WO2020085021A1 - Procédé de fabrication de verre feuilleté - Google Patents

Procédé de fabrication de verre feuilleté Download PDF

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Publication number
WO2020085021A1
WO2020085021A1 PCT/JP2019/038879 JP2019038879W WO2020085021A1 WO 2020085021 A1 WO2020085021 A1 WO 2020085021A1 JP 2019038879 W JP2019038879 W JP 2019038879W WO 2020085021 A1 WO2020085021 A1 WO 2020085021A1
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Prior art keywords
thermoplastic resin
resin film
laminated glass
plasticizer
film
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PCT/JP2019/038879
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English (en)
Japanese (ja)
Inventor
直也 森
健介 泉谷
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セントラル硝子株式会社
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Publication of WO2020085021A1 publication Critical patent/WO2020085021A1/fr

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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
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10825—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts
    • B32B17/10834—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid
    • B32B17/10844—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid using a membrane between the layered product and the fluid
    • B32B17/10853—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid using a membrane between the layered product and the fluid the membrane being bag-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10871—Making laminated safety glass or glazing; Apparatus therefor by pressing in combination with particular heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10981—Pre-treatment of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the present disclosure relates to a method for manufacturing a laminated glass in which two glass plates are bonded and integrated with a thermoplastic resin film, and more particularly to a method for manufacturing a laminated glass using a sound insulating thermoplastic resin film having improved sound insulating performance. .
  • PVB polyvinyl butyral
  • EVA ethylene-vinyl acetate copolymer
  • the above laminated glass can suppress a decrease in sound insulation performance due to the coincidence effect, and thus when used as a window material, it is possible to improve sound insulation performance.
  • the sound insulation performance of laminated glass depends on the rigidity of the above thermoplastic resin film, and when the rigidity becomes high, swelling occurs, and a transmission phenomenon similar to the coincidence effect newly occurs, which is desirable. It is said that the sound insulation performance of will not be obtained. Therefore, it has been studied to improve the flexibility of the thermoplastic resin film used as the intermediate film for the purpose of further improving the sound insulation performance of the laminated glass.
  • Patent Document 1 proposes to use PVB resin having a laminated structure of two or more layers as an intermediate film in order to improve the sound insulation performance of laminated glass. According to this document, when laminating two or more layers of PVB resin, it is possible to improve the sound insulation performance and the penetration resistance performance by making the plasticizer content of each layer different. There is. In addition, the examples of the document disclose that the sound insulation performance is improved by increasing the content of the plasticizer.
  • Patent Document 2 when a laminate of a PVB resin layer and an EVA resin layer is used as an interlayer film for a laminated glass having excellent impact resistance, penetration resistance, moisture resistance and sound insulation, the PVB resin layer has a solubility.
  • An interlayer film for laminated glass is disclosed, which contains a plasticizer having a parameter of 17 to 26 (J / cm 3 ) 1/2 and a molecular weight of 820 or more. The document discloses that by using the PVB resin layer as described above, it is possible to suppress the plasticizer contained in the PVB resin layer from migrating to the EVA resin layer over time.
  • an intermediate layer film for laminated glass which is composed of at least two partial films based on a plasticizer-containing polyvinyl acetal, for the purpose of improving the soundproofing performance of the intermediate film
  • the partial film contains a polyvinyl acetal having a polyvinyl acetate group in a proportion of 0.1 to 11 mol%
  • the second partial film contains a polyvinyl acetal having a polyvinyl acetate group in a proportion of 5 to 8 mol%.
  • Patent Document 4 at least 1 having a conventional plasticizer content of 24 to 36% by mass for the purpose of obtaining an intermediate film which is a multilayer film having good acoustic properties and easy to manufacture. Proposals have been made to combine one sheet of thicker PVB film with at least one thinner additional film having a lower plasticizer content.
  • JP-A-3-124440 Japanese Patent Laid-Open No. 2008-11929 JP, 2010-37193, A JP, 2014-156390, A
  • thermoplastic resin film used as the intermediate film As mentioned above, in order to improve the sound insulation performance of laminated glass, a method of improving the sound insulation performance of the thermoplastic resin film used as the intermediate film is required. In general, it is said that increasing the content of the plasticizer contained in the thermoplastic resin film improves the flexibility of the thermoplastic resin film.
  • a method is known in which the flexibility of the thermoplastic resin film is set within a desired range by adjusting the content of the plasticizer contained in the plastic resin film to an appropriate amount to improve the sound insulation performance.
  • thermoplastic resin film When incorporating a plasticizer into the thermoplastic resin film as described above, usually, the plasticizer is mixed with the thermoplastic resin material before the film is formed, and the film is formed by extrusion molding or the like.
