WO2012025685A1 - Procede de selection d'un intercalaire pour un amortissement vibro-acoustique, intercalaire et vitrage comprenant un tel intercalaire - Google Patents
Procede de selection d'un intercalaire pour un amortissement vibro-acoustique, intercalaire et vitrage comprenant un tel intercalaire Download PDFInfo
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- WO2012025685A1 WO2012025685A1 PCT/FR2011/051927 FR2011051927W WO2012025685A1 WO 2012025685 A1 WO2012025685 A1 WO 2012025685A1 FR 2011051927 W FR2011051927 W FR 2011051927W WO 2012025685 A1 WO2012025685 A1 WO 2012025685A1
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- thickness
- interlayer
- glazing
- glass
- laminated
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/22—Investigating strength properties of solid materials by application of mechanical stress by applying steady torsional forces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—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
- B32B17/1055—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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/001—Double glazing for vehicles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/20—Accessories, e.g. wind deflectors, blinds
- B60J1/2097—Accessories, e.g. wind deflectors, blinds means to prevent rattling of vehicle windows
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/08—Insulating elements, e.g. for sound insulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/08—Insulating elements, e.g. for sound insulation
- B60R13/0815—Acoustic or thermal insulation of passenger compartments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
- E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
- E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
- E06B3/6707—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased acoustical insulation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N19/00—Investigating materials by mechanical methods
- G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating
-
- G—PHYSICS
- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/162—Selection of materials
- G10K11/168—Plural layers of different materials, e.g. sandwiches
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- 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.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- 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.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
Definitions
- the invention relates to a method of selecting a spacer with acoustic damping property to be incorporated in a laminated glazing, intended in particular for locomotion machines, in particular a motor vehicle.
- Vehicle shapes have also been modified to improve air penetration and reduce turbulence which is itself a source of noise.
- Laminated glazing also has other advantages such as eliminating the risk of splashing fragments in case of sudden breakage, constitute a burglar-proofing device.
- the reference to a damping film is related to a viscoelastic plastic film which provides improved vibration damping to provide the glazing with a noise reduction function.
- the loss factor is the ratio between the energy dissipated in caloric form and the energy of elastic deformation; it characterizes the ability of the material to dissipate energy. The higher the loss factor, the higher the energy dissipated, the more the material plays its damping function.
- This loss factor varies with temperature and frequency. For a given frequency, the loss factor reaches its maximum value at a temperature, called the glass transition temperature.
- the materials used as laminated glazing interleaves are viscoelastic plastic films, such as acrylic polymers or acetal resins or polyurethane, for example, which have a fairly high loss factor, such as at least greater than 0, 6 for a given temperature range and for a given range of frequencies.
- the loss factor tan ⁇ is estimated using a viscoanalyzer.
- the viscoanalyzer is an apparatus which makes it possible to subject a sample of material to stresses of deformation under precise temperature and frequency conditions, and thus to obtain and process all the rheological quantities characterizing the material.
- the shear modulus G ' is also estimated using a viscoanalyzer. This document describes that the loss factor tan ⁇ of the interlayer is greater than 0.6 and the shear modulus G 'of the interlayer is less than 2.10 7 Pa for temperatures between 10 ° C and 60 ° C and frequencies between 50 Hz and 10 000 Hz, in order to dampen more particularly the noise of solid origin.
- the laminated glazing when used as a windshield, it is subjected to acoustic vibrations that are specific to it.
- the first four The eigenfrequencies of the windscreen, and in particular the second and third eigenfrequencies of the windscreen, between 100 Hz and 240 Hz, are particularly troublesome acoustically speaking.
- the insert of EP-A-844 075 is suitable for the damping of solid noise, but not for the vibro-acoustic damping of the first eigenfrequencies of the windshield, in particular the second and third eigenfrequencies.
- the invention provides a method of selecting a viscoelastic plastic interlayer comprising two outer layers and a central layer and intended to be incorporated between two glass sheets of a glazing unit, the method comprising the following steps:
- first viscoelastic plastic material element intended to constitute the central layer and a second element made of viscoelastic plastic material intended to constitute the outer layers are provided,
- the shear modulus G 'of the first element and the second element are measured by means of a visco-analyzer
- the material of the second element is selected only if its shear modulus G 'is greater than or equal to 3.10 7 Pa at 20 ° C and for a frequency range between 100 Hz and 240 Hz,
- the thickness h of the first element is fixed such that h is between 0.50 and 0.90 mm and G7h is between 7.56.10 8 Pa / m and 1, 42.10 9 Pa / m at 20 ° C and for a frequency range between 100 Hz and 240 Hz.
- the method further comprises, before the step of fixing the thickness h, the following steps: the loss factor tan ⁇ of the first element is measured using the visco-analyzer,
- the first element is selected only if its loss factor tan ⁇ is greater than 0.6.
- the method further comprises the following step:
- the material of the second element is selected only if its shear modulus G 'is between 10 8 Pa and 2.10 8 Pa at 20 ° C and for a frequency range between 100 Hz and 240 Hz.
