JP2016172324A - Thermoplastic resin film and glazing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin film which has high rigidity due to high modulus of tensile elasticity, and also has high sound insulating properties in a high-frequency region.SOLUTION: A thermoplastic resin film has a plurality of first thermoplastic resin layers containing a thermoplastic resin and a plurality of second thermoplastic resin layers containing a thermoplastic resin, and has a multilayer structure in which the first thermoplastic resin layers and the second thermoplastic resin layers have multilayer structures layered in a thickness direction. The total of the number of layers of the first thermoplastic resin layers and the second thermoplastic resin layers in the thickness direction is 5 or more layers, the thermoplastic resin in the first thermoplastic resin is an ethylene-vinyl acetate copolymer, and modulus of tensile elasticity in one layer of the second thermoplastic resin layer is 1 GPa or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermoplastic resin film in which a plurality of layers containing a thermoplastic resin are laminated. The present invention also relates to glazing using the thermoplastic resin film as an intermediate film for glazing.

  Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc. The laminated glass is manufactured, for example, by sandwiching an interlayer film for laminated glass between a pair of glass plates.

  In recent years, in order to reduce the weight of laminated glass, it has been studied to reduce the thickness of the laminated glass. However, when the thickness of the laminated glass is reduced, the sound insulation and rigidity are lowered.

  When laminated glass using thin glass is used for a windshield of a car, etc., there is a problem that sufficient sound insulation cannot be obtained for sounds in the range of about 5000 Hz such as wind noise or wiper driving sound. is there.

  Therefore, it has been studied to improve the sound insulation of the laminated glass by changing the material of the interlayer film.

  For example, in the following Patent Document 1, 100 parts by mass of a polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and at least one metal salt of an alkali metal salt and an alkaline earth metal salt is 0.001 to 1. A sound insulation layer containing 0.0 part by mass and a plasticizer exceeding 30 parts by mass is disclosed. This sound insulation layer can be used as a single layer as an intermediate film or laminated with other layers as a multilayer intermediate film.

  Patent Document 2 below discloses an intermediate film in which two or more layers having different Young's moduli are stacked. Examples 1 and 2 of Patent Document 2 describe a multilayer intermediate film in which two layers A and B are stacked in a stacked structure of A / B / A.

JP 2007-070200 A JP 2003-192402 A

  In the laminated glass using the interlayer film described in Patent Document 1, the sound insulation can be improved to some extent, but further improvement of the sound insulation is required.

  In the interlayer film described in Patent Document 1, it is difficult to sufficiently improve the sound insulation in a high frequency range of about 5000 Hz, particularly in laminated glass using thin glass, and the rigidity can be sufficiently increased. Have difficulty. Conventionally, in laminated glass using thin glass, it is difficult to achieve both rigidity and sound insulation in a high frequency range at a high level.

  An object of the present invention is to provide a thermoplastic resin film having high rigidity due to high tensile elastic modulus and high sound insulation in a high frequency range. Another object of the present invention is to provide glazing using the thermoplastic resin film as an intermediate film for glazing.

  According to a wide aspect of the present invention, the first thermoplastic resin includes a plurality of first thermoplastic resin layers including a thermoplastic resin and a plurality of second thermoplastic resin layers including a thermoplastic resin. The layer and the second thermoplastic resin layer have a multilayer structure laminated in the thickness direction, and the number of layers in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer is Total is 5 layers or more, the thermoplastic resin in the first thermoplastic resin layer is an ethylene-vinyl acetate copolymer, and the tensile elastic modulus in one layer of the second thermoplastic resin layer A thermoplastic resin film having a thickness of 1 GPa or more is provided.

  In a specific aspect of the thermoplastic resin film according to the present invention, a ratio of a total thickness of the first thermoplastic resin layer to a total thickness of the second thermoplastic resin layer is 1 or more.

  In a specific aspect of the thermoplastic resin film according to the present invention, the total number of laminated layers in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer is 10 layers or more. In a specific aspect, the total number of the layers is 160 layers or more.

  On the specific situation with the thermoplastic resin film which concerns on this invention, the said thermoplastic resin film is a said 1st thermoplastic resin layer, a said 2nd thermoplastic resin layer, a said 1st thermoplastic resin layer, and the said The second thermoplastic resin layer has a portion laminated in this order.

  In a specific aspect of the thermoplastic resin film according to the present invention, the number of the second thermoplastic resin layers is three or more.

