WO2019020923A1 - Polymère hybride pour intercalaire plastique viscoélastique - Google Patents
Polymère hybride pour intercalaire plastique viscoélastique Download PDFInfo
- Publication number
- WO2019020923A1 WO2019020923A1 PCT/FR2018/051887 FR2018051887W WO2019020923A1 WO 2019020923 A1 WO2019020923 A1 WO 2019020923A1 FR 2018051887 W FR2018051887 W FR 2018051887W WO 2019020923 A1 WO2019020923 A1 WO 2019020923A1
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- WO
- WIPO (PCT)
- Prior art keywords
- inner layer
- glazing
- interlayer
- thickness
- khz
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Definitions
- the invention relates to a viscoelastic plastic interlayer intended to be incorporated between two sheets of glass to form a laminated glazing unit having vibroacoustic damping properties, intended for a locomotion machine, in particular a motor vehicle.
- the invention also relates to a method of manufacturing such an interlayer, in particular via a liquid deposition process.
- Acoustic glazing is used in the transport and building sectors.
- noises such as those emitted by the engine, bearings or suspensions, are damped at their origin and during their propagation air or solid.
- laminated type glazing having a thickness of less than 6 mm.
- These laminated glazings are generally in the form of an interlayer arranged between two outer glass sheets according to a known method of manufacturing laminated glazing, for example by assembling hot and under pressure.
- this spacer is itself composed of an inner layer arranged between two outer layers of thermoplastic adhesive.
- the inner layer consists of a viscoelastic polymer which, even in relatively thin layers, produces a noise-canceling effect.
- This polymer must fulfill in the long term, that is to say throughout the life of the vehicle, all the conditions inherent to the targeted transport area. These conditions include a low degree of turbidity, high transparency and good resistance to oxidation and corrosion. In addition, this polymer must ensure a quality and durable assembly with the adjacent layers and maintain its good noise damping properties, even at extreme temperatures.
- the interlayer can not affect the properties of the glazing in terms of safety.
- the glazing in the case of a windshield application, the glazing must in particular have sufficient rigidity to meet all the requirements of United Nations Regulation No. 43 (so-called R43) for mechanical resistance to hard shocks.
- the proposed technique relates to a viscoelastic plastic interlayer intended to be arranged between two glass sheets of a glazing to provide vibro-acoustic damping properties, the interlayer comprising two outer layers of thermoplastic adhesive, preferably of standard polyvinylbutyral (PVB), the thickness of which is preferably between 0.2 and 0.8 mm,
- PVB polyvinylbutyral
- a first and a second barrier layer arranged respectively between said outer layers and the inner layer, and composed of a viscoelastic plastic material, preferably polyester, in particular polyethylene terephthalate (PET).
- a viscoelastic plastic material preferably polyester, in particular polyethylene terephthalate (PET).
- thermoplastic glue denote the various resins and / or films making it possible to qualify the type of interlayer used.
- Thermoplastic adhesives also called “skins” in the context of a multi-layer interlayer, thus form a group comprising at least polyvinyl butyral (PVB), vinyl acetate-ethylene (EVA), polymers lonoplast, polyurethane Thermoplastic (TPU) and casting resins.
- PVB polyvinyl butyral
- EVA vinyl acetate-ethylene
- TPU polyurethane Thermoplastic
- PVB due to its synthesis by radical polymerization of vinyl acetate, hydrolysis of polyvinyl acetate which results in the production of polyvinyl alcohol (PVOH), then acetalization with butyraldehyde, is always a terpolymer consisting of vinyl alcohol, vinyl acetate and vinyl butyral units.