- the method further comprises the steps of:
- the adhesion of the material of the second element is compatible with the requirements of regulation R43 by twisting an interlayer sample consisting of the material of the second element integral with two sheets of glass, by measuring the torsional force for which the splitting of the interlayer consisting of the material of the second element with the glass sheets is initiated, and calculating from this force the corresponding adhesion shear stress, and comparing this value of the adhesion stress to a range of permissible values for any laminated glazing to withstand the efforts corresponding to the regulation R43; and
- the thickness e of the second element is fixed as follows:
- a reference laminated glazing unit which resists the efforts corresponding to the regulation R43 and which comprises two sheets of glass and an interlayer consisting of the material of the second element;
- the tear resistance of the interlayer of the reference laminated glazing unit, the interlayer thickness of the reference laminated glazing unit and the thickness of glass sheets of the reference laminated glazing unit are determined;
- the thickness e of the second element is fixed such that e is greater than or equal to said optimum value of spacer thickness.
- the invention proposes a viscoelastic plastic interlayer intended to be incorporated between two glass sheets of a glazing unit to provide vibro-acoustic damping properties, the interlayer comprising:
- the central layer being between the two outer layers.
- the thickness h of the central layer is such that h is between 0.50 and 0.90 mm and G7h is between 7.56.10 8 Pa / m and 1, 42.10 9 Pa / m at 20 ° C and for a frequency range between 100 Hz and 240 Hz.
- the central layer has a loss factor tan ⁇ greater than 0.6.
- the outer layers have a shear modulus G 'of between 10 8 Pa and 2.10 8 Pa at 20 ° C and for a frequency range between 100 Hz and 240 Hz.
- each of the outer layers has a thickness e such that:
- the adhesion of the material of the outer layers is compatible with the requirements of regulation R43, the adhesion being determined by twisting an interlayer sample consisting of the material of the outer layers integral with two sheets of glass, by measuring the twisting force for which the dissociation of the interlayer consisting of the material of the outer layers with the glass sheets is initiated, and calculating from this force the corresponding adhesion shear stress, and then comparing this value of the stress adhering to a range of permissible values for any laminated glazing to withstand the efforts corresponding to the regulation R43; and
- the thickness e of each of the outer layers is set so as to satisfy the requirements of regulation R43, the thickness e being determined as follows:
- a reference laminated glazing unit which withstands the efforts corresponding to regulation R43 and which comprises two sheets of glass and an interlayer consisting of the material of the outer layers;
- the tear resistance of the interlayer of the reference laminated glazing unit, the interlayer thickness of the reference laminated glazing unit and the thickness of glass sheets of the reference laminated glazing unit are determined;
- the central layer comprises:
- a damping film of viscoelastic plastic material A having a thickness h A and a shearing parameter g A ,
- the invention also relates to a glazing unit comprising:
- the interlayer being between the glass sheets.
- the thickness e of each of the outer layers and the total thickness of the glass sheets are such that:
- the adhesion of the material of the outer layers is compatible with the requirements of regulation R43, the adhesion being determined by twisting an interlayer sample consisting of the material of the outer layers integral with two sheets of glass, by measuring the twisting force for which the dissociation of the interlayer consisting of the material of the outer layers with the glass sheets is initiated, and calculating from this force the corresponding adhesion shear stress, and then comparing this value of the stress membership to a range of allowable values for a any laminated film withstands the corresponding efforts of Regulation R43; and
- the thickness e of each of the outer layers and the total thickness of the glass sheets are set so as to satisfy the requirements of regulation R43; they are determined as follows:
- a reference laminated glazing unit which withstands the efforts corresponding to regulation R43 and which comprises two sheets of glass and an interlayer consisting of the material of the outer layers;
- the tear strength of the interlayer of the reference laminated glazing, the interlayer thickness of the reference laminated glazing unit and the thickness of glass sheets of the reference laminated glazing unit are determined;
- the thickness e of each outer layer is fixed such that e is greater than or equal to said optimum value of spacer thickness and the thickness of the glass sheets is fixed greater than or equal to said optimum thickness value; of glass sheets.
- the invention also relates to a vehicle comprising the glazing described above, the glass sheet having a thickness of between 1.4 mm and 2.1 mm being turned towards the outside of the vehicle and the glass sheet of thickness between 1, 1 mm and 1, 6 mm being turned towards the interior of the vehicle.
- the invention also relates to a use of the spacer described above for vibro-acoustic damping of the second and third eigenfrequencies of a windshield consisting of two sheets of glass and the interlayer incorporated between the glass sheets .
- the invention also relates to a use of the glazing described above as vehicle windshield, vehicle side window or vehicle roof glass.