  The thermoplastic resin film according to the present invention is used to obtain glazing, and is used by being disposed between the first glazing member and the second glazing member, and the thermoplastic resin film is an intermediate film for glazing. Preferably there is. The thickness of the first glazing member is preferably 1.5 mm or less. The glazing is a laminated glass, the first glazing member is a first laminated glass member, the second glazing member is a second laminated glass member, and the intermediate film for glazing is an intermediate for laminated glass A membrane is preferred.

  According to a wide aspect of the present invention, the glazing member includes the first glazing member, the second glazing member, and the intermediate film for glazing that is the thermoplastic resin film described above, and the first glazing member and the second glazing member are provided. A glazing is provided in which the glazing interlayer is disposed between the glazing members.

  The first glazing member is a first laminated glass member, the second glazing member is a second laminated glass member, the glazing interlayer is a laminated glass interlayer, and the glazing is laminated. It is glass.

  The thermoplastic resin film according to the present invention includes a plurality of first thermoplastic resin layers containing a thermoplastic resin and a plurality of second thermoplastic resin layers containing a thermoplastic resin, and the first thermoplastic resin The resin layer and the second thermoplastic resin layer have a multilayer structure laminated in the thickness direction, and the number of laminates in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer. The thermoplastic resin in the first thermoplastic resin layer is an ethylene-vinyl acetate copolymer, and the elastic modulus of the second thermoplastic resin layer is one layer. Since the tensile elastic modulus of the material is 1 GPa or more, the rigidity can be increased by a high tensile elastic modulus, and the sound insulation in a high frequency region of about 5000 Hz can be improved.

FIG. 1 is a schematic cross-sectional view showing a thermoplastic resin film according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a laminated glass provided with the thermoplastic resin film shown in FIG. FIG. 3 is a schematic diagram for explaining the manufacturing process of the thermoplastic resin film. FIG. 4 is a schematic diagram for explaining a manufacturing process of the thermoplastic resin film. FIG. 5 is a schematic diagram for explaining a manufacturing process of the thermoplastic resin film. FIG. 6 is a schematic diagram for explaining the manufacturing process of the thermoplastic resin film.

  Details of the present invention will be described below.

  The thermoplastic resin film according to the present invention includes a plurality of first thermoplastic resin layers containing a thermoplastic resin and a plurality of second thermoplastic resin layers containing a thermoplastic resin. The thermoplastic resin film according to the present invention has a multilayer structure in which the first thermoplastic resin layer and the second thermoplastic resin layer are laminated in the thickness direction. The total number of laminated layers in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer is 5 or more.

  In the thermoplastic resin film according to the present invention, the thermoplastic resin in the first thermoplastic resin layer is preferably different from the thermoplastic resin in the second thermoplastic resin layer. The thermoplastic resin in the first thermoplastic resin layer is an ethylene-vinyl acetate copolymer. The tensile elastic modulus in one layer of the second thermoplastic resin layer is 1 GPa or more.

  In the present invention, since the above-described configuration is provided, a high tensile elastic modulus can be ensured derived from the second thermoplastic resin layer, and thus rigidity can be increased. Furthermore, in the present invention, since the above-described configuration is provided, a large number of specific first thermoplastic resin layers and specific second thermoplastic resin layers are laminated, so that the rigidity can be increased. Not only can the sound insulation in a high frequency range be improved. Conventionally, it has been difficult to achieve both rigidity and sound insulation in a high frequency range at a high level, but the present invention achieves both rigidity and sound insulation in a high frequency range at a high level. Can do. Furthermore, in this invention, the thermoplastic resin film and laminated glass suitable as an intermediate film for laminated glasses are obtained, without requiring a complicated process.

  Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing a thermoplastic resin film according to an embodiment of the present invention. Hereinafter, the thermoplastic resin film may be abbreviated as a resin film.

  A resin film 1 shown in FIG. 1 is a thermoplastic resin film. The resin film 1 has a plurality of thermoplastic resin layers 11. The resin film 1 includes a plurality of first thermoplastic resin layers 11A and a plurality of second thermoplastic resin layers 11B. The first thermoplastic resin layer 11 </ b> A and the second thermoplastic resin layer 11 </ b> B are laminated in the thickness direction of the resin film 1. In the present embodiment, the first thermoplastic resin layers 11 </ b> A and the second thermoplastic resin layers 11 </ b> B are alternately stacked in the thickness direction of the resin film 1. The resin film 1 has a multilayer structure.