- standard PVB in the present application means PVB whose molar content of vinyl butyral units (VB) is included in the following ranges:
- the molar level of BV is greater than 42%, preferably greater than 44%, preferably greater than 46%, preferably greater than 48%, preferably greater than 50%, preferentially greater than 52%, preferentially greater than 53%, preferentially greater than 50%; 53.5%, preferably greater than 54%, preferably greater than 54.5%, preferably greater than 55%, preferentially greater than 55.5%, and less than 60%, preferably less than 59.5%, preferentially less than at 59%, preferentially less than 58.5%, preferably less than 58%, preferentially less than 58.5%, preferentially less than 58%, preferentially less than 57.5%, preferentially less than 57%, preferentially less than 56%. , 5%, based on the total number of monomer units of the PVB,
- the mass content of plasticizers expressed in parts per 100 parts of PVB resin (phr) is greater than 5 phr, preferably greater than 10 phr, preferably greater than 20 phr, preferably greater than 22.5 phr, preferably greater than 25 phr, and is less than 120 phr, preferentially less than 110 phr, preferably less than 90 phr, preferably less than 75 phr, preferably less than 60 phr, preferably less than 50 phr, preferably less than 40 phr, preferably less than 35 phr, preferentially less than 30 phr, the glass transition temperature for a frequency of 100 Hz, is greater than 30 ° C, preferably greater than 40 ° C, and is less than 60 ° C, preferably less than 56 ° C.
- the thickness of the outer layers of thermoplastic adhesive is greater than 0.2 mm, so as not to harm by too low rigidity to the properties of the glazing in terms of safety.
- barrier layers describes two layers whose function is to prevent any chemical diffusion between the inner layer, also called “heart”, and the outer layers, also called “skins”.
- at least one of these barrier layers is composed of PET.
- the superficial properties of PET make it possible to unite as well with the material constituting the core as with the layers of thermoplastic glue, so that the laminated glazings according to the invention satisfy all the technical requirements even with regard to long term resistance and safety.
- the loss factor tan ⁇ corresponds to the ratio between the energy dissipated in caloric form and the elastic strain energy. It therefore corresponds to a technical characteristic of the nature of a material and reflects its ability to dissipate energy, especially acoustic waves.
- This loss factor tan ⁇ varies as a function of the temperature and the frequency of the incident wave. For a given frequency, the loss factor reaches its maximum value at a temperature, called the glass transition temperature.
- This loss factor tan ⁇ can be estimated using a viscoanalyzer or other suitable known device. Note that the loss factor tan ⁇ of the inner layer determines the loss factor tan ⁇ of the spacer, which is substantially of the same value, as the volume fraction of the inner layer is not too low.
- the invention is based on a new and inventive concept of providing a spacer with a core whose characteristics make it possible to obtain a laminated glazing having improved acoustic insulation, both aerial and solid, while maintaining satisfactory characteristics in terms of rigidity, finesse, and lightness. It has been observed that this improvement of the acoustic insulation is significant in the frequency range between 2000 Hz and 8000 Hz, in which area the human ear is the most sensitive, and in particular at the frequency of coincidence, where the glazing usually has a drop in sound insulation performance.
- said loss factor tan ⁇ of the inner layer is greater than or equal to 2, preferably 2.5, preferably 3, preferably 3.5, preferably 4, preferentially 4.5.
- the loss factor tan ⁇ is generally less than 5.
- An interlayer with such mechanical characteristics in shear has satisfactory rigidity and acoustic insulation performance.
- the inner layer is obtained from a colloid, preferably from an emulsion, preferably from an aqueous emulsion of at least one polymer.
- the term "colloid” refers to a suspension of one or more substances, regularly dispersed in another substance, forming a separate two-phase system. In a fluid, this colloid forms a homogeneous dispersion of particles whose dimensions range from nanometer to micrometer.
- An emulsion is a colloid in which these substances are in the liquid state.
- an aqueous polymer emulsion is also called a "polymer latex", these two terms being equivalent.
- colloids present on the market, and in particular the polymer emulsions, have the particularity of presenting a milky appearance. This at least partial opacity is a priori a crippling disadvantage prohibiting any implementation between two transparent glass sheets.
- the colloids are not always suitable for being deposited in the form of layers of reduced thickness.
- the inner layer is obtained from an aqueous emulsion of at least two polymers structured in interpenetrating networks, said two polymers being preferably acrylate and acrylic.
- the two polymers structured in interpenetrating networks form a single particle suspended in water.
- the inner layer comprises between 33 and
- Such an inner layer is characterized by a loss factor tan ⁇ greater than or equal to 3, and therefore has excellent acoustic insulation performance.
- said inner layer has a thickness of between 0.5 and 50 microns, preferably between 10 and 40 microns, preferably between 20 and 30 microns.