  • the plasticizer is mixed with the thermoplastic resin material before the film is formed, and the film is formed by extrusion molding or the like.
  • dedicated equipment and advanced technology are required, and without such equipment or technology, there is a problem that there are few methods for improving the properties of the thermoplastic resin film.
  • the present disclosure aims to obtain a method of improving the flexibility of a thermoplastic resin film by a simpler method than the conventional method and improving the sound insulation performance of a laminated glass using the thermoplastic resin film.
  • thermomechanical analysis (TMA) device When the elongation rate of the PVB film was measured by a thermomechanical analysis (TMA) device, it was found that the elongation rate was higher than that of the PVB film before applying the plasticizer.
  • TMA thermomechanical analysis
  • the laminated glass using the PVB film is manufactured, the loss coefficient of the laminated glass is measured, and the sound transmission is performed by the method conforming to ISO16940 Glass in-building-Glazing and and airborne sound insulation-Measurement of of the mechanical The loss was calculated. As a result, it was found that at 20 ° C., the sound transmission loss was higher than that of the laminated glass using the PVB film before applying the plasticizer.
  • thermoplastic resin film is formed into a film shape in a state where a resin as a raw material is mixed with a plasticizer.
  • a step 1 of applying a plasticizer used for the resin on the surface of the thermoplastic resin film, and a temperature of the thermoplastic resin film within a range of 40 to 90 ° C. after the step 1 are applied.
  • ⁇ 3> A manufacturing process of the laminated glass according to ⁇ 1> or ⁇ 2>, further comprising a wiping step of wiping the surface of the sound insulating thermoplastic resin film after the permeation step, and performing the laminating step after the wiping step.
  • ⁇ 4> The method for producing a laminated glass according to any one of ⁇ 1> to ⁇ 3>, which includes a preliminary bonding step between the degassing step and the combining step.
  • the sound-insulating thermoplastic resin film is the laminated glass according to any one of ⁇ 1> to ⁇ 4>, wherein the weight reduction ratio of the weight after the laminating step to the weight before the laminating step is 0.01 to 15%. Production method.
  • ⁇ 6> The method for producing a laminated glass according to any one of ⁇ 1> to ⁇ 5>, wherein the glass plate is a bent glass plate.
  • a method for producing a sound insulating thermoplastic resin film for laminated glass Penetration to obtain a sound-insulating thermoplastic resin film by further permeating the plasticizer from the surface of the thermoplastic resin film into a thermoplastic resin film formed into a film shape in the state where a plasticizer is mixed with a resin as a raw material
  • a method for producing a sound-insulating thermoplastic resin film for laminated glass comprising the steps of:
  • a step 1 of applying a plasticizer used for the resin on the surface of the thermoplastic resin film, and a temperature of the thermoplastic resin film within a range of 40 to 90 ° C. after the step 1 are applied.
  • the sound insulating thermoplastic resin film has a thickness of 10 ⁇ m or more
  • TMA thermomechanical analysis
  • the elongation percentage of the sound insulating thermoplastic resin film is 6.8% or more when the measurement temperature is 25 ° C. and the load is 10 mN / min and the additional load is 200 mN or more. Is a sound insulating thermoplastic resin film.
  • the sound insulating thermoplastic resin film is obtained by allowing the plasticizer used in the thermoplastic film to penetrate into the thermoplastic resin film from the surface of the thermoplastic resin film, ⁇ 10> Alternatively, the sound insulating thermoplastic resin film according to ⁇ 11>.
  • the sound insulating thermoplastic resin film has a thickness of 10 ⁇ m or more,
  • the laminated glass had a maximum loss coefficient of 0.1 at a frequency of 2000 Hz and a temperature of 10 to 20 ° C. when measured by a method conforming to the vibration damping characteristic test method of unconstrained vibration damping composite beams described in JIS K7391. The above is the laminated glass.
  • FIG. 5 is a diagram showing a weight reduction rate with respect to elapsed time when the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure is left in a constant temperature bath. It is the figure which showed the sound transmission loss with respect to the frequency about the laminated glass obtained in Example 1. It is the figure which showed the sound transmission loss with respect to the frequency about the laminated glass obtained in the comparative example 1. It is the figure which showed the sound transmission loss with respect to the frequency about the laminated glass obtained in the comparative example 2.
  • the “film” in this specification may be in the form of a film, and may have an arbitrary layer on its surface or an arbitrary layer inside.