  The first thermoplastic resin layer 11A contains a thermoplastic resin. The second thermoplastic resin layer 11B includes a thermoplastic resin. The total number of laminated layers in the thickness direction of the first thermoplastic resin layer 11A and the second thermoplastic resin layer 11B is five or more.

  The first thermoplastic resin layer 11A includes an ethylene-vinyl acetate copolymer. The second thermoplastic resin layer 11B includes a thermoplastic resin. The thermoplastic resin in the second thermoplastic resin layer 11B is appropriately selected so that the tensile elastic modulus in one layer of the second thermoplastic resin layer 11B is 1 GPa or more. For this reason, the thermoplastic resin contained in the second thermoplastic resin layer 11B is usually different from the ethylene-vinyl acetate copolymer.

  The ratio (T1 / T2) of the total thickness (T1) of the first thermoplastic resin layer to the total thickness (T2) of the second thermoplastic resin layer is preferably 0.1 or more, more preferably Is 0.3 or more, more preferably 0.5 or more, particularly preferably 1 or more, preferably 20 or less, more preferably 10 or less, still more preferably 6 or less, particularly preferably 5 or less, and most preferably 3 or less. is there. When the ratio is equal to or higher than the lower limit, particularly when the ratio is equal to or higher than 1, the sound insulation in a high frequency region is effectively enhanced. When the ratio is not more than the upper limit, the rigidity is effectively increased.

  The ratio (L1 / L2) of the total number of laminated layers (L1) of the first thermoplastic resin layers to the total number of laminated layers (L2) of the second thermoplastic resin layers is preferably 0.9 or more, more Preferably it is 1 or more, preferably 1.2 or less, more preferably 1.1 or less.

  The number of the first thermoplastic resin layers is preferably 3 or more, more preferably 5 or more. The number of the second thermoplastic resin layers is preferably 3 or more, more preferably 5 or more.

  The tensile modulus of elasticity in one layer of the first thermoplastic resin layer is preferably less than 1 GPa, more preferably 500 MPa or less, still more preferably 100 MPa or less.

  The tensile elastic modulus in one layer of the second thermoplastic resin layer is 1 GPa or more, preferably 2 GPa or more, more preferably 3 GPa or more. When the tensile modulus is equal to or higher than the lower limit, the rigidity is effectively increased. It is preferable that the tensile elastic modulus in one layer of the first thermoplastic resin layer is different from the tensile elastic modulus in one layer of the second thermoplastic resin layer.

  The tensile elastic modulus in one layer of the first thermoplastic resin layer is measured according to the following procedure. The composition for forming the first thermoplastic resin layer is extruded as a single layer using an extruder to obtain a single layer resin film having an average thickness of 760 μm. Using a sharp razor, a test piece sampled in a strip shape having a width of 10 mm and a length of 150 mm of the obtained single layer resin film is prepared. About this test piece, a tensile elasticity modulus is measured at 23 degreeC by the method based on ASTM D882: 2012 using the universal testing machine RTC-1310A by Orientec. By the same procedure, the tensile elastic modulus in one layer of the second thermoplastic resin is also measured.

  The tensile elastic modulus of the thermoplastic resin film is preferably 50 MPa or more, more preferably 100 MPa or more.

  In the thermoplastic resin film according to the present invention, the total number of laminated layers in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer is 10 layers or more, preferably 40 layers or more. More preferably, it is 160 layers or more, More preferably, it is 320 layers or more. Although the sum total of the said lamination | stacking number is not specifically limited, For example, it is 100,000 or less layers from a practical surface.

  The thermoplastic resin film includes a portion in which the first thermoplastic resin layer, the second thermoplastic resin layer, the first thermoplastic resin layer, and the second thermoplastic resin layer are laminated in this order. It is preferable to have a plurality of portions.

  The first thermoplastic resin layer (A) and the second thermoplastic resin layer (B) may be alternately laminated as A / B / A / B. The same thermoplastic resin layer may overlap like / A / A / B / A / ... and A / B / B / A / B / B /. Further, a resin layer other than the first thermoplastic resin layer and the second thermoplastic resin layer may be laminated. From the viewpoint of ease of bonding when making a laminated glass, the one surface layer in the thermoplastic resin layer is preferably the first thermoplastic resin layer, and the other surface layer is the first heat layer. A plastic resin is preferred. One or two of the first thermoplastic resin layers are preferably located on the outermost surface in the thermoplastic resin film.

