, and mixtures thereof. If the metal cation is multivalent, complexing agents such as stearate, oleate, salicylate and phenolate radicals may be included as described in US Pat. No. 3,404,134. In a preferred ionomer, the metal cation used is a monovalent or divalent metal cation. In a preferred ionomer, the metal cation is selected from sodium, lithium, magnesium, zinc, potassium and mixtures thereof. In a preferred ionomer, the metal cation is selected from cations of sodium, zinc and mixtures thereof. In a specifically preferred ionomer, the metal cation is a sodium cation.
The ionomer film may further include other additives known in the art. Additives include processing aids, flow promoting additives, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents, antiblocking agents such as silica, heat stabilizers, UV absorbers, UV stabilizers, dispersants, surfactants, chelating agents, coupling agents, reinforcing additives such as glass fibers, fillers and the like. An especially preferred ionomer is a SentryGlas® ionomer film obtainable by from Kuraray Europe GmbH.
In another preferred embodiment of the present invention, the film contains a film B comprising a polyvinyl acetal PB and at least one plasticiser WB in an amount of equal to or more than 15 % by weight and a film A comprising a polyvinyl acetal PA and optionally at least one plasticiser WA in an amount of equal to or less than 10 % by weight.
Laminates according to the invention may comprise one or more films A, but at least one thin film A is oriented adjacent to a glass surface of the laminated glass according to the invention. It is also possible to apply a film A to both glass surfaces, such that a laminated glass laminate with a layer sequence glass/film A/film B/film A/glass is provided.
In order to optimize adhesion to the surface of a film substrate, corona- or a related treatment can be used for activation of film's surface prior every individual printing or coating step.
Film A in the starting state prior to lamination preferably has a thickness ratio to film B of less than 0.2.
The thickness of a film A in the starting state prior to lamination is 10 - 250 pm, preferably 20 - 160 pm, preferably 30 - 120 pm, preferably 40 - 100 pm and most preferably 50 - 80 pm. This range of thickness does not include additional printing layer / coating layer on the films. In the laminated glass, the thickness of the film can increase by transfer of plasticiser from film B. Film A is produced separately from film B (for example extruded or solvent cast) and has either no plasticiser at all or sufficiently small proportion of plasticiser so that subsequent functionalization and processing is not adversely influenced.
Since film A will preferably in direct contact with one of the inner surface of the laminated glass, it is desirable to control its adhesion to an intermediate level in order to reach satisfactory penetration resistance mandatory for the different glazing positions of a motor vehicle as stipulated in the different safety glass standards like ECE 43R. To this end, film A may contain alkali metal ion and/or earth alkali metal ion to adjust their adhesion level to glass (so called Anti-Adhesion Additives).
As alkali metal ion, potassium or sodium or lithium are preferred. Preferred ranges of concentration of the alkali metal ions are 7 - 210, preferably 14 - 140 and more preferably 21 - 140 ppm in the case of lithium, 23 - 690, preferably 46 - 460 and more preferably 69 - 460 ppm in the case of sodium and 39 - 1170, preferably 78 - 780 ppm and more preferably 117 - 780 in the case of potassium. It is furthermore preferred to add the alkali metal ions in form of salts of carboxylic acids having 1 to 10 carbon atoms. Especially preferred is potassium acetate as adhesion control agent.
The total amount of alkali metal salts may be as low as 0.005 % by weight based on the weight of film A. Preferred ranges of alkali metal salt are 0.01 % - 0.1 %; 0.02 - 0.08 %; 0.03 - 0.06 %, each weight % based on the weight of film A.
Film A used in the laminates of the invention may additionally comprise alkaline earth ions, but since their effect on adhesion is limited, only small amounts as compared to the alkali ion should be used. In a first embodiment of the invention film A comprises 0 to 20 ppm alkaline earth ions, preferable 0 to 5 ppm.
However, it is known that alkaline earth ions have a balancing effect of adhesion when a plasticized PVB film faces two glass sheets with different surface chemistry. Accordingly, in a second embodiment of the invention, film A comprises 5- 20 ppm alkaline earth ions. The alkaline earth ions can be added in form salts of carboxylic acids having 1 to 10 carbon atoms. Especially preferred is magnesium acetate as secondary adhesion control agent. In this embodiment, the ratio of alkali ions to alkaline earth ions in ppm in film A is preferable at least than 1, especially higher than 5 and more preferred higher than 10.