  • thermomechanical analysis (TMA) device Rive Thermo Plus TMA8310
  • TMA thermomechanical analysis
  • Loss factor As the loss factor in this specification, a value measured by a method conforming to the vibration damping characteristic test method of the unrestrained damping composite beam described in JIS K7391 was used. Specifically, a loss coefficient measurement system (manufactured by Brüel & Kj ⁇ r Japan) was used to obtain the loss coefficient with respect to the resonance frequency of the sample in the temperature range of ⁇ 20 to 80 ° C. by the central vibration method.
  • the measurement sample was prepared by the following method. First, a plasticizer (triethylene glycol bis2-ethylhexanate 90 + ⁇ %, manufactured by ALFA Acer, H54406) is applied to a thermoplastic resin film, and the plasticizer is permeated by leaving it in a constant temperature bath at 60 ° C for 30 hours. Then, a sound insulating thermoplastic resin film was produced. Next, the sound-insulating thermoplastic resin film was laminated between two glass plates (250 mm ⁇ 10 mm, plate thickness 2 mm), deaerated by a vacuum bag, and then pressured / heated by an autoclave. gave. The obtained laminated glass was used as a sample for measurement.
  • a plasticizer triethylene glycol bis2-ethylhexanate 90 + ⁇ %, manufactured by ALFA Acer, H54406
  • the plasticizer is permeated by leaving it in a constant temperature bath at 60 ° C for 30 hours.
  • a sound insulating thermoplastic resin film was produced.
  • the sound insulating thermoplastic resin film causes a weight loss when left at room temperature of about 20 to 30 ° C. for a predetermined time. It is considered that the permeated plasticizer enters the gaps between the thermoplastic resins of the film, and the film is in a swollen state, and part of the plasticizer exudes with the passage of time and temperature changes. It is thought to be because it will be.
  • the weight reduction also occurs due to the heating in the above-mentioned combining step. It is considered that during this combining step, the thermoplastic resin flows, the plasticizer permeated in the permeation step is taken into the network of the thermoplastic resin, and then reconstituted in that state. Therefore, it is considered that the weight loss at this time occurs because the excess plasticizer, water, and the like are removed from the film by volatilization or the like.
  • the weight loss rate in this specification was measured by the following method.
  • the weight reduction rate before and after the combining step is a value obtained by subtracting the weight of the glass plate from the weight of the laminated body before the combining step, and a value obtained by subtracting the weight of the glass plate from the weight of the laminated body after the combining step, It was calculated from the difference.
  • the weight reduction rate of the sound insulating thermoplastic resin film at 20 to 30 ° C. is as follows. First, the temperature of the sound insulating thermoplastic resin film is set to 20 to 30 ° C., then the surface is lightly wiped, and an electronic balance (made by METTLER TOLEDO, The weight was measured by PE3600).
  • the sample was left in a constant temperature bath at 20 to 30 ° C., taken out after about 0.5 to 1200 hours, and weighed.
  • the weight reduction rate was calculated from the difference between the weight at the time of measurement and the weight before being left in the constant temperature bath.
  • a method for producing laminated glass according to an embodiment of the present disclosure is a method for producing laminated glass, which comprises integrating at least two glass plates via a thermoplastic resin film.
  • the resin film is molded into a film shape in a state where a plastic material is mixed with a resin as a raw material, and the plasticizer used in the resin is further added to the thermoplastic resin film from the surface of the thermoplastic resin film.
  • An infiltration step of infiltrating to obtain a sound-insulating thermoplastic resin film, a laminating step of laminating the sound-insulating thermoplastic resin film between at least two glass plates to form a laminate after the infiltration step, and after the laminating step A degassing step of degassing each layer of the laminated body, and a combining step of integrating the degassed laminated body by applying pressure / heat treatment.
  • the permeation step is a step of obtaining a sound-insulating thermoplastic resin film by further permeating the plasticizer used for the resin from the surface into the thermoplastic resin film formed into a film shape in the state where the plasticizer is mixed. Further, in this step, a sound insulating thermoplastic resin film may be obtained by infiltrating a plasticizer usable in the thermoplastic resin while maintaining the film shape of the thermoplastic resin film.
  • the plasticizer to be permeated at this time may be the same as or different from the plasticizer originally contained in the thermoplastic resin film.
  • the plasticizer physically enters the gap between the thermoplastic resins in the process. Therefore, as the plasticizer permeates, the film may swell with the plasticizer and the thickness may increase by about 0.01 to 0.3 mm. Therefore, when an increase in thickness is observed, the plasticizer may penetrate into the thermoplastic resin film.
  • the plasticizer may be applied to the surface of the thermoplastic resin film with a brush or coater, sprayed or sprayed with a spray, or the thermoplastic resin may be dipped in a container containing the plasticizer. Further, the surface of the thermoplastic resin film may be roughened or scratched in advance so that the plasticizer can easily penetrate. Further, the above plasticizer may be one dispersed in a solvent as long as it is a solvent that does not dissolve the thermoplastic resin film.