- the inner layer represents a volume fraction of the interlayer of between 0.2% and 8%, preferably between 0.5% and 6%, preferably between 2.5% and 4%.
- said first and second barrier layers each have a thickness of between 1 and 50 microns, preferably between 1 and 30 microns, preferably between 5 and 15 microns.
- This thickness must be thick enough not to allow the migration of chemical species between the inner layer 3 and the outer layers (4, 5). On the other hand, beyond a certain thickness value of the outer layer (4, 5), the increase in the stiffness of the interlayer is too great and poses a problem during the shaping of the interlayer.
- the interlayer is tinted in the mass on a part of its surface and / or has a cross-section decreasing wedge-shaped from the top to the bottom of a laminated glazing in which it is intended to be arranged and / or comprises particles with an infrared radiation filter function.
- the invention also relates to a laminated glazing unit comprising:
- interlayer as described above, the interlayer being arranged between the first and second sheets of glass.
- said first sheet of glass has a thickness of between 0.5 and 2.1 mm, preferably between 1.4 and 2.1 mm
- said second sheet of glass has a thickness of between 0.5 and 2.1 mm, preferably between 1.1 and 1.6 mm.
- the invention also relates to the use of glazing as described above as a vehicle windshield.
- the invention also relates to the use of glazing as described above as building glazing, either in single glazing or integrated in a multiple glazing unit.
- the invention also relates to a method for manufacturing an interlayer as described above, comprising at least one deposition step on the first or the second barrier layer, via a method of liquid deposition, of an inner layer. from an aqueous emulsion of at least one polymer.
- liquid deposition of an aqueous emulsion having been previously diluted in a volume of water greater than or equal to 1.5 times its own volume makes it possible to reduce the viscosity of the mixture and thus to allow its subsequent deposition in the form of a layer of reduced thickness.
- Figure 1 is a schematic sectional view of a glazing according to a particular embodiment of the invention.
- FIG. 2 is a graph representing an evaluation of the properties of airborne sound insulation (STL) as a function of frequency, for a laminated glazing unit according to the invention and for a known laminated glazing unit;
- STL airborne sound insulation
- Figure 3 is a flow diagram of a method of manufacturing a spacer according to one embodiment of the invention.
- the invention relates to a viscoelastic plastic interlayer intended to be arranged between two glass sheets (1, 2) of a glazing unit to provide vibroacoustic damping properties, the interlayer comprising:
- thermoplastic glue two outer layers (4, 5) of thermoplastic glue
- the interlayer comprises a total of three active layers in the sound insulation effort, separated from each other by barrier layers whose function is to prevent any chemical diffusion between the inner layer 3 and the outer layers (4, 5).
- This interlayer structure in particular this alternation of more rigid and less damped layers and a less rigid and more damped layer, gives the glazing an improvement in its acoustic insulation properties, in particular in a frequency range between 2000 Hz and 8000 Hz.
- the interlayer according to the invention is intended to be incorporated between two sheets of glass (1, 2) to form a laminated glazing unit.
- Figure 1 shows a sectional view of a glazing according to a first embodiment of the invention.
- the glazing comprises two sheets of glass (1, 2) between which is inserted the interlayer according to the invention.
- the outer layers (4, 5) are thus in contact with the glass sheets respectively (1, 2).
- the heart 3 is interposed between these outer layers (4, 5).
- the interlocking of the interlayer with the glass sheets is for example carried out by known means, for example by stacking the glass sheets and the interlayer and by passing the assembly in an autoclave.
- each glass sheet (1, 2) is for example between 0.5 mm and 2.1 mm for an automotive glazing application, for example windshield, and between 0.5 mm and 15, 0 mm for building glazing application.
- the glazing meets all the requirements of the United Nations Regulation No. 43 (known as R43) of resistance to hard shocks to ensure its mechanical strength.
- 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 for example thicker than the glass sheet 2 so that the glazing allows better protection against external attacks (inclement weather, projection of gravel, etc.).
- 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 outer layers (4, 5) are composed of standard PVB. These outer layers (4, 5) have a shear modulus G 'greater than or equal to 1.10 8 Pa and a loss factor tan ⁇ less than 0.4, at 20 ° C and for a frequency range between 1 kHz and 10 kHz. They thus allow good mechanical strength of the interlayer.