- Figure 1 shows a curve of the modal damping of a laminated windshield according to the shear parameter of a central layer of the interlayer of the laminated windshield for frequencies between 100 Hz and 240 Hz to 20 ° C, and for thicknesses of the central layer between 0.10 and 1, 20 mm;
- Figure 2 shows a sectional view of a glazing according to the invention
- Figure 3 shows a sectional view of a glazing according to the invention according to another embodiment
- FIG. 4 represents a representative graph of the minimum interlayer tear resistance required for a laminated glazing to withstand the forces corresponding to the regulation R43, as a function of the interlayer thickness of the laminated glazing, established for a glazing unit.
- laminated film comprising two 2.1 mm thick glass substrates and an adhesion stress interlayer of between 2 MPa and 5 MPa and a fall height of 4 m;
- FIG. 5 is a three-dimensional graph representative of the minimum interlayer tear strength required for a laminated glazing to withstand the forces corresponding to regulation R43, as a function of both the thickness of the interlayer and the glass thickness of the laminated glazing, established for a laminated glazing comprising an adhesion stress interlayer between 2MPa and 5MPa and for a fall height of 4 m;
- FIG. 6 represents a schematic front view of an experimental device for evaluating the adhesion of an interlayer with respect to glass sheets with which it is associated
- FIG. 7 represents a perspective view of an alternative device for evaluating the adhesion of an interlayer vis-à-vis the glass sheets with which it is associated
- FIG. 8 is a schematic view of an experimental device for evaluating the tear resistance of a spacer.
- the invention proposes a method of selecting a viscoelastic plastic interlayer comprising two outer layers and a central layer and intended to be incorporated between two glass sheets of a glazing unit.
- the method comprises the following steps:
- a first viscoelastic plastic material element intended to constitute the central layer and a second element of viscoelastic plastic material intended to constitute the outer layers are provided,
- the shear modulus G 'of the first element and the second element are measured by means of a visco-analyzer
- the material of the second element is selected only if its shear modulus G 'is greater than or equal to 3.10 7 Pa at 20 ° C and for a frequency range between 100 Hz and 240 Hz,
- the frequency range between 100 Hz and 240 Hz comprises the first four eigenfrequencies of a laminated windshield, and in particular the second and third eigenfrequencies, as the inventors were able to measure it by vehicle tests.
- the inventors have demonstrated that a material that satisfies the conditions of h and g described above makes it possible to optimize the damping of the first eigenfrequencies of a laminated windshield, in particular second and third eigen frequencies of the windshield comprising two sheets of glass and a spacer selected as described above.
- the material of the first element is such that its shearing parameter g can not be between 5.58 ⁇ 10 8 Pa / m and 2.37 ⁇ 10 9 Pa / m for a thickness of between 0.31 and 1, 20 mm. , the material is not selected to make the interlayer.
- the outer layers be more rigid than the central layer, which is achieved with the elasticity conditions as defined.
- the invention also relates to a viscoelastic plastic interlayer intended to be incorporated between two glass sheets of a glazing to provide vibro-acoustic damping properties, the interlayer comprising:
- the interlayer is obtained by the selection method described above.
- the interlayer optimizes the damping of the first eigenfrequencies of a laminated windshield, in particular the second and third eigenfrequencies of the windshield, the laminated windshield comprising two sheets of glass and the integrated interlayer between the sheets of glass.
- the interlayer is intended to be integrated in a glazing unit.
- the glazing is intended for use in a vehicle, particularly as a windshield.
- the invention also relates to a glazing comprising such an interlayer.
- the invention also relates to a vehicle comprising such a glazing unit.
- Figure 2 shows a sectional view of a glazing unit according to the invention.
- the glazing comprises two sheets of glass 1, 2 between which is inserted the interlayer.
- the interlocking of the interlayer with the glass sheets is carried out by known means, for example by stacking the glass sheets and the interlayer and by passing the assembly in an autoclave.
- the glass sheet 1 of the glazing is intended to be turned towards the outside of the vehicle while the glass sheet 2 is intended to be turned towards the inside of the vehicle.
- the glass sheet 1 is thicker than the glass sheet 2 so that the glazing allows better protection against external attacks (inclement weather, projection of chippings, etc.). Indeed, the thicker the glass, the more mechanically resistant it is. However, the thicker the glass, the heavier it is. We must therefore find a compromise between the mechanical strength and the weight of the glazing.
- the thickness of the glass sheet 1 is for example between 1.4 mm and 2.1 mm and the thickness of the glass sheet 2 is for example between 1.1 mm and 2.1 mm.
- the thickness of the glass sheet 1 is generally 2.1 mm and the thickness of the glass sheet 2 is generally 1.6 mm.
- the thickness of the glass sheet 1 is 1, 8 mm and the thickness of the glass sheet 2 is 1.4 mm in order to limit the weight of the windshield, which makes it easier to handle and save material. This also reduces the fuel consumption of a vehicle equipped with such a windshield. These reduced thicknesses of the glass sheets are possible without loss of acoustic or mechanical performance compared to existing glazing, as will be seen below.
- the invention can also be applied to windscreens whose thickness of the glass sheet 1 is 1, 6 mm and the thickness of the glass sheet 2 is 1, 2 mm, or to windshield whose thickness of the glass sheet 1 is 1, 4 mm and the thickness of the glass sheet 2 is 1.1 mm.