  • the amount of the plasticizer used may be determined by the coating method, spraying method, dipping method, etc., and is not particularly limited. For example, it is preferable that the amount can be supplied to at least one entire surface of the thermoplastic resin film. Further, since the amount of the plasticizer that permeates is leveled off to some extent, an excessive amount of the plasticizer may be applied, sprayed, sprayed, dipped or the like on the thermoplastic resin film. Among the above-mentioned plasticizer supply methods, the application method is preferable because the plasticizer can be supplied without waste. At this time, it is preferable to apply 20 to 600 g / m 2 of a plasticizer to one surface of the thermoplastic resin film.
  • the plasticizer By bringing the plasticizer into contact with the surface of the thermoplastic resin film, the plasticizer penetrates into the thermoplastic resin film, but more plasticizer can be obtained by allowing the plasticizer to stand in an environment at a temperature higher than room temperature for a predetermined time. Can be penetrated. That is, in the infiltration step, the temperature of the thermoplastic resin film is set in the range of 40 to 90 ° C. after the step 1 of applying a plasticizer to the surface of the thermoplastic resin film, and after the step 1, It is preferable to have the step 2 of permeating When the temperature of the thermoplastic resin film is 40 ° C. or higher, the penetration of the plasticizer can be promoted and the plasticizer can be sufficiently permeated. Further, when the temperature of the thermoplastic resin film is 90 ° C. or lower, the film shape can be surely maintained. More preferably, it may be 40 to 60 ° C.
  • a desired amount of the plasticizer may infiltrate into the thermoplastic resin film, and the infiltration time is not particularly limited.
  • the infiltration time is not particularly limited.
  • the permeation time varies depending on the temperature of the constant temperature bath, for example, when the temperature of the thermoplastic resin film is in the range of 40 to 90 ° C., the permeation time may be preferably 6 hours or longer, more preferably 8 hours or longer. .
  • thermoplastic resin film when the permeation step is performed in an environment having a temperature higher than room temperature as described above, when a stretchable film obtained by being stretched in the manufacturing process is used as the thermoplastic resin film, the tension in the film is relaxed. The edges of the film may shrink or extend.
  • the thermoplastic resin having a larger area than the glass plate area tends to shrink in the machine direction (MD direction) and expand in the width direction (TD direction). It is preferable to use a film.
  • step 1 it is preferable to apply the plasticizer to the surface of the thermoplastic resin film using a coating device such as a brush coater or various coaters.
  • a coating device such as a brush coater or various coaters.
  • the thermoplastic resin film may be placed in a thermostatic bath or room in which the temperature is adjusted and allowed to stand, or the air may be kept at a predetermined temperature.
  • the method include spraying and heating with a heater or the like.
  • the plasticizer may be attached to the surface of the obtained sound-insulating thermoplastic resin film depending on the method used in the infiltration step, the amount of the plasticizer used, and the like. Since there is less adhesion of the plasticizer, it is less likely to cause degassing failure in the subsequent degassing step, and therefore, after the permeation step, there is a wiping step of wiping the sound insulating thermoplastic resin film surface, and the wiping step. After that, it is preferable to perform the laminating step.
  • the wiping step may be performed by wiping with a wiping material such as cloth, or by blowing air or the like to remove from the film surface.
  • the laminating step is a step of laminating a sound insulating thermoplastic resin film between at least two glass plates after the infiltration step to form a laminated body.
  • the sound insulating thermoplastic resin film, the glass plate and the respective members may be laminated on the glass plate in this order, or the members may be laid on a jig or the like to be laminated in order.
  • the sound insulating thermoplastic resin film is more flexible than the thermoplastic resin film, it may be difficult to handle if the temperature of the film is high. for that reason. After the infiltration step, the temperature may be once returned to room temperature and then the lamination step may be performed. Further, in the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure, when left at about 20 to 30 ° C., the plasticizer permeated from the film gradually exudes, It is preferable to start the laminating step immediately after the infiltration step of 1) or immediately after the wiping step.
  • the term "immediately" means that the sound insulation thermoplastic resin film is intentionally not left for a period of time except the time for which the film can be handled, for example, the temperature of the film is lowered or the time for transportation. Shall be pointed out.
  • the degassing step is a step of degassing the layers of the laminate after the laminating step.
  • a known degassing method may be used, and examples thereof include a method of pushing air between layers using a roll and a method of depressurizing each layer by depressurizing the layers.
  • cracking or the like may occur in the glass plate depending on the thickness or shape of the glass plate when deaeration is performed using a roll. For example, when the glass plate has a thickness of 1 mm or less, it is preferable that deaeration is performed by reducing the pressure between the layers of the laminate.