  The thickness of each layer of the second thermoplastic resin layer is preferably 11 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, and particularly preferably 2 μm or less. When the thickness of each one layer of the second thermoplastic resin layer is not more than the above upper limit, the first thermoplastic resin layer becomes more difficult to break when the second thermoplastic resin layer breaks, The resin film is more difficult to break. The thickness of each of the second thermoplastic resin layers is preferably 0.01 μm or more.

  The thermoplastic resin film may be stretched. The stretching temperature is preferably 50 ° C or higher, more preferably 60 ° C or higher, still more preferably 64 ° C or higher, preferably lower than 90 ° C, more preferably lower than 70 ° C, still more preferably lower than 66 ° C. When the stretching temperature is equal to or higher than the above lower limit, shrinkage due to the elasticity of the resin hardly occurs, and molecular orientation is effectively expressed. When the stretching temperature is not more than the above upper limit or less than the above upper limit, it becomes difficult to deform so that the resin flows, and molecular orientation is effectively expressed. The draw ratio is preferably 1.5 times or more, more preferably 2 times or more, and further preferably 3 times or more.

  When the thermoplastic resin film is an interlayer film for laminated glass, the penetration resistance of the laminated glass provided with the interlayer film is increased by increasing the tear strength of the interlayer film. Therefore, it becomes possible to use a glass plate that is thinner than a conventional glass plate while maintaining equivalent penetration resistance performance, in order to obtain laminated glass, and the laminated glass can be reduced in weight.

  The thermoplastic resin film according to the present invention may be used as a composite film by laminating another thermoplastic resin film on the surface.

  The surface of the thermoplastic resin film may be embossed. Examples of the embossing method include an embossing roll method and a lip embossing method. Among these, the embossing roll method is preferable because embossing can be performed so that a certain uneven pattern is quantitatively formed.

  From the viewpoint of further improving the adhesion to the laminated glass member and further improving the penetration resistance of the laminated glass, the ten-point average roughness Rz of the outer surface of the embossed resin film is preferably 0. .1 μm or more, more preferably 1 μm or more, preferably 100 μm or less, more preferably 50 μm or less. The ten-point average roughness Rz is measured according to JIS B0601: 1994.

  Hereinafter, the detail of each component contained in the resin film which concerns on this invention is demonstrated.

(Thermoplastic resin contained in the thermoplastic resin layer)
The thermoplastic resin in the first thermoplastic resin layer is an ethylene-vinyl acetate copolymer. As for the said ethylene-vinyl acetate copolymer, only 1 type may be used and 2 or more types may be used together.

  The ethylene-vinyl acetate copolymer may be a non-crosslinked ethylene-vinyl acetate copolymer or a crosslinked ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer includes a modified resin of ethylene-vinyl acetate such as a saponified ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer can be obtained by a known method.

  The vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 35% by mass or less. More preferably, it is 33% by mass or less. If the vinyl acetate content is not less than the above lower limit and not more than the upper limit, the rigidity of the resulting thermoplastic resin film can be further enhanced. From the viewpoint of further increasing the transparency of the thermoplastic resin film, the vinyl acetate content preferably exceeds 19% by mass. The vinyl acetate content is measured according to JIS K6730 “Ethylene / vinyl acetate resin test method”.

  The thermoplastic resin in the second thermoplastic resin layer is appropriately selected so that the tensile elastic modulus in one layer of the second thermoplastic resin layer is 1 GPa or more. As the thermoplastic resin in the second thermoplastic resin layer, polystyrene, acrylic resin, phenol resin, vinyl chloride resin, AS resin, polycarbonate, polyester, ABS resin, acetal resin, polyamide resin, cellulose acetate, MS resin, MBS Resin, SB resin, ionomer resin and the like. Among these, acrylic resin and ionomer resin are preferable as the thermoplastic resin contained in the second thermoplastic resin layer because the tear resistance of the obtained thermoplastic resin film is further improved. Examples of the acrylic resin include polymethyl methacrylate (PMMA). Examples of the ionomer resin include an ethylene-methacrylic acid copolymer resin. As for the thermoplastic resin in a 2nd thermoplastic resin layer, only 1 type may be used and 2 or more types may be used together.

(Other ingredients)
Each layer in the resin film is made of an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture-proofing agent, a fluorescent whitening agent, and an infrared ray as necessary. An additive such as an absorbent may be included.