Film B may be any plasticized PVB-film known in the art. The films A and B may contain, in the starting state prior to lamination and/or in a stack prepared for lamination between glass sheets, a single plasticiser as well as mixtures of plasticisers both of different and identical composition. The term "different composition" refers to both the type of plasticiser and proportion thereof in the mixture. Film A and film B after lamination, i.e. in the finished laminated glass, preferably have the same plasticisers WA and WB. In a preferred variant, film A in its starting state, however, does not contain any plasticiser and after lamination contains plasticiser WB in equilibrium amount.
Plasticiser-containing films B used in accordance with the invention contain, in the starting state prior to lamination, at least 22 % by weight, such as 22.0 - 45.0 % by weight, preferably 25.0 - 32.0 % by weight and in particular 26.0 - 30.0 % by weight plasticiser. Films A used in accordance with the invention may contain, in the starting state prior to lamination, less than 22 % by weight (such as 21.9 % by weight), less than 18 % by weight less than 16 % by weight, less than 12 % by weight, less than 8 % by weight, less than 4 % by weight, less than 2 % by weight, less than 1 % by weight or even no plasticiser (0.0 % by weight). In a preferred embodiment of the invention, films A with a low plasticiser content preferably contain 0.0 - 8 % by weight of plasticiser, most preferred 0 - 4 % by weight.
The films A or B preferably contain polyvinyl acetals having a proportion of polyvinyl acetate groups, either identically or differently, of 0.1 to 20 mol %, preferably 0.5 to 3 mol %, or 5 to 8 mol %.
The thickness of film B in the starting state is 450 - 2500 pm, preferably 600 - 1000 pm, preferably 700 - 900 pm. A plurality of films B may be used in the invention, either being stacked on each other or separated by films A.
The films A and B used in accordance with the invention contain polyvinyl acetals, which are produced by acetalisation of polyvinyl alcohol or ethylene vinyl alcohol copolymer.
The films can contain polyvinyl acetals, each having a different polyvinyl alcohol content, degree of acetalisation, residual acetate content, ethylene proportion, molecular weight and/or different chain lengths of the aldehyde of the acetal groups.
The films A or B preferably contain polyvinyl acetals having a proportion of polyvinyl acetate groups, either identically or differently, of 0.1 to 20 mol %, preferably 0.5 to 3 mol %, or 5 to 8 mol %. The polyvinyl alcohol content of the polyvinyl acetal PA used in film A may be between 6 - 26 % by weight, 8 - 24 % by weight, 10 - 22 % by weight, 12 - 21 % by weight, 14 - 20 % by weight, 16 - 19 % by weight and preferably between 16 and 21 % by weight or 10 - 16 % by weight.
Independent of film A, the polyvinyl alcohol content of the polyvinyl acetals PB used in film B may be between 14 - 26 % by weight, 16 - 24 % by weight, 17 - 23 % by weight and preferably between 18 and 21 % by weight.
In a preferred embodiment of the invention, film A comprises a polyvinyl acetal PA with a proportion of vinyl alcohol groups from 6 to 26 % by weight and the film B comprises a polyvinyl acetal B with a proportion of vinyl alcohol groups from 14 to 26 % by weight.
Specifically, the polyvinyl acetals according to the present invention are polyvinyl butyral.
Films A and/or B used in accordance with the invention may contain, as plasticiser, one or more compounds selected from the following groups:
- esters of polyvalent aliphatic or aromatic acids, for example dialkyl adipates, such as dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, mixtures of heptyl adipates and nonyl adipates, diisononyl adipate, heptyl nonyl adipate, and esters of adipic acid with cycloaliphatic ester alcohols or ester alcohols containing ether compounds, dialkyl sebacates, such as dibutyl sebacate, and also esters of sebacic acid with cycloaliphatic ester alcohols or ester alcohols containing ether compounds, esters of phthalic acid, such as butyl benzyl phthalate or bis-2-butoxyethyl phthalate. - esters or ethers of polyvalent aliphatic or aromatic alcohols or oligo ether glycols with one or more unbranched or branched aliphatic or aromatic substituents, for example esters of glycerol, diglycols, triglycols or tetraglycols with linear or branched aliphatic or cycloaliphatic carboxylic acids; Examples of the latter group include diethylene glycol-bis- (2-ethyl hexanoate), triethylene glycol-bis-(2-ethyl hexanoate), triethylene glycol-bis-(2-ethyl butanoate), tetraethylene glycol-bis-n-heptanoate, triethylene glycol- bis-n-heptanoate, triethylene glycol-bis-n-hexanoate, tetraethylene glycol dimethyl ether and/or dipropylene glycol benzoate
- phosphates with aliphatic or aromatic ester alcohols, such as tris(2-ethylhexyl)phosphate (TOF), triethyl phosphate, diphenyl-2-ethylhexyl phosphate, and/or tricresyl phosphate
- esters of citric acid, succinic acid and/or fumaric acid.