- the interlayer consists of two outer layers 4, 5 between which is inserted a central layer 3.
- the outer layers 4, 5 have a shear modulus G 'greater than or equal to 3.10 7 Pa at 20 ° C and for a frequency range between 100 Hz and 240 Hz.
- the shear modulus G' of the outer layers is between 10 8 Pa and 2.10 8 Pa to further improve the vibro-acoustic damping of the core layer.
- the outer layers are, for example, polyvinyl butanol (PVB).
- the central layer 3 thus has acoustic performances optimized for frequencies between 100 Hz to 240 Hz.
- the central layer is, for example, composed of the central layer of the three-layer acoustical PVB of the trade name SAF RZN-12 marketed by the Sekisui Company, or else the central layer of the three-layer acoustical PVB with the trade name QC 55 marketed by the Solutia Company.
- the central layer is preferably chosen so that h is between 0.50 and 0.90 mm and G7h is between 7.56.10 8 Pa / m and 1, 42.10 9 Pa / m at 20 ° C and for a frequency range between 100 Hz and 240 Hz.
- the acoustic properties of the central layer 3 are also defined by its loss factor tan ⁇ .
- the central layer 3 is chosen such that its loss factor is greater than 0.6 at 20 ° C and for a frequency range between 100 Hz and 240 Hz, to allow satisfactory damping.
- the shear modulus G 'and the loss factor tan ⁇ are measured using a visco-analyzer.
- the glass sheets participate in the vibro-acoustic properties of a glazing.
- optimizing the acoustic performance of the interlayer for frequencies between 100 Hz and 240 Hz makes it possible to reduce the thickness of the glass sheets up to 1, 8 mm, or even up to 1, 6 mm or even 1, 4 mm, for the sheet of glass intended to be turned towards the outside of the vehicle and up to 1.4 mm, or even up to 1.2 mm or even 1.1 mm, for the glass sheet intended to be turned towards the interior of the vehicle, without acoustic loss compared with existing glazings.
- the existing windscreen windows have glass sheets with respective thicknesses of 2.1 mm and 1.6 mm, between which is inserted a spacer comprising a central layer of viscoelastic plastic material thickness 0.12 mm with a shear modulus G 'between 5.10 5 and 2.10 7 Pa and a loss factor greater than 0.6 for a temperature of 20 ° C. and a frequency of 100 Hz.
- the reduction in the thickness of the glass sheets allows a reducing the weight of the glazing, thus improved handling, as well as a reduction in material, and a reduction in the fuel consumption of a vehicle equipped with such a windshield.
- the two outer layers 4, 5 have the same thickness e.
- the thickness e of each outer layer 4, 5 is determined both so that it is as small as possible, and so that the mechanical properties of the outer layers are sufficient to meet the mechanical strength standards. defined for the automobile, in particular the United Nations Regulation No. 43 (so-called Regulation R43), of resistance to hard shocks.
- United Nations Regulation R43 concerns the adoption of uniform technical prescriptions for the approval of safety glazing and the installation of such glazing on wheeled vehicles. It is indeed desirable that the total thickness of the spacer is as small as possible for reasons of weight of the windshield on the one hand, which reduces the fuel consumption of a vehicle equipped with a such windshield, and saving material on the other hand.
- the thickness e is minimized by taking into account both the adhesion of a spacer consisting of the material of the outer layers vis-à-vis two sheets of glass and the tear resistance of the material of the external layers.
- the adhesion is evaluated on the basis of the test and calculation method described in EP-A-1 495 305, which is repeated hereinafter.
- a torsion force is exerted on a laminated glazing sample consisting of two sheets of glass and an interlayer consisting of the material of the outer layers, until the separation of the interlayer consisting of the material begins. outer layers with respect to at least one of the glass sheets.
- the test is performed on a round sample 50 of glazing, of radius r equal to 10 mm, for example by means of a known type of torsion device 500 illustrated in FIG.
- the device 500 comprises three jaws 51, 52, 53, a pulley 54 of radius R equal to 100 mm and connected to a drive chain 55 of vertical axis.
- the jaws are shaped circular arcs of 120 ° each, so as to enclose the entire sample.
- the surface coating of the jaws is in a material mechanically compatible with glass, for example aluminum, Teflon ® , or polyethylene.
- One of the jaws is held fixed against a frame, while another jaw is fixed on the pulley 54 which is intended to rotate to exert a torsion on the sample.
- the rotation of the pulley 54 is caused by the movement of the chain 55 connected to the pulley.
- the chain is towed at a constant speed of at least 35 to 50 mm / min.
- R is the radius of the pulley 54 and r is the radius of the sample.
- the device 500 is however bulky, which requires that the tests must be done in the laboratory.
- the device 500 is therefore not suitable for measurements of the "process indicator" type on a laminated glazing production line.