- the core 3 of the interlayer has a thickness of 25 microns and its volume is about 3% of the total volume of the interlayer.
- the heart 3 consists for example of an aqueous acrylate emulsion and acrylic named QuietGlue ®, which is described in the patent document US2005 / 0050846.
- the heart 3 can also be composed of GreenGlue ®.
- the QuietGlue ® once integrated into a spacer in the form of a layer of reduced thickness, via a new deposition process, has properties of outstanding acoustic damping, while satisfying the other technical requirements expected of a core material.
- the dynamic characterization of the interlayer film is carried out on a viscoanalyzer of the Metravib viscoanalyzer type, under certain measurement conditions which are set out below:
- double shear test tube consisting of two rectangular parallelepipeds of dimension:
- the viscoanalyzer makes it possible to subject a sample of material to stresses of deformation under precise conditions of temperature and frequency, and thus to obtain and process all the rheological quantities characterizing the material.
- the exploitation of the raw data of the force, displacement and phase shift measurements, as a function of frequency, at each temperature makes it possible in particular to calculate the elastic component (or shear modulus) G 'and the loss factor tan ⁇ .
- FIG. 2 represents an estimated curve of airborne sound insulation performance (STL) as a function of frequency, evaluated on two laminated glazings according to standard NF EN ISO 10140 and with a sample size of 0.8 ⁇ 0, 5 m 2 : a laminated glazing according to the invention and a known laminated glazing.
- STL airborne sound insulation performance
- a first laminated glazing (known as "known") includes:
- an acoustic PVB interlayer comprising two external standard PVB layers and an internal viscoelastic plastic layer with improved vibro-acoustic damping properties.
- the first laminated glazing corresponds to a conventional glass windshield composition with an interlayer with known acoustic damping properties.
- the interlayer could for example be replaced by the Trosifol VG + SC interlayer marketed by Kuraray or by the Saflex ® Vanceva Quiet Q.C41 interlayer marketed by Solutia or by the S-Lec Acoustic Film interlayer HI-RZN12 marketed by Sekisui. This is known as "known" laminated glazing.
- the acoustic damping properties of this acoustic PVB remain limited by the very nature of this polymer, whose loss factor tan ⁇ is generally less than 1.2, at 20 ° C and for a frequency range between 2 kHz and 8 kHz.
- the airborne sound insulation curve of the first laminated glazing is represented by diamonds.
- a second laminated glazing unit (named “according to the invention") comprises:
- an interlayer according to the invention comprising two outer layers of standard PVB and an inner layer of a thickness of 25 microns in QuietGlue ® .
- the second laminated glazing corresponds to a laminated glazing unit according to the invention.
- the airborne sound insulation curve of the second laminated glazing is represented by squares.
- the airborne sound insulation curve (represented by squares) of the second laminated glazing shows an improvement of the sound insulation to the airborne noise over the entire frequency range, that is to say between 2000 Hz and 8000 Hz, compared to the first laminated reference glazing. It is particularly in the region between about 2000 and 8000 Hz and in the region of the coincidence frequency at about 6300 Hz, in which the damping curves of the glazings have the largest valleys in the case of laminated glazing. that the measured noise damping levels are significantly higher.
- a gain in acoustic insulation of 3.4 dB is observed between the respective values of 37.7 dB for the acoustic PVB and 41.2 dB for the interlayer according to the invention. A considerable improvement in the noise damping is thus achieved overall.
- the invention also relates to a laminated glazing unit comprising:
- an interlayer according to the invention for example comprising a QuietGlue ® core 25 microns thick.
- the technique according to the invention proposes a laminated glazing for a vehicle comprising an interlayer film having a good damping of the noises transmitted by the solids. This damping can also meet the isolation criteria for aerodynamic noise and external noise.
- the glazing according to the invention makes it possible to obtain a good general acoustic protection.
- the interlayer according to the invention may furthermore:
- tinted in the mass on a part of its surface to allow a respect of the intimacy of the people inside a vehicle or to protect the driver of a vehicle against glare in the light of the sun or simply for an aesthetic effect, and / or
- HUD Head Up Display
- infrared radiation filter function to limit the rise in temperature inside a vehicle due to the infrared radiation of the sun, to improve the comfort of the passengers.