By definition, plasticisers are organic liquids having a high boiling point. For this reason, further types of organic liquids having a boiling point above 120 °C can also be used as plasticiser.
In addition, films A and B may contain further additives, such as residual quantities of water, UV absorber, antioxidants, adhesion regulators, optical brighteners or fluorescent additives, stabilisers, colorants, processing aids, inorganic or organic nanoparticles, pyrogenic silicic acid and/or surface active substances.
In particular, film B may comprise 0.001 to 0.1 % by weight of alkaline metal salts and/or alkaline earth salts of carboxylic acids as adhesion control agent. It is preferred that film B contains magnesium ions in an amount of at least 10 ppm, preferably 20 ppm and most preferably 30 ppm. It is also possible for the films B to have a wedge-shaped thickness profile. The laminated glass laminate according to the invention obtains a wedge-shaped thickness profile even with plane-parallel thickness profile of the film A and can be used in motor vehicle windscreens for HUD displays.
In the simplest case, film B is a commercially available PVB film with or without ink ribbon and with or without a wedge-like thickness profile. Films B with nanoparticles dispersed therein for IR protection can also be used as coloured films. Of course, a film B may also be a film having an acoustic function, such that soundproofing properties that are further improved are obtained by combination with a film A. Of course, a film B may already also combine more than one of the mentioned functions.
The thin films A are generally produced by extrusion with use of a cast-film line or in the form of a blown film. Here, a surface roughness may also be produced by controlled melt fracture or with the cast-film method additionally by use of a structured chill roll and/or structure back roll. Alternatively, solvent- cast method can be used for producing film A prior to functionalization and use in the described penetration resistant glass laminates. Films used in accordance with the invention preferably have a one-sided surface structure with a roughness Rz from 0 to 25 pm, preferably Rz from 1 to 20 pm, particularly preferably Rz from 3 to 15 pm and in particular Rz from 4 to 12 pm. It is particularly preferable if the side of film A coming into contact with the glass sheet has a surface roughness Rz of no more than 20 % of its thickness.
Another aspect of the present invention concerns a process for testing a genuineness of an interlayer for laminated glazing comprising the steps of a.providing an interlayer for laminated glazing comprising a film containing a ionomer and/or a polyvinyl acetal and optionally at least one plasticiser with at least one identification compound absorbing light having a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm wherein the identification compound is provided in a pattern or shape adapted to bear information, b.laminating the interlayer of step a between two sheets of glass, and c.analyse the laminated glazing in a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm to verify that the identification compound in the film is still present in the same pattern or shape as provided in step a.
Yet another aspect of the present invention concerns a laminated glazing comprising at least two sheets of transparent material and at least one interlayer according to the present invention as described above.
Examples
Example 1
In a first example Tinopal® OB CO fluorescent optical brightener (CAS: 7128-64-5, produced by BASF) was dissolved in OXSOFT® 3G8 (CAS: 94-28-0, produced by OXEA) in a concentration of 0,5g/100ml. The mixture was then applied by hand on a PVB film (B100 MR CLEAR 0.76, produced by Kuraray Europe GmbH) using a Dragonhawk® Tattoo Needle Round Liner 1003R.
The needle was dipped in the UV-light active mixture and drawn over the surface of the PVB film in straight lines from top to bottom and from left to right, resulting in a grid of lines with a spacing of 5 cm, on the surface of the film. The mixture was then dried at air at room temperature overnight.
This film and a film without the above described treatment were then placed between two 300x300 mm sheets of 2 mm thick glass. The glass-film sandwiches were put into a rubber bag and vacuum (50mbar) was applied on the bag for 15 minutes at room temperature. The bag was then placed in an oven at 85°C for 15 minutes. The bag was let cooled to room temperature, before the vacuum was turned off and the bag was opened. The pre laminates were then placed in an autoclave and laminated at 140°C and 12 bar for 90 minutes. After this process both laminates appeared completely transparent and no lines were observable with the naked eye on either of them. Using an UltraFire® WF-5018 UV flash light with a wave length of 395-410nm made the lines visible on the laminate with the above described treatment. With this technique the laminate with the lines and the one without the lines could be differentiated.