(Method for producing thermoplastic resin film)
Examples of the method for producing the thermoplastic resin film include a wet lamination method, a dry lamination method, an extrusion coating method, a multilayer melt extrusion method, a hot melt lamination method, and a heat lamination method.

  Since a thermoplastic resin film that is easy to manufacture and excellent in tensile strength can be obtained, the resin film is preferably obtained by a multilayer melt extrusion method. Examples of the multilayer melt extrusion method include a multi-manifold method and a feed block method.

(Glazing)
The thermoplastic resin film according to the present invention is suitably used for obtaining glazing. The thermoplastic resin film according to the present invention is preferably used by being disposed between the first glazing member and the second glazing member. The thermoplastic resin film according to the present invention is preferably an intermediate film for glazing.

  The glazing according to the present invention includes a first glazing member, a second glazing member, and an intermediate film for glazing that is the thermoplastic resin film. The interlayer film for glazing is disposed between the first glazing member and the second glazing member.

  The first glazing member is preferably a first laminated glass member. The second glazing member is preferably a second laminated glass member. It is preferable that the said intermediate film for glazing is an intermediate film for laminated glasses.

  The thermoplastic resin film according to the present invention is suitably used for obtaining laminated glass. The thermoplastic resin film according to the present invention is preferably used by being disposed between the first laminated glass member and the second laminated glass member. The thermoplastic resin film according to the present invention is preferably an interlayer film for laminated glass.

  When the glazing is a laminated glass, the laminated glass includes a first laminated glass member, a second laminated glass member, and an interlayer film for laminated glass that is the thermoplastic resin film. The interlayer film for laminated glass is disposed between the first laminated glass member and the second laminated glass member.

  FIG. 2 is a schematic cross-sectional view showing glazing provided with the thermoplastic resin film shown in FIG.

  The glazing 51 shown in FIG. 2 includes a first glazing member 52, a second glazing member 53, and the resin film 1. The resin film 1 is disposed between the first glazing member 52 and the second glazing member 53 and is sandwiched. The first glazing member 52 is laminated on the first surface 1 a of the resin film 1. The second glazing member 53 is laminated on the second surface 1 b of the resin film 1. Therefore, the glazing 51 is configured by laminating the first glazing member 52, the resin film 1, and the second glazing member 53 in this order.

  Examples of the glazing member include a glass plate, a polycarbonate film, a cycloolefin film, an acrylic film, and a polyester film.

  Laminated glass can be obtained by using at least one glass plate as the glazing member. Laminated glass includes not only laminated glass in which a resin film is sandwiched between two glass plates, but also laminated glass in which a resin film is sandwiched between a glass plate and a PET film or the like. Laminated glass is a laminated body provided with a glass plate, and preferably at least one glass plate is used. Each of the first laminated glass member and the second laminated glass member is preferably a glass plate or a PET film, and the laminated glass is glass as at least one of the first laminated glass member and the second laminated glass member. It is preferable to provide a plate.

  Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, netted plate glass, and lined plate glass. The organic glass is a synthetic resin glass substituted for inorganic glass. Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

  The thickness of the glazing member is preferably 0.5 mm or more, more preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. Moreover, when a glazing member is a glass plate, the thickness of this glass plate becomes like this. Preferably it is 1 mm or more, Preferably it is 3 mm or less. When the glazing member is a PET film, the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.

  The use of the thermoplastic resin film according to the present invention can sufficiently enhance rigidity and sound insulation in a high frequency range. Therefore, the thickness of the glazing member, particularly the thickness of the glass plate, is preferably 2 mm or less, more preferably. Is 1.8 mm or less, more preferably 1.5 mm or less, still more preferably 1 mm or less, still more preferably 0.8 mm or less, and particularly preferably 0.7 mm or less. When such thin glazing and thin glass plate are used, rigidity and sound insulation generally tend to be low, but by using the thermoplastic resin film according to the present invention, rigidity and sound insulation in a high frequency range are reduced. Both can be achieved at a high level.

  Only the thickness of the first glazing member may be not more than the above upper limit. It is preferable that the thickness of both the first glazing member and the second glazing member is not more than the above upper limit.