- the composition of the polymeric interlayer is developed to meet the stress values set by the invention, poor adhesion of the interlayer may nevertheless appear in the finished product due to parameters. related to the glazing manufacturing process, such as conditions of storage of the interlayer, the quality of washing of the glass, or the temperature and the pressure forces during the calendering step during the assembly of the glass and the interlayer, which influence the quality of the bonding.
- This device 600 In order to carry out measurements during the manufacturing follow-up near the production line, and thus to intervene rapidly on the process in response to the wrong measured stress values, it is possible alternatively to use another measuring device 600 which, advantageously, is of small size and easily transportable.
- This device 600 shown in FIG. 7, is miniaturized at about 60 cm by 20 cm and comprises two three jaw systems 60 and 61, a rotation shaft 62, a motor 63 for the rotation of the shaft, an apparatus for torque measurement 64 and a box 65 housing the calculation elements.
- the round sample of the laminated glazing consisting of two sheets of glass and an interlayer made of the material of the outer layers, is intended to be sandwiched between the two jaw systems 60 and 61, one of the systems 60 being fixed while the other is able to be movable and rotated through its connection to the shaft 62.
- the torque measuring apparatus is disposed between the motor and the movable jaw system 61.
- the rotational speed of the shaft depends on the thickness of the spacer. By way of example, for a spacer made of the material of the external layers having a thickness of 0.76 mm, the rotation is of the order of 0.08 revolutions / min.
- the system 61 rotates and when the moment of the measured torque reverses, the initiation of the separation of the interlayer consisting of the material of the outer layers has taken place.
- the measuring apparatus is connected to the calculation elements of the box 65, which comprises a display part on which is directly readable the value of the adhesion stress ⁇ .
- the range of allowable values for regulation R43 within which any value of the adhesion stress ⁇ is suitable to satisfy the adhesion criterion, is the set of values below 5 MPa.
- the range of admissible values of the adhesion stress ⁇ for regulation R43 is between 2 MPa and 5 MPa, the lower limit of this range of values being determined to ensure good transparency of the glazing, regardless of considerations of mechanical strength of the glazing.
- the adhesion stress ⁇ of the interlayer consisting of the material of the outer layers is situated in the aforementioned range of admissible values, the actual sizing of the outer layers of the interlayer is carried out.
- the graphs in FIGS. 4 and 5 illustrate two possible approaches for sizing these outer layers so that they meet the requirements of the hard shock resistance regulation R43.
- a glazing unit is dimensioned with a total thickness e g -di m of glass sheets in the laminated window, fixed and equal to 4.2 mm, which corresponds to for example at a thickness of each glass sheet of 2.1 mm, and an interlayer made of the material of the outer layers, of specific composition c, for example a spacer based on PVB.
- the central layer is ignored for determining the thickness of the outer layers.
- a curve C 3 representative of the minimum interlayer tear strength J c - m , is drawn. It is necessary for any laminated glazing to withstand the forces corresponding to the regulation R43, depending on the thickness of the interlayer e, of the laminated glazing of any kind, this curve being established for a thickness of glass sheet e g equal to 4.2 mm.
- the curve C 3 is obtained from standardized strength tests defined in the R43 regulation, made on laminated glazing of different compositions in terms of thickness of their interlayer.
- a reference laminated glazing unit which withstands the forces corresponding to the regulation R43, with a glass substrate thickness equal to 4.2 mm, and which has an interlayer having the specific composition c 1, is then identified.
- An example of such a laminated reference glazing is known glazing 2.1 / 0.76 / 2.1, which comprises two glass substrates 2.1 mm thick each and two interlayer layers of standard thickness. 0.38 mm having the composition c , which corresponds to an interlayer thickness i-ref of the reference laminated glazing equal to 0.76 mm.
- the resistance of this reference glazing to the forces corresponding to regulation R43 is verified by a standardized test of mechanical strength, in this example with an impactor drop height of 4 m.
- the tear strength J c - re f of the interlayer of the reference glazing 2.1 / 0.76 / 2.1 is then determined by the Tieiking method.
- This method developed by M. Tieiking, consists of evaluating the tensile strength of a material on the basis of a method for calculating the energy of the crack bottom J.
- the method of Tieiking is explained in particular. in the patent applications EP-A-1 151 855 and EP-A-1 495 305, and incorporated in part below.
- the tear resistance of an interlayer is an intrinsic characteristic of the material constituting it. It is characterized by an energy value representative of the energy necessary for the propagation of an initialized crack in the material. This energy, called critical energy J c , is different for each type of material and is independent of the thickness of the interlayer film.
- ei is the thickness of the sample
- U the potential energy of the sample.
- the experimental device for the determination of the tear strength is illustrated in FIG. 8.
- Tensile tests using a traction-compression machine 700 are carried out on several samples Ex n , for example four, the same material and surface equal to 100 mm 2 (50 mm long by 20 mm wide). Each sample is notched on its sides and perpendicular to the tensile force, of a distinct crack length a for each sample Ex n , and corresponding respectively to 5, 8, 12 and 15 mm.