If the film with the above described treatment is re-extruded, for example during recycling, the applied pattern is destroyed and is therefore an indication if the sample film is genuine or not.
Therefore, the original film can be distinguished from re extruded or counterfeit film.
Example 2
In a second example Tinopal® OB CO fluorescent optical brightener (CAS: 7128-64-5, produced by BASF) was dispersed in Adhesion Pro® (produced by Qdel) in a concentration of 0,5g/100ml. The mixture was then applied by hand on a ionomer film (SentryGlas® 5000 0,89, produced by Kuraray Europe GmbH) using a Dragonhawk® Tattoo Needle Round Liner 1003R. The needle was dipped in the UV-light active mixture and drawn over the surface of the PVB film in straight lines from top to bottom and from left to right, resulting in a grid of lines with a spacing of 5 centimeters, on the surface of the film. The mixture was then dried at air at room temperature overnight.
This film and a film without the above described treatment were then placed between two 300x300 mm sheets of 2 mm thick glass. The glass-film sandwiches were put into a rubber bag and vacuum (50mbar) was applied on the bag for 15 minutes at room temperature. The bag was then placed in an oven at 85°C for 15 minutes. The bag was let cooled to room temperature, before the vacuum was turned off and the bag was opened. The pre laminates were then placed in an autoclave and laminated at 140°C and 12 bar for 90 minutes. After this process both laminates appeared completely transparent and no lines were observable with the naked eye on either of them. Using an UltraFire® WF-5018 UV flash light with a wave length of 395-410nm made the lines visible on the laminate with the above described treatment. With this technique the laminate with the lines and the one without the lines could be differentiated.
If the film with the above described treatment is re-extruded, for example during recycling, the applied pattern is destroyed and is therefore an indication if the sample film is genuine or not.
Therefore, the original film can be distinguished from re extruded or counterfeit film.
Example 3
100 parts by mass of polyvinyl butyral (degree of polymerization 1700), 38 parts by mass of triethylene glycol-bis-(2- ethylhexanoate), and 0.15 parts by mass of Tinuvin® 326 (50 g in total) were kneaded using a mill (manufactured by Toyo Seiki Co., Ltd., Laboplast® 4M150, blade shape; roller type) for 5 minutes at 150° C and 60 rpm to obtain a kneaded product. The kneaded product obtained was pressed at 150° C and 100kg/cm2 for 10 min using a thermal pressing machine to obtain a sheet having the dimensions 60cmx60cmx0.76mm.
Using a silk screen printing plate (manufactured by Ideal Science and Industrial Co., Ltd., #200 mesh) and a fluorescent ink solution (prepared by adding 5 parts by mass of polyvinyl butyral and 0.05 parts by mass of tris(hexafluoroacetylacetonato)-mono- (1,10-phenanthrolinato)europium (III) to 100 parts by mass of ethanol), a two-dimensional code (QR code, version 3, margin 4 cell, number of cells 29 c 29, area of code in the plane direction of the sheet: 24.6 mm x 24.6 mm = 605.16 mm2) showing "Kuraray Co., Ltd.") was printed onto one surface of the sheet. After drying, the printing thickness of the two-dimensional code was 15 pm.
The thus printed sheet was sandwiched between two sheets of glass of 60cmx60cmx 3mm, temporarily bonded using a vacuum bag, and laminated using an autoclave at 140° C for 30 min to obtain a laminated glass.
Print two-dimensional code of interlayer film-4 for laminated glass by reading the two-dimensional code from the same surface as the surface irradiated with ultraviolet rays with an ultraviolet lamp (manufactured by AzOne Corporation, Handy UV lamp (long wavelength 36 5nm type)) on interlayer film-4 for laminated glass using a QR code reader.
When an attempt was made to read the QR code with a commercially available UV lamp (manufactured by AzOne Corporation, long wavelength 365 nm type) from each side of the laminated glass, the information of "Kuraray Co., Ltd" could only be read from the side on which the two-dimensional code was printed. On the other side, the QR code could not be read from the other side due to the presence of Tinuvin® UV absorber in the polyvinyl butyral sheet.

Claims

Claims
1.An interlayer for laminated glazing comprising a film containing an ionomer and/or a polyvinyl acetal and optionally at least one plasticiser characterised in that the film is provided with at least one identification compound having its absorption maximum at a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm wherein the identification compound is provided in a pattern or shape adapted to bear information.