  The manufacturing method of the said glazing is not specifically limited. For example, the first glazing member and the resin are sandwiched between a first glazing member and a second glazing member, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure. Air remaining between the membrane and between the first glazing member and the resin membrane is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, glazing can be obtained. In the case where embossing is formed on the outer surface of the second layer opposite to the laminate side, between the first glazing member and the intermediate film and between the second glazing member and the intermediate film The air remaining therebetween can be degassed more effectively.

  Glazing can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Glazing can be used in addition to these. The glazing is preferably architectural or vehicle glazing, and more preferably vehicle glazing. Glazing can be used for the windshield, side glass, rear glass or roof glass of automobiles. In addition, the glazing can be used as a functional glazing such as a sound insulating glazing imparted with a sound insulating property by being laminated with another inorganic film or an organic film.

  The haze value of the glazing is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.4% or less. The haze value of glazing can be measured according to JIS K6714. In order to reduce the glazing haze, it is preferable that each layer constituting the resin film does not contain a filler.

  The thermoplastic resin film of the present invention can also be used as a damping material by laminating with a rigid body other than glass, for example, laminating with a metal, an inorganic material, or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples.

Example 1
(1) Production of Thermoplastic Resin Film An ethylene-vinyl acetate copolymer (“Evaflex EV260” manufactured by Mitsui DuPont) was prepared as a resin for forming the first thermoplastic resin layer. As a resin for forming the second thermoplastic resin layer, PMMA (polymethyl methacrylate) (acrylic resin, “Acrypet V001” manufactured by Mitsubishi Rayon Co., Ltd.) was prepared.

  A resin for forming the first thermoplastic resin layer is supplied to the extruder 1 heated to 200 ° C., and the second thermoplastic resin layer is formed in the extruder 2 heated to 200 ° C. Resin for was supplied. At this time, the amount of extrusion per time was set such that the weight ratio between the extruder 1 and the extruder 2 was 6: 1. Each of the molten resin extruded from the extruder 1 and the molten resin extruded from the extruder 2 are alternately laminated via a gear pump, and merged in a field block where 40 layers are laminated together. A laminate 21 was obtained (see FIG. 3). Then, the laminated body 21 was supplied to the square mixer, and the laminated body 22 of 80 layers was obtained (refer FIGS. 4-6). Then, it supplied to the 2nd square mixer and obtained the laminated body of 160 layers. Then, it supplied to the 3rd square mixer, and obtained the laminated body of 320 layers.

  In addition, the square mixer is a flow path that can double the number of layers by dividing the thermoplastic resin that has passed through the flow path having a rectangular cross-section into two by a branch flow path, and stacking and joining them. It is a cylinder which has. In the square mixer, the number of layers is 40 by compressing the flow path in the direction of the arrow X1 so that the 40-layer laminate 21 shown in FIG. 3 is divided into two at the center as shown in FIG. In addition, two compressed products having a thickness of ½ can be obtained. Next, by expanding the flow path in the direction of the arrow X2 as shown in FIG. 5, it is possible to obtain a laminate 22 having 80 layers, which is twice as many as shown in FIG. By repeating the same operation, a 160-layer laminate and a 320-layer laminate can be obtained.

  The 320-layer laminate thus obtained is supplied to a T-die and molded into a sheet shape, and then taken up by a take-up roll to obtain a 320-layer resin film having an overall thickness (average thickness) of 760 μm It was. However, when using for evaluation of an Example and a comparative example, the part of thickness 760 micrometers was selected and sampled.

(2) Production of laminated glass The obtained resin film was cut into a size of 30 cm long × 30 cm wide. Next, an interlayer film was sandwiched between two pieces of green glass (length 30 cm × width 30 cm × thickness 1.1 mm) conforming to JIS R3208 to obtain a laminate. This laminated body is put in a rubber bag, deaerated at a vacuum degree of 2.6 kPa for 20 minutes, transferred to an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum-pressed. Crimped. The pre-pressed laminate was pressed for 20 minutes in an autoclave at 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass.

(Example 2)
320 layers of resin films and laminated glass were obtained in the same manner as in Example 1 except that the amount of extrusion per hour was changed so that the weight ratio between the extruder 1 and the extruder 2 was 3: 1. .

(Example 3)
320 layers of resin films and laminated glass were obtained in the same manner as in Example 1 except that the amount of extrusion per hour was changed so that the weight ratio of the extruder 1 and the extruder 2 was 1: 1. .