- Each sample Ex n is stretched perpendicular to the cracks 20 at a stretching speed of 100 mm / min and over a given stretching length or distance d, and in an environment where the temperature is 20 ° C.
- the value of the tear strength J c - re f measured for the composition interlayer c, of the reference glazing 2.1 / 0.76 / 2.1 is 31000 J / m 2 .
- the minimum interlayer thickness required EI- mi n corresponding to a resistance value to the minimum required interlayer tear J c - min equal to the resistance to tearing of the interlayer of the laminated reference glazing J c - re f.
- the minimum required interlayer thickness ⁇ TM is equal to 0.45 mm.
- the interlayer thickness of the laminated glazing is greater than the required minimum interlayer thickness value ⁇ TM only within a limit of 20% above this value, i.e., in the preceding example, e id im is preferably such that 0.45 mm ⁇ 0.55 mm.
- a laminated glazing unit satisfying the requirements of regulation R43 is thus obtained, which comprises two sheets of glass 1, 2 with a thickness of 2.1 mm and one interlace with a central layer 3 and two outer layers 4, 5, each of the layers having a thickness of between 0.225 mm and 0.275 mm.
- Curve C 3 can be drawn for other values of glass sheets, for example 1, 8 mm and 1.4 mm. Each of the outer layers then has a thickness of between 0.2 mm and 0.37 mm.
- a laminated glazing is dimensioned without arbitrarily fixing the thickness of the glass sheets, the glazing comprising an interlayer consisting of the material of the outer layers.
- the graph C 4 of FIG. 5 is obtained from standardized strength tests defined in the regulation R43, made on laminated glazings with different compositions in terms of the thickness of the interlayer and the thickness of the substrate.
- the tear strength J c - re f of a reference laminated glazing unit which withstands the forces corresponding to the regulation R43 and which has an interlayer having the specific composition c 1, is then determined.
- the known laminated glazing 2.1 / 0.76 / 2.1 described above can for example serve as laminated reference glazing, as well as the laminated glazing 2.1 / 0.76 / 1, 8, also known, which comprises two glass sheets of respective thicknesses 2.1 mm and 1.8 mm and two interlayer layers consisting of the material of the outer layers of standard thickness 0.38 mm having the composition c , which corresponds to a e- ref spacer thickness equal to 0.76 mm.
- the resistance to tearing J c - re f of one or the other glazing of reference to the corresponding efforts Regulation R43 is assessed as previously by the Tielking method.
- each of the optimum values e i-0 pt or e g - 0 pt is not necessarily, individually, a minimum value of the interlayer thickness consisting of the material of the outer layers or a minimum value of the thickness of glass sheets. It is the combination of the values e i-0 pt and e g - 0 pt which leads to a minimized value of the overall thickness of the laminated glazing.
- the laminated glazing with a thickness ei-dim of the interlayer consisting of the material of the outer layers greater than or equal to 0.5 mm and thicknesses e g - d im of glass sheets of 1.8 mm and 1.4 mm, respectively, this laminated glazing meeting the requirements of Regulation R43.
- composition interlayer c considered in the above examples, exhibits average performance in tear strength and tear strength levels of the best performing interlayer compositions known at the time. current allow to consider combinations of optimal values e i-0 pt, e g - op still reduced compared to the values given above.
- the thickness of EI- mi n minimum interlayer may descend up to about 0.4 mm. Therefore, the interlayer thickness of EI-im optimized laminated glazing meeting the requirements of Regulation R43 and comprising two glass substrates of respective thicknesses 1, 8 mm and 1, 4 mm is, in general, such that 0.4 mm ⁇ ei- d im ⁇ 0 , 74 mm, the lower limit of this range corresponding to interlayer compositions having high performance in tear resistance.
- a laminated glazing unit satisfying the requirements of regulation R43 is thus obtained, which comprises two sheets of glass 1, 2 with respective thicknesses 1, 8 mm and 1.4 mm and an interlayer with a central layer 3 and two outer layers 4, 5 each of the outer layers having a thickness of between 0.2 mm and 0.37 mm.
- each outer layer 4, 5 is fixed so that they provide sufficient mechanical properties to the glazing, namely mechanical properties that comply with regulation R43.
- a reference laminated glazing unit which withstands the efforts corresponding to regulation R43 and which comprises two sheets of glass and an interlayer consisting of the material of the outer layers;
- the thickness e of each outer layer is fixed such that e is greater than or equal to said optimum value of spacer thickness (e i-0 pt).
- both the thickness e of each outer layer 4, 5 and the thickness of the glass sheets are fixed so that the assembly provides sufficient mechanical properties to the glazing, namely mechanical properties which satisfy the Regulation R43.