  • a tube made of a rubber-based resin is attached to the periphery of the laminate to exhaust air from an exhaust nozzle to degas, or a method of degassing in a vacuum bag.
  • the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure is one in which the plasticizer penetrated from the film gradually exudes when left at about 20 to 30 ° C. Therefore, it is preferable to start the degassing step immediately after the above-mentioned laminating step.
  • the term "immediately" means that no intentional leaving time is provided as described above.
  • the combining step is a step of integrating the degassed laminated body by applying pressure / heat treatment. It is convenient and preferable to use a general-purpose autoclave for the step.
  • pressure and temperature are appropriately selected according to the type of the sound insulating thermoplastic resin film to perform integration. For example, when a PVB film or EVA film is used as the thermoplastic resin film, the temperature is raised until the maximum temperature falls within the range of 100 to 150 ° C., and then the temperature is maintained for about 20 to 40 minutes. The above integration is possible.
  • pressurization is performed so as to be within a pressure range of 0.9 to 1.5 MPa. Either pressurization or heating may be performed first, or both may be performed simultaneously. Further, the pressure may be applied during the heating process. A press capable of heating may be used as long as it does not damage the glass plate.
  • the weight of the laminated glass is reduced before and after the laminating step. This is because the thermoplastic resin flows due to the heat during the combining process, and the thermoplastic resin is reconstituted with the permeated plasticizer being taken into the network, so that excess plasticizer, water, etc. volatilize. It is considered that this is caused by separation from the film. Therefore, the weight reduction ratio of the weight of the sound-insulating thermoplastic resin film after the bonding step to the weight before the bonding step is preferably 0.01 to 15%, more preferably 0.5 to 15%, and further preferably It may be 1 to 15%.
  • Pre-bonding process When the laminates are integrated in the above-mentioned joining step, water remaining in the laminates, components contained in the sound-insulating thermoplastic resin film, and the like may volatilize by heating, resulting in bubbles in the laminates. Further, depending on the conditions of heating and pressurization, air may enter between the glass plate and the sound insulating thermoplastic resin film. Therefore, it is preferable to heat and pressurize the laminated body under conditions that are milder than the bonding step, such that the sound insulating thermoplastic resin film has adhesiveness in advance, to suppress or remove the bubbles. This is referred to as "pre-bonding step" in the present specification. That is, it is preferable to have a preliminary bonding step between the degassing step and the combining step.
  • the temperature during the pre-bonding step is preferably such that the maximum temperature is about the glass transition temperature of the sound-insulating thermoplastic resin film + 10 ° C. or higher and the maximum temperature of the bonding step ⁇ 10 ° C. or lower, preferably 70 to 100. It may be set to ° C. As a result of investigations by the present inventors, it was found that a significant weight reduction does not occur before and after the preliminary bonding step within the above temperature range. Further, the temperature may be more preferably 80 to 100 ° C. In this step, it is preferable that the temperature is maintained for 10 to 30 minutes after heating to raise the temperature to 70 to 100 ° C.
  • the preliminary bonding step may be carried out a plurality of times as necessary, and in that case, the heating and pressurizing conditions of the respective preliminary bonding steps may be different or the same.
  • the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure is one in which the plasticizer penetrated from the film gradually exudes when left at about 20 to 30 ° C. Therefore, the pre-bonding step is preferably started immediately after the degassing step.
  • the term "immediately" means that no intentional leaving time is provided as described above.
  • the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure is a sound insulating thermoplastic resin film for laminated glass, has a thickness of 10 ⁇ m or more, and has a thermomechanical analysis. (TMA) device, the elongation rate of the sound insulating thermoplastic resin film is 6.8% or more when the measurement temperature is 25 ° C. and the load application rate is 10 mN / min and the applied load is 200 mN or more. It is characterized by being. By setting the elongation rate to 6.8% or more, the flexibility can be improved to the same level as or higher than that of a commercially available thermoplastic resin film, and therefore the sound insulation performance when used for laminated glass is improved. Is possible. Preferably, it may be 6.8 to 10.0%.
  • the sound insulating thermoplastic resin film may be one in which the plasticizer is evenly dispersed in the film, or one in which the plasticizer is non-uniformly dispersed.
  • the sound insulating thermoplastic resin film and an arbitrary layer may be laminated and used as a film for laminated glass.
  • a sound insulating thermoplastic resin film having a thickness of 380 to 760 ⁇ m is used, and particularly an arbitrary layer is used. It may be used as a single film having no boundary surface without being laminated. Further, a plurality of sound insulating thermoplastic resin films having a thickness of 10 to 50 ⁇ m may be laminated.