(Comparative Example 1)
As a resin for forming the first thermoplastic resin layer, polyvinyl butyral resin (PVB1, average polymerization degree 1700, acetalization degree 69 mol%, acetylation degree 1 mol%, hydroxyl group content 30 mol%, manufactured by Sekisui Chemical Co., Ltd. ) Was prepared. As a resin for forming the second thermoplastic resin layer, polyvinyl butyral resin (PVB2, average polymerization degree 2300, acetalization degree 64 mol%, acetylation degree 13 mol%, hydroxyl group content 23 mol%, manufactured by Sekisui Chemical Co., Ltd. ) Was prepared. Triethylene glycol di-2-ethylhexanoate (3GO) was prepared as a plasticizer.

  The extruder 1 was supplied with 100 parts by mass of the resin for forming the first thermoplastic resin layer and 40 parts by mass of the plasticizer as a composition for forming the first thermoplastic resin layer. The heating temperature of the extruder 1 when supplying the resin for forming the first thermoplastic resin layer is changed to 180 ° C., and the second thermoplastic resin layer is formed in the extruder 2. 100 parts by mass of the resin and 60 parts by mass of the plasticizer were supplied as a composition for forming the second thermoplastic resin layer, and a resin for forming the second thermoplastic resin layer was used. Example 1 except that the heating temperature of the extruder 2 at the time of feeding was changed to 180 ° C., the feed block to be used was changed to a field block laminated in three layers, and the square mixer was not used. Similarly, all A three-layer resin film and laminated glass laminated in the order of the first thermoplastic resin layer / the second thermoplastic resin layer / the first thermoplastic resin layer in the thickness direction in which the thickness (average thickness) is 760 μm. Obtained.

(Comparative Example 2)
As a resin for forming the first thermoplastic resin layer, polyvinyl butyral resin (PVB1, average polymerization degree 1700, acetalization degree 69 mol%, acetylation degree 1 mol%, hydroxyl group content 30 mol%, manufactured by Sekisui Chemical Co., Ltd. ) Was prepared. Triethylene glycol di-2-ethylhexanoate (3GO) was prepared as a plasticizer.

  The extruder 1 was supplied with 100 parts by mass of the resin for forming the first thermoplastic resin layer and 35 parts by mass of the plasticizer as a composition for forming the first thermoplastic resin layer. In the same manner as in Example 1 except that the heating temperature of the extruder 1 at the time of supplying the resin for forming the first thermoplastic resin layer was changed to 180 ° C., the 320-layer resin film and the laminate were combined. Glass was obtained.

(Comparative Example 3)
An ethylene-vinyl acetate copolymer (“Evaflex EV260” manufactured by Mitsui DuPont) was prepared. The resin is supplied to an extruder heated to 200 ° C., supplied to a T-die via a gear pump, formed into a sheet shape, taken up by a take-up roll, and a single-layer resin film having an average thickness of 760 μm and A laminated glass was obtained.

(Evaluation)
(1) Overall thickness The thickness of the thermoplastic resin film (total thickness of the first thermoplastic resin layer and the second thermoplastic resin layer) was measured using a micrometer MCD130-25 manufactured by Niigata Seiki Co., Ltd. It measured by the method based on K7127: 1999.

(2) Thickness ratio between the first layer and the second layer (T1 / T2)
The thickness of each layer was measured using a digital microscope VHX-2000 manufactured by Keyence Corporation at the center in the width direction of the cross section obtained by cutting the center of the resin film with a sharp razor. The ratio (T1 / T2) of the total thickness (T1) of all the first thermoplastic resin layers to the total thickness (T2) of all the second thermoplastic resin layers was determined.

(3) Tensile elastic modulus of the first thermoplastic resin layer and the second thermoplastic resin layer Using a sharp razor, a test piece sampled in a strip shape having a width of 10 mm and a length of 150 mm was prepared. About this test piece, the tensile elastic modulus was measured at 23 degreeC by the method based on ASTMD882: 2012 using the universal testing machine RTC-1310A by Orientec. The tensile elastic modulus of the single layer resin film of Comparative Example 3 (corresponding to the first resin layer in Examples 1 to 3) was 11 MPa. The tensile elastic moduli of the first thermoplastic resin layers in Comparative Examples 1 and 2 and Examples 1 to 3 and the second thermoplastic resin layers in Comparative Examples 1 and 2 are the first in Comparative Examples 1 and 2, respectively. A composition for forming a thermoplastic resin layer of Example 1, a composition or a resin for forming a second thermoplastic resin layer in Examples 1 to 3 and Comparative Examples 1 and 2, using an extruder. Then, a single layer resin film having an average thickness of 760 μm was prepared, and then measured by the same measurement procedure using the obtained single layer resin film.