- the invention also relates to a method of manufacturing an interlayer as described above.
- a given amount of an aqueous emulsion of at least one polymer, e.g. QuietGlue ®, is first diluted in place (step) in at least one and a half times or three (3) times its volume in water, in particular to reduce the viscosity of the mixture and thus to allow its subsequent deposition in the form of a layer of reduced thickness.
- at least one polymer e.g. QuietGlue ®
- the assembly is subsequently deposited (step S2) via a liquid deposition process on a first outer layer 4 of conventional PVB surmounted by a barrier layer 6 of PET.
- step S3 The whole is then dried (step S3) for 1 hour, at a temperature of 80 ° C.
- the drying time normally recommended for QuietGlue ® is significantly reduced, making it industrially viable for use as a core material.
- the transparency of the QuietGlue ® is also considerably increased, to the point of allowing its implementation within a device optical. Note that according to alternative embodiments, it is possible to vary the time and / or the drying temperature of the QuietGlue ® , without departing from the scope of the invention.
- the QuietGlue ® returns to its original composition. It can then be covered (step S4) with a second barrier layer 7 made of PET and then with a second external layer 5 made of standard PVB. An interlayer according to the invention is thus obtained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Joining Of Glass To Other Materials (AREA)
- Laminated Bodies (AREA)
- Vibration Prevention Devices (AREA)
Abstract
Description
Claims
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR112020000517-7A BR112020000517B1 (pt) | 2017-07-24 | 2018-07-23 | Camada intercalar de plástico viscoeslástico, vidraça laminada, uso de uma vidraça e método de fabricação de uma camada intercalar |
| CA3069765A CA3069765A1 (fr) | 2017-07-24 | 2018-07-23 | Polymere hybride pour intercalaire plastique viscoelastique |
| RU2020107418A RU2760698C2 (ru) | 2017-07-24 | 2018-07-23 | Гибридный полимер для вязкоупругого пластичного разделителя |
| EP18773525.3A EP3658373A1 (fr) | 2017-07-24 | 2018-07-23 | Polymère hybride pour intercalaire plastique viscoélastique |
| US16/633,322 US11413851B2 (en) | 2017-07-24 | 2018-07-23 | Hybrid polymer for visco-elastic plastic spacer |
| CN201880001837.4A CN109562610B (zh) | 2017-07-24 | 2018-07-23 | 用于粘弹性塑料中间层的混合聚合物 |
| PE2020000036A PE20200658A1 (es) | 2017-07-24 | 2018-07-23 | Polimero hibrido para espaciador plastico visco-elastico |
| KR1020247013461A KR20240068059A (ko) | 2017-07-24 | 2018-07-23 | 점탄성 플라스틱 이격체를 위한 혼성 중합체 |
| AU2018306367A AU2018306367B2 (en) | 2017-07-24 | 2018-07-23 | Hybrid polymer for visco-elastic plastic spacer |
| JP2020503309A JP7270599B2 (ja) | 2017-07-24 | 2018-07-23 | 粘弾性プラスチックスペーサのためのハイブリッドポリマー |
| MYPI2020000347A MY200618A (en) | 2017-07-24 | 2018-07-23 | Hybrid polymer for visco-elastic plastic spacer |
| KR1020207001998A KR20200035261A (ko) | 2017-07-24 | 2018-07-23 | 점탄성 플라스틱 이격체를 위한 혼성 중합체 |
| CONC2020/0000237A CO2020000237A2 (es) | 2017-07-24 | 2020-01-13 | Polímero híbrido para espaciador plástico visco-elástico |
| ZA2020/00336A ZA202000336B (en) | 2017-07-24 | 2020-01-17 | Hybrid polymer for visco-elastic plastic spacer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1757020 | 2017-07-24 | ||
| FR1757020A FR3069187B1 (fr) | 2017-07-24 | 2017-07-24 | Polymere hybride pour intercalaire plastique viscoelastique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2019020923A1 true WO2019020923A1 (fr) | 2019-01-31 |
Family