2.The interlayer according to claim 1 wherein the identification compound is provided in form of a barcode, a plurality of dots, one or more lines or a grid to the film.
3.The interlayer according to claim 1 or 2 wherein the at least one identification compound is printed or coated onto at least one surface of the film.
4.The interlayer according to any one of the claims above wherein the identification compound has a decomposition temperature defined as the onset temperature of thermogravimetric analysis in accordance with ISO 11358-1 between equal to or more than 80 °C and equal to or less than 180 °C.
5.The interlayer according to any one of the claims above wherein at least two identification compounds are provided which absorb light at different wavelengths.
6.The interlayer according to any one of the claims above wherein the at least one identification compound is chosen from carbon based materials, doped metal sulfides, doped metal oxides, rare earth doped oxides, metal oxy-sulfides of lanthanides, mixed oxides capable of fluorescing, fluorescent dyes or phosphors, up-converting phosphors, phosphorescent materials, photochromic materials, metal nanoparticles and luminescent metal complexes.
7.The interlayer according to any one of the claims above wherein the at least one identification compound is a phosphorescent material.
8.The interlayer according to any one of the claims above wherein the film contains an ionomer.
9.The interlayer according to any one of the claims above wherein the film contains a film B comprising a polyvinyl acetal PB and at least one plasticiser WB in an amount of equal to or more than 15 % by weight and a film A comprising a polyvinyl acetal PA and optionally at least one plasticiser WA in an amount of equal to or less than 10 % by weight.
10. The interlayer according to any one of the claims above wherein the polyvinyl acetal is polyvinyl butyral.
11. A process for testing a genuineness of an interlayer for laminated glazing comprising the steps of a.providing an interlayer for laminated glazing comprising a film containing an ionomer and/or a polyvinyl acetal and optionally at least one plasticiser with at least one identification compound absorbing light having a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm wherein the identification compound is provided in a pattern or shape adapted to bear information, b.laminating the interlayer of step a between two sheets of glass, and c.analyse the laminated glazing in a wavelength of 50 to 350 nm and/or a wavelength of 800 to 1500 nm to verify that the identification compound in the film is still present in the same pattern or shape as provided in step a.
12. A laminated glazing comprising at least two sheets of transparent material and at least one interlayer according to any one of the claims 1 to 10.
PCT/EP2021/068612 2020-07-08 2021-07-06 Laminated glass with anti-counterfeiting properties WO2022008489A1 (en)

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Citations (6)

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US3404134A (en) 1961-08-31 1968-10-01 Du Pont Process of crosslinking polymers
DE3147385A1 (en) * 1980-12-16 1982-09-16 Vereinigte Glaswerke Gmbh, 5100 Aachen Process for treating a laminated glass pane, in particular for the forgery-proof marking of a laminated glass pane
DE4406969A1 (en) * 1993-03-15 1994-09-22 Volkswagen Ag Forgery-proof identification of an object equipped with a glass pane, especially a motor vehicle
US20150308659A1 (en) * 2012-12-24 2015-10-29 Saint-Gobain Glass France Laminated glass panel including phosphors
WO2018141742A1 (en) * 2017-02-03 2018-08-09 Basf Se Laminated glazing comprising a composite structure of laminated layers
WO2019128970A1 (en) * 2017-12-29 2019-07-04 Saint-Gobain Glass France Vehicle windshield with two-dimensional code and manufacturing process thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404134A (en) 1961-08-31 1968-10-01 Du Pont Process of crosslinking polymers
DE3147385A1 (en) * 1980-12-16 1982-09-16 Vereinigte Glaswerke Gmbh, 5100 Aachen Process for treating a laminated glass pane, in particular for the forgery-proof marking of a laminated glass pane
DE4406969A1 (en) * 1993-03-15 1994-09-22 Volkswagen Ag Forgery-proof identification of an object equipped with a glass pane, especially a motor vehicle
US20150308659A1 (en) * 2012-12-24 2015-10-29 Saint-Gobain Glass France Laminated glass panel including phosphors
WO2018141742A1 (en) * 2017-02-03 2018-08-09 Basf Se Laminated glazing comprising a composite structure of laminated layers
WO2019128970A1 (en) * 2017-12-29 2019-07-04 Saint-Gobain Glass France Vehicle windshield with two-dimensional code and manufacturing process thereof

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Title
CAS, no. 7128-64-5

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