(4) Tensile elastic modulus of thermoplastic resin film Using a sharp razor, a test piece sampled in a strip shape having a width of 10 mm and a length of 150 mm was prepared. About this test piece, the tensile elastic modulus was measured at 23 degreeC by the method based on ASTMD882: 2012 using the universal testing machine RTC-1310A by Orientec.

(5) Sound insulation of laminated glass The laminated glass is vibrated with a vibration generator for vibration testing ("Vibrator G21-005D" manufactured by KENKEN Co., Ltd.), and the vibration characteristics obtained therefrom are measured with a mechanical impedance measuring device ( The vibration spectrum was analyzed with an FFT spectrum analyzer (“FFT analyzer HP3582A” manufactured by Yokogawa Hewlett-Packard Co.).

  From the ratio of the loss factor thus obtained and the resonance frequency of the laminated glass, a graph showing the relationship between the sound frequency (Hz) at 20 ° C. and the sound transmission loss (dB) is created. The minimum sound transmission loss (TL value) in the vicinity of 000 Hz was determined. The higher the TL value, the higher the sound insulation.

  The evaluation results are shown in Table 1. In Table 1 below, “EVA” represents an ethylene-vinyl acetate copolymer, “PMMA” represents polymethyl methacrylate, and PVB represents a polyvinyl butyral resin.

DESCRIPTION OF SYMBOLS 1 ... Resin film 1a ... 1st surface 1b ... 2nd surface 11 ... Thermoplastic resin layer 11A ... 1st thermoplastic resin layer 11B ... 2nd thermoplastic resin layer 21 ... Laminated body (40 layers)
22 ... Laminated body (80 layers)
51 ... Glazing 52 ... First glazing member 53 ... Second glazing member

Claims (11)

A plurality of first thermoplastic resin layers containing a thermoplastic resin, and a plurality of second thermoplastic resin layers containing a thermoplastic resin,
The first thermoplastic resin layer and the second thermoplastic resin layer have a multilayer structure laminated in the thickness direction;
The total number of stacks in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer is 5 layers or more;
The thermoplastic resin in the first thermoplastic resin layer is an ethylene-vinyl acetate copolymer;
A thermoplastic resin film having a tensile modulus of elasticity of 1 GPa or more in one layer of the second thermoplastic resin layer.   The thermoplastic resin film according to claim 1, wherein a ratio of a total thickness of the first thermoplastic resin layer to a total thickness of the second thermoplastic resin layer is 1 or more.   The thermoplastic resin film of Claim 1 or 2 whose sum total of the lamination | stacking number of the thickness direction of a said 1st thermoplastic resin layer and a said 2nd thermoplastic resin layer is 10 layers or more.   The thermoplastic resin film according to any one of claims 1 to 3, wherein the total number of laminated layers in the thickness direction of the first thermoplastic resin layer and the second thermoplastic resin layer is 160 or more. .   The first thermoplastic resin layer, the second thermoplastic resin layer, the first thermoplastic resin layer, and the second thermoplastic resin layer have a portion laminated in this order. 5. The thermoplastic resin film according to any one of 4 above.   The thermoplastic resin film according to any one of claims 1 to 5, wherein the second thermoplastic resin layer has three or more layers. Used to obtain glazing,
It is used by being arranged between the first glazing member and the second glazing member,
The thermoplastic resin film according to any one of claims 1 to 6, wherein the thermoplastic resin film is an intermediate film for glazing.   The thermoplastic resin film according to claim 7, wherein the thickness of the first glazing member is 1.5 mm or less. The glazing is a laminated glass, the first glazing member is a first laminated glass member, and the second glazing member is a second laminated glass member,
The thermoplastic resin film according to claim 7 or 8, wherein the intermediate film for glazing is an intermediate film for laminated glass. A first glazing member;
A second glazing member;
An intermediate film for glazing that is the thermoplastic resin film according to claim 7 or 8,
Glazing wherein the glazing interlayer is disposed between the first glazing member and the second glazing member. The first glazing member is a first laminated glass member, the second glazing member is a second laminated glass member, and the glazing interlayer is a laminated glass interlayer;
The glazing of claim 10, wherein the glazing is a laminated glass.

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