  • the inventors of the present invention have conducted a study and found that the above-mentioned sound-insulating thermoplastic resin film shows a weight reduction rate after 0.5 to 1200 hours from the start of standing when left in an environment of 20 to 30 ° C. , 0.01 to 30%. Therefore, the sound-insulating thermoplastic resin film may have a weight loss rate at 20 to 30 ° C. of 0.01 to 30%, preferably 0.1 to 20%.
  • the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure can be obtained by impregnating the thermoplastic resin film with a plasticizer, and specifically, the above-mentioned "2: Laminated glass". It can be obtained by the "penetration step” of "Production method”. Moreover, it is preferable to perform the above-mentioned (wiping step) after the permeation step.
  • thermoplastic resin films and plasticizers that can be used as materials for the sound insulating thermoplastic resin film.
  • thermoplastic resin film is an adhesive material that adheres and integrates two glass plates, and a film obtained by molding a thermoplastic resin into a film shape can be used.
  • the thermoplastic resin film is formed into a film shape in a state where a plastic as a raw material is mixed with a plasticizer.
  • the sound insulating thermoplastic resin film is obtained by further permeating the thermoplastic resin film as described above with a plasticizer used for the resin.
  • thermoplastic resin polyvinyl butyral resin
  • the film used may be a commercially available film containing the above resin, for example, Saflex standard clear PVB (Eastman Chemical, RF41), S-LEC Film clear PVB (Sekisui Chemical Co., Ltd., HI RZN-10). And so on. Further, it is also applicable to a heat-shielding polyvinyl butyral resin obtained by containing heat-shielding fine particles in a polyvinyl butyral resin and a wedge-shaped polyvinyl butyral resin used for head-up display applications.
  • thermoplastic resin film may be a commercially available one as described above, and is not particularly limited. Therefore, the content of the plasticizer is also not particularly limited, but it is common to have about 10 to 70 parts, more preferably 30 to 45 parts (phr) of the plasticizer per 100 parts of the resin.
  • the thickness of the thermoplastic resin film is not particularly limited, but generally it is considered that the thicker it is, the higher the rigidity becomes, and the thicker it is, the more the laminated glass tends to deteriorate the visibility.
  • a thickness of 10 to 1500 ⁇ m is preferable because it has a sound insulating property after the plasticizer is infiltrated, and the visibility of the laminated glass is not impaired.
  • a general thermoplastic resin film used for laminated glass has a thickness of 380 to 760 ⁇ m, and in the case of the sound insulating thermoplastic resin film according to at least some embodiments of the present disclosure, the sound insulating material is within the above range. It is possible to improve performance.
  • the "plasticizer used in the resin" used in the above-mentioned infiltration step may be a material capable of entering the gaps of the thermoplastic resin or the network of the resin and imparting flexibility to the resin, It is not particularly limited.
  • a material capable of entering the gaps of the thermoplastic resin or the network of the resin and imparting flexibility to the resin It is not particularly limited.
  • a laminated glass according to at least some embodiments of the present disclosure is a laminated glass in which at least two glass plates are integrated via a sound insulating thermoplastic resin film, and the sound insulating thermoplastic resin film is included.
  • the maximum loss coefficient at 0.1 is 0.1 or more.
  • the laminated glass according to the embodiment the calculated value of the sound transmission loss at 2000 Hz or higher is 32 dB or higher even in the range of -10 ° C or higher and lower than 10 ° C.
  • the laminated glass according to at least some embodiments of the present disclosure may have a sound transmission loss of 32 dB or more in a range of ⁇ 10 ° C. or higher and lower than 10 ° C.
  • the above laminated glass uses a sound insulating thermoplastic resin film having suitable flexibility even when the temperature is low, it absorbs the impact when an object collides with it. Since it is easy, it can be suitably used as a safety glass for automobiles.
  • Glass plate The type of glass plate used for the above laminated glass is not particularly limited.
  • expanded crystallized glass, zero expanded crystallized glass, or the like it is possible to use expanded crystallized glass, zero expanded crystallized glass, or the like.
  • colored glass that absorbs ultraviolet rays, infrared rays, and the like may be used.
  • the thickness of the glass plate is not particularly limited, but when used as architectural window glass, it may be 3 to 25 mm which is generally used. When used as a window glass for automobiles, it may be about 0.1 to 3 mm.
  • the shape of the glass plate may be at least two glass plates that can be stacked without a gap, and may be flat glass, bent glass, or glass having irregularities.
  • a building window glass it is common to use a flat glass plate having no curved surface.
  • a bent glass plate having a curved surface When used as a window glass for automobiles, it is preferable to use a bent glass plate having a curved surface.