- a reference laminated glazing unit which withstands the efforts corresponding to regulation R43 and which comprises two sheets of glass and an interlayer consisting of the material of the outer layers; the resistance to tearing (J c - re f) of the interlayer of the reference laminated glazing, the thickness of the interlayer (2e- ref ) of the reference laminated glazing and the thickness of glass sheets ( e g - ref ) of the laminated reference glazing unit;
- the thickness e of each outer layer is fixed such that e is greater than or equal to said optimum value of interlayer thickness (e i-0 pt) and the thickness of the glass sheets is fixed (e g -di m ) greater than or equal to said optimum thickness value of glass sheets (e g - op t).
- Figure 3 shows a sectional view of a glazing unit according to the invention according to another embodiment.
- the glass sheets 1, 2 and the outer layers 4, 5 of the interlayer are identical to those of FIG. 2.
- the central layer 3 comprises two damping films 6, 7.
- the damping film 6 is made of a viscoelastic plastic material A, which is different from the viscoelastic material B of which the damping film 7 is made.
- the materials A, B are coextruded. Alternatively, they are laminated.
- the damping films 6, 7 constituting the central layer 3 make it possible to optimize the damping of the acoustic vibrations over different temperature ranges.
- the film 6 optimally dampens the acoustic vibrations over a first temperature range
- the film 7 optimally dampens the acoustic vibrations over a second temperature range.
- the first and second temperature ranges do not overlap. This allows optimizes the damping of frequencies between 100 Hz and 240 Hz over a wider range of temperatures.
- the material A is chosen to present, over a temperature range t A, and for a frequency of between 100 Hz and 240 Hz, a loss factor greater than 0.6 and a shear parameter of between 5, 58.10 8 Pa / m and 2.37 x 10 9 Pa / m.
- the material B is chosen to present, over a temperature range t B, and for a frequency of between 100 Hz and 240 Hz, a loss factor greater than 0.6 and a shear parameter of between 5.58 ⁇ 10 8 Pa. / m and 2.37 ⁇ 10 9 Pa / m.
- the equivalent shear parameter corresponds to the shear modulus.
- the given temperature range is the first temperature range or the second temperature range in which film 6 or 7 respectively optimally dampens acoustic vibrations at frequencies between 100 Hz and 240 Hz.
- the loss factor of each of the films 6, 7 be greater than 0.6 and that the shearing parameter of the material of each of the films be between 5.58 ⁇ 10 8 Pa / m and 2.37 ⁇ 10. 9 Pa / m in its corresponding range of temperatures, but the most damped film (highest tan ⁇ ) in the corresponding temperature range must have a much lower equivalent shear modulus than the other film. In this way, the interlayer will exhibit similar behavior to the most damped film in each temperature range. The interlayer will thus ensure optimum damping on each of the temperature ranges for which each of the films constituting the interlayer plays an optimal damping role. We will now provide proof that the damping of frequencies between 100 Hz and 240 Hz is optimal for the ranges of g described above.
- FIG. 1 represents a curve of the modal damping of a laminated windshield as a function of the shear parameter g of a central layer of the interlayer of the laminated windshield for frequencies between 100 Hz and 240 Hz at 20 ° C. This curve was calculated by a finite element method.
- the interlayer comprises three layers: a central layer incorporated between two outer layers.
- Each point of the curve of FIG. 1 represents the modal damping value as a function of the shear parameter for a thickness h of the central layer, the various points corresponding to thicknesses h between 0.10 mm and 1, 20 mm.
- Table 1 above includes shear parameter values g and modal damping values for each value of h.
- the range of shear parameter g between 5.58 ⁇ 10 8 Pa / m and 2.37 ⁇ 10 9 Pa / m for a central layer 3 having a thickness h of between 0.31 mm. and 1, 20 mm, at 20 ° C and for a frequency range between 100 Hz and 240 Hz, allows a damping- modal ratio greater than or equal to 0.327, so very good since the maximum of the curve is 0.338 for a central layer thickness of 0.7 mm.
- the invention therefore makes it possible to optimize the vibro-acoustic damping of the first natural frequencies of a windshield comprising the spacer as described above.
- the interlayer according to the invention also allows a good vibro-acoustic damping outside the frequency range for which it is optimized.
- the interlayer according to the invention is preferably used for a windshield between two sheets of glass. It can also be used in a side glazing or in a vehicle roof glazing, for example a motor vehicle.