ID=60020088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2018/051887 Ceased WO2019020923A1 (fr) | 2017-07-24 | 2018-07-23 | Polymère hybride pour intercalaire plastique viscoélastique |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US11413851B2 (fr) |
| EP (1) | EP3658373A1 (fr) |
| JP (1) | JP7270599B2 (fr) |
| KR (2) | KR20200035261A (fr) |
| CN (1) | CN109562610B (fr) |
| AU (1) | AU2018306367B2 (fr) |
| CA (1) | CA3069765A1 (fr) |
| CO (1) | CO2020000237A2 (fr) |
| FR (1) | FR3069187B1 (fr) |
| MA (1) | MA49695A (fr) |
| MY (1) | MY200618A (fr) |
| PE (1) | PE20200658A1 (fr) |
| RU (1) | RU2760698C2 (fr) |
| WO (1) | WO2019020923A1 (fr) |
| ZA (1) | ZA202000336B (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024141582A1 (fr) * | 2022-12-29 | 2024-07-04 | Saint-Gobain Glass France | Intercalaire acoustique comprenant une couche de coeur adhésive d'amortissement viscoélastique transparente |
| WO2024213700A1 (fr) | 2023-04-14 | 2024-10-17 | Saint-Gobain Glass France | Titre de l'invention : structure de batiment comportant une fenetre a vitrage, et procede d'assemblage d'une telle structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117416113B (zh) * | 2023-10-11 | 2024-04-09 | 常州佳尔科仿真器材有限公司 | 一种用于假目标的轻质多层多波段高反射tpu复合材料 |
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- 2018-07-23 CA CA3069765A patent/CA3069765A1/fr active Pending
- 2018-07-23 MY MYPI2020000347A patent/MY200618A/en unknown
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- 2018-07-23 CN CN201880001837.4A patent/CN109562610B/zh active Active
- 2018-07-23 WO PCT/FR2018/051887 patent/WO2019020923A1/fr not_active Ceased
- 2018-07-23 JP JP2020503309A patent/JP7270599B2/ja active Active
- 2018-07-23 EP EP18773525.3A patent/EP3658373A1/fr active Pending
- 2018-07-23 US US16/633,322 patent/US11413851B2/en active Active
- 2018-07-23 PE PE2020000036A patent/PE20200658A1/es unknown
- 2018-07-23 MA MA049695A patent/MA49695A/fr unknown
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- 2018-07-23 RU RU2020107418A patent/RU2760698C2/ru active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024141582A1 (fr) * | 2022-12-29 | 2024-07-04 | Saint-Gobain Glass France | Intercalaire acoustique comprenant une couche de coeur adhésive d'amortissement viscoélastique transparente |
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| WO2024213700A1 (fr) | 2023-04-14 | 2024-10-17 | Saint-Gobain Glass France | Titre de l'invention : structure de batiment comportant une fenetre a vitrage, et procede d'assemblage d'une telle structure |
| FR3147830A1 (fr) | 2023-04-14 | 2024-10-18 | Saint-Gobain Glass France | Structure de batiment comportant une fenetre a vitrage, et procede d’assemblage d’une telle structure |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2020107418A3 (fr) | 2021-10-11 |
| MA49695A (fr) | 2020-06-03 |
| US20200156354A1 (en) | 2020-05-21 |
| FR3069187B1 (fr) | 2019-08-02 |
| ZA202000336B (en) | 2021-08-25 |
| AU2018306367A1 (en) | 2020-01-30 |
| JP7270599B2 (ja) | 2023-05-10 |
| AU2018306367B2 (en) | 2023-05-25 |
| BR112020000517A2 (pt) | 2020-07-14 |
| KR20200035261A (ko) | 2020-04-02 |
| CA3069765A1 (fr) | 2019-01-31 |
| KR20240068059A (ko) | 2024-05-17 |
| EP3658373A1 (fr) | 2020-06-03 |
| JP2020528040A (ja) | 2020-09-17 |
| CN109562610B (zh) | 2021-07-27 |
| CO2020000237A2 (es) | 2020-04-24 |
| US11413851B2 (en) | 2022-08-16 |
| CN109562610A (zh) | 2019-04-02 |
| RU2020107418A (ru) | 2021-08-25 |
| FR3069187A1 (fr) | 2019-01-25 |
| MY200618A (en) | 2024-01-05 |
| RU2760698C2 (ru) | 2021-11-29 |
| PE20200658A1 (es) | 2020-06-11 |
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