  • the bent glass plate may have any desired shape. For example, when it is used as a front glass of a vehicle, a glass plate preliminarily bent three-dimensionally is widely used.
  • the standing time (hereinafter, also referred to as “penetration time”) was set to 2 h, 4 h, 8 h, 24 h, and 112 h, respectively, and the surface was wiped if necessary after the penetration.
  • peeling time As the film B, Saflex standard clear PVB (RF41 manufactured by Eastman Chemical) was used.
  • Film C As the film C, Saflex premium acoustic PVB (QF51 manufactured by Eastman Chemical) was used.
  • thermomechanical analysis (TMA) device (Thermo Plus TMA8310 manufactured by Rigaku) was used to set the measurement temperature to 25 ° C. and the applied load to 10 mN / min to apply a load to the measurement sample. It was done by adding. The elongation percentage when the applied load reached 200 mN was measured and taken as the elongation percentage of each film. Further, regarding the film A, the thickness of the film at this time was also measured.
  • the weight reduction rate is defined as the difference between the weight at the time of 20h and the weight at each time with respect to the weight at the time of 20h, immediately after leaving the sample in a constant temperature bath at 60 ° C for 20h.
  • the ratio was calculated.
  • the weight of the thermoplastic resin film before applying the plasticizer was 0.27 g, and the weight after 20 hours was 0.37 g for the sample placed in the 20 ° C. constant temperature bath, and the sample placed in the 30 ° C. constant temperature bath. was 0.38g.
  • the obtained results are shown in FIG.
  • Example 1 Saflex standard clear PVB (RF41 manufactured by Eastman Chemical Co., Ltd.) was cut to a size slightly larger than 250 mm ⁇ 10 mm, and the weight (a) was measured with an electronic balance (PE3600 manufactured by METTLER TOLEDO). Next, a plasticizer (triethylene glycol bis2-ethylhexanate 90 + ⁇ %, manufactured by ALFA Acer, H54406) was applied to both sides of the film, and left in a constant temperature bath at 60 ° C for 30 hours to obtain a sound insulating thermoplastic resin film. It produced (penetration process).
  • the plasticizer attached to the film surface is wiped with a non-woven fabric (wiping step), and the weight (b) of the sound-insulating thermoplastic resin film is measured by an electronic balance to determine the permeation amount (weight) of the plasticizer.
  • B) -Weight (a)) was calculated.
  • the sound insulating thermoplastic resin film was laminated (lamination step) between two soda lime glass plates (250 mm ⁇ 10 mm, plate thickness 2 mm), and the weight of the obtained laminate was measured by an electronic balance.
  • the weight (c) was calculated by subtracting the weight of the glass plate from the measured value.
  • the laminate was placed in an autoclave and subjected to deaeration treatment with a vacuum bag (deaeration step), followed by pressure / heat treatment at about 90 ° C. and 0.25 MPa for about 10 minutes (pre-bonding step).
  • pre-bonding step was applied.
  • the weight of the laminated glass was measured by an electronic balance, and the weight of the glass plate was subtracted from the measured value to calculate the weight (d).
  • the laminated glass was put into an autoclave and subjected to pressure / heat treatment at about 135 ° C. and 1.3 MPa for about 30 minutes to integrate the laminated glass (lamination step).
  • the weight of the obtained laminated glass was measured by an electronic balance, and the weight of the glass plate was subtracted from the measured value to calculate the weight (e). In addition, the weight reduction rate before and after the combining step was calculated from the obtained values. After the measurement, the film protruding from the edge of the laminated glass was cut off.
  • Example 1 A laminated glass was obtained in the same manner as in Example 1 except that the infiltration step and the wiping step were not performed, and the weight was not measured after each step.
  • Comparative example 2 A laminated glass was obtained in the same manner as in Comparative Example 1 except that Saflex premium acoustic PVB (QF51, manufactured by Eastman Chemical) was used as the thermoplastic resin film.
  • Saflex premium acoustic PVB QF51, manufactured by Eastman Chemical
  • Example 1 The respective weights measured in Example 1 were (a) 2.8 g, (b) 4.7 g, (c) 4.7 g, (d) 4.7 g, and (e) 4.4 g. From the above, the permeation amount (weight (b) -weight (a)) of the plasticizer in Example 1 was 1.9 g. It was also found that the weight (d) after the pre-bonding step did not significantly change from the weight (c) after the lamination, and that the plasticizer was not significantly reduced after the degassing step and the pre-bonding step.