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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PL11758517T PL2608958T3 (pl) | 2010-08-24 | 2011-08-18 | Sposób wyboru wkładki międzywarstwowej do tłumienia drgań akustycznych, wkładka międzywarstwowa i oszklenie zawierające taką wkładkę |
ES11758517.4T ES2675543T3 (es) | 2010-08-24 | 2011-08-18 | Procedimiento de selección de una capa intermedia para amortiguación vibroacústica, capa intermedia y acristalamiento que comprende dicha capa intermedia |
JP2013525335A JP5986085B2 (ja) | 2010-08-24 | 2011-08-18 | 振動音響減衰のための中間層の選択方法、中間層、およびこのような中間層を含むグレージングユニット |
MX2013001651A MX345676B (es) | 2010-08-24 | 2011-08-18 | Metodo para seleccionar una capa intermedia para amortiguacion vibroacustica, una capa intermedia y encristalado que comprende dicha capa intermedia. |
CA2806531A CA2806531C (fr) | 2010-08-24 | 2011-08-18 | Procede de selection d'un intercalaire pour un amortissement vibro-acoustique, intercalaire et vitrage comprenant un tel intercalaire |
BR112013002111-0A BR112013002111B1 (pt) | 2010-08-24 | 2011-08-18 | Processo de seleção de um intercalar plástico viscoelástico, intercalar plástico viscoelástico, vidraça compreendendo tal intercalar, veículo compreendendo tal vidraça, utilização de tal intercalar e utilização de tal vidraça |
EA201390279A EA026166B1 (ru) | 2010-08-24 | 2011-08-18 | Способ выбора элементов для формирования вязкоупругой пластической вставки, вязкоупругая пластическая вставка, узел остекления, содержащий такую вставку, и транспортное средство, содержащее такой узел остекления |
KR1020137004452A KR101890956B1 (ko) | 2010-08-24 | 2011-08-18 | 음향 진동 감쇠를 위한 중간층을 선택하기 위한 방법, 중간층, 및 그러한 중간층을 포함하는 창유리 유닛 |
EP11758517.4A EP2608958B1 (fr) | 2010-08-24 | 2011-08-18 | Procédé de sélection d'un intercalaire pour un amortissement vibro-acoustique, intercalaire et vitrage comprenant un tel intercalaire |
ZA2013/00966A ZA201300966B (en) | 2010-08-24 | 2013-02-05 | Method for selecting an iinterlayer for vibroacoustic damping, interlayer and glazing unit comprising such an interlayer |
Applications Claiming Priority (2)
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FR1056725A FR2964100B1 (fr) | 2010-08-24 | 2010-08-24 | Procede de selection d'un intercalaire pour un amortissement vibro-acoustique, intercalaire et vitrage comprenant un tel intercalaire |
FR1056725 | 2010-08-24 |
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WO2012025685A1 true WO2012025685A1 (fr) | 2012-03-01 |
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PCT/FR2011/051927 WO2012025685A1 (fr) | 2010-08-24 | 2011-08-18 | Procede de selection d'un intercalaire pour un amortissement vibro-acoustique, intercalaire et vitrage comprenant un tel intercalaire |
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US (2) | US9102122B2 (fr) |
EP (1) | EP2608958B1 (fr) |
JP (1) | JP5986085B2 (fr) |
KR (1) | KR101890956B1 (fr) |
CN (2) | CN202117506U (fr) |
AR (1) | AR082658A1 (fr) |
BR (1) | BR112013002111B1 (fr) |
CA (1) | CA2806531C (fr) |
DE (1) | DE202010008579U1 (fr) |
EA (1) | EA026166B1 (fr) |
ES (1) | ES2675543T3 (fr) |
FR (1) | FR2964100B1 (fr) |
MX (1) | MX345676B (fr) |
PL (1) | PL2608958T3 (fr) |
PT (1) | PT2608958T (fr) |
WO (1) | WO2012025685A1 (fr) |
ZA (1) | ZA201300966B (fr) |
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US11407204B2 (en) | 2018-01-31 | 2022-08-09 | Saint-Gobain Glass France | Laminated glazing with an electrically controllable device and manufacture |
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Also Published As
Publication number | Publication date |
---|---|
CN102373867A (zh) | 2012-03-14 |
EA201390279A1 (ru) | 2013-07-30 |
DE202010008579U1 (de) | 2011-10-05 |
BR112013002111B1 (pt) | 2020-01-07 |
EP2608958B1 (fr) | 2018-03-14 |
CN102373867B (zh) | 2018-04-24 |
MX345676B (es) | 2017-02-10 |
BR112013002111A2 (pt) | 2016-05-17 |
EA026166B1 (ru) | 2017-03-31 |
FR2964100B1 (fr) | 2015-10-16 |
JP5986085B2 (ja) | 2016-09-06 |
JP2013541484A (ja) | 2013-11-14 |
CN202117506U (zh) | 2012-01-18 |
CA2806531C (fr) | 2018-04-03 |
PL2608958T3 (pl) | 2018-08-31 |
US9102122B2 (en) | 2015-08-11 |
US20150283959A1 (en) | 2015-10-08 |
PT2608958T (pt) | 2018-05-29 |
US9733173B2 (en) | 2017-08-15 |
CA2806531A1 (fr) | 2012-03-01 |
EP2608958A1 (fr) | 2013-07-03 |
MX2013001651A (es) | 2013-03-21 |
KR101890956B1 (ko) | 2018-08-22 |
AR082658A1 (es) | 2012-12-26 |
US20120052274A1 (en) | 2012-03-01 |
FR2964100A1 (fr) | 2012-03-02 |
ES2675543T3 (es) | 2018-07-11 |
ZA201300966B (en) | 2014-04-30 |
KR20130140619A (ko) | 2013-12-24 |
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