  • the weight reduction rate after the combining step ⁇ (weight (b) -weight (e)) / weight (b) ⁇ 100 ⁇ was 6.4% with respect to the weight (b) immediately after the infiltration step
  • the weight loss rate before and after the process ⁇ (weight (d) -weight (e)) / weight (d) ⁇ 100 ⁇ was 6.4%. Since the reduction amount was smaller than the total amount of the plasticizer used in the permeation step, it was found that the plasticizer permeated into the thermoplastic resin film remained in the film even after the combining step.
  • Table 2 shows the maximum loss coefficient at a frequency of 2000 Hz and -10 to 20 ° C.
  • Example 1 From Table 2, it was found that the maximum loss coefficient of Example 1 at a frequency of 2000 Hz and ⁇ 10 to 20 ° C. is higher than that of Comparative Example 1 using a thermoplastic resin film not impregnated with a plasticizer. . It is considered that the larger the maximum loss coefficient, the higher the sound insulation performance. Further, the value was smaller than that of Comparative Example 2 using a film conventionally used as a sound insulating PVB film.
  • Example 1 the calculated value of the sound transmission loss at ⁇ 10 ° C. to 20 ° C. was 2000 dB or higher at 2000 Hz or higher.
  • Comparative Example 1 the calculated value of the sound transmission loss at ⁇ 10 to 10 ° C. was 30 dB or less. That is, it has been shown that the method of the present disclosure improves the sound insulation performance at low temperatures as compared with the case where the plasticizer is not permeated.
  • Comparative Example 2 the lowest sound transmission loss value at ⁇ 10 ° C. at 2000 Hz was 31 dB.
  • the technique of the present disclosure was able to improve the flexibility of the thermoplastic resin film in a simpler method than the conventional technique. Furthermore, by manufacturing a laminated glass using the thermoplastic resin film obtained by using the method, it becomes possible to improve the sound insulation performance of the laminated glass.

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un verre feuilleté qui comprend l'intégration d'au moins deux feuilles de verre par l'intermédiaire d'un film de résine thermoplastique, le film de résine thermoplastique étant préparé par mélange d'une résine de départ avec un plastifiant suivi de la mise en forme du mélange dans un film. Ce procédé de fabrication d'un verre feuilleté comprend : une étape de perméation pour imprégner davantage le plastifiant utilisé pour la résine dans le film de résine thermoplastique à partir de la surface du film de résine thermoplastique pour donner un film de résine thermoplastique d'isolation sonore; une étape de stratification pour, après l'étape de perméation, stratifier le film de résine thermoplastique d'isolation sonore entre au moins deux plaques de verre pour donner un stratifié; une étape de dégazage pour, après l'étape de stratification, dégazer les espaces entre les couches individuelles du stratifié; et une étape de liaison pour chauffer le stratifié dégazé sous une pression élevée pour ainsi intégrer celui-ci.
PCT/JP2019/038879 2018-10-22 2019-10-02 Procédé de fabrication de verre feuilleté WO2020085021A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57209861A (en) * 1981-06-01 1982-12-23 Ppg Industries Inc Manufacture of laminated glass window
JP2003503237A (ja) * 1999-06-25 2003-01-28 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 層間の制御された結合を有する合せガラス用中間膜複合構造体および中間膜構造体の製造方法
JP2013006731A (ja) * 2011-06-23 2013-01-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JP2015147725A (ja) * 2014-02-05 2015-08-20 クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツングＫｕｒａｒａｙ Ｅｕｒｏｐｅ ＧｍｂＨ 可塑剤を含有するポリビニルアセタールシートと、可塑剤含分が少ないポリビニルアセタールシートとを有する層状体から、合わせガラス積層体を製造する方法
WO2016052673A1 (fr) * 2014-09-30 2016-04-07 積水化学工業株式会社 Film de résine pour le collage à une plaque de verre, stratifié contenant une plaque de verre et procédé de production d'un film de résine pour le collage à une plaque de verre

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57209861A (en) * 1981-06-01 1982-12-23 Ppg Industries Inc Manufacture of laminated glass window
JP2003503237A (ja) * 1999-06-25 2003-01-28 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 層間の制御された結合を有する合せガラス用中間膜複合構造体および中間膜構造体の製造方法
JP2013006731A (ja) * 2011-06-23 2013-01-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JP2015147725A (ja) * 2014-02-05 2015-08-20 クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツングＫｕｒａｒａｙ Ｅｕｒｏｐｅ ＧｍｂＨ 可塑剤を含有するポリビニルアセタールシートと、可塑剤含分が少ないポリビニルアセタールシートとを有する層状体から、合わせガラス積層体を製造する方法
WO2016052673A1 (fr) * 2014-09-30 2016-04-07 積水化学工業株式会社 Film de résine pour le collage à une plaque de verre, stratifié contenant une plaque de verre et procédé de production d'un film de résine pour le collage à une plaque de verre

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