JP6360704B2 - Intermediate film for laminated glass, method for producing interlayer film for laminated glass, laminated glass and method for producing laminated glass - Google Patents

Description

  The present invention relates to an interlayer film for laminated glass used for laminated glass and a method for producing an interlayer film for laminated glass. Moreover, this invention relates to the laminated glass using the said intermediate film for laminated glasses.

  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 by sandwiching an interlayer film for laminated glass between a pair of glass plates. Laminated glass is required to have high penetration resistance because it is not easily damaged even when subjected to an external impact.

  As an example of the interlayer film for laminated glass, the following Patent Document 1 discloses a resin layer (A) containing two transparent adhesive resins and a resin layer (B) containing polyethylene terephthalate between the two resin layers (a). ) Is disclosed.

  In Patent Document 2 below, there is an intermediate film that is a laminate formed of a plasticized polyvinyl acetal resin film or a laminate formed of a plasticized polyvinyl acetal resin film and a polyester film. It is disclosed.

  Patent Document 3 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 3 describe an intermediate film in which two layers A and B are stacked in a stacked structure of A / B / A.

JP 2008-303084 A JP 2001-106556 A JP 2003-192402 A

  The conventional intermediate films described in Patent Documents 1 to 3 have a problem that workability is low at the time of producing laminated glass. For example, misalignment between the intermediate film and the glass plate may occur.

  In addition, regarding an intermediate film in which a plastic layer and a resin layer containing a polyvinyl acetal resin or the like are laminated, the adhesive force between the plastic layer and the polyvinyl acetal resin layer may be low. Furthermore, there is a problem that the plastic layer and the resin layer are easily peeled off and the handling property of the intermediate film is low.

  An object of the present invention is to provide an interlayer film for laminated glass and a method for producing the interlayer film for laminated glass, which can enhance the adhesion between the plastic layer and the resin layer and can improve the handleability of the laminated glass. It is. Moreover, the objective of this invention is providing the laminated glass using said intermediate film for laminated glasses.

  According to a wide aspect of the present invention, a plastic layer having a Young's modulus of 1 GPa or more and a first resin layer laminated on a first surface of the plastic layer, the first surface of the plastic layer The second resin layer laminated on the second surface opposite to the above is provided or not provided, and is laminated on the plastic layer as the first resin layer before being laminated on the plastic layer. An interlayer film for laminated glass is provided, which is obtained by using the first resin layer having a ten-point average roughness Rz of 45 μm or less measured according to JIS B0601-1982 on the surface on the other side.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, when the Young's modulus of the plastic layer is higher than the Young's modulus of the first resin layer, and the interlayer film includes the second resin layer, The Young's modulus of the plastic layer is higher than the Young's modulus of the second resin layer.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, when the interlayer film includes the second resin layer, the plastic layer is used as the second resin layer before being stacked on the plastic layer. The tenth-point average roughness Rz measured in accordance with JIS B0601-1982 on the surface laminated on the surface is obtained using a second resin layer of 45 μm or less.

  The first resin layer preferably contains a polyvinyl acetal resin and a plasticizer. The second resin layer preferably contains a polyvinyl acetal resin and a plasticizer.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the first resin layer and the plastic layer are heated at a temperature of 65 ° C. or higher and 150 ° C. or lower and a pressure of 0 at the time of pressure bonding by a roll-to-roll method. It is thermocompression bonded under conditions of 1 kN or more and 5 kN or less and a tension of 100 N or less during conveyance.

  On the specific situation with the intermediate film for laminated glasses which concerns on this invention, the said intermediate film for laminated glasses is equipped with the said 2nd resin layer.

  The first resin layer preferably contains an ultraviolet shielding agent. The second resin layer preferably contains an ultraviolet shielding agent. The first resin layer preferably contains an antioxidant. The second resin layer preferably contains an antioxidant.

  According to a wide aspect of the present invention, a 10-point average roughness Rz measured according to JIS B0601-1982 of a plastic layer having a Young's modulus of 1 GPa or more and a surface laminated on the plastic layer is 45 μm. The first resin layer and the plastic layer are thermocompression-bonded using the following first resin layer, and the plastic layer and the first layer laminated on the first surface of the plastic layer An interlayer film for laminated glass comprising one resin layer is obtained, or measured according to JIS B0601-1982 on the surface of the plastic layer having a Young's modulus of 1 GPa or more and the side laminated on the plastic layer. Measured according to JIS B0601-1982 on the surface of the first resin layer having a 10-point average roughness Rz of 45 μm or less and the side laminated on the plastic layer. Using the second resin layer having a ten-point average roughness Rz of 45 μm or less, the first resin layer, the plastic layer, and the second resin layer are thermocompression bonded, A plastic layer; the first resin layer laminated on the first surface of the plastic layer; and a second resin layer laminated on a second surface opposite to the first surface of the plastic layer. The manufacturing method of the intermediate film for laminated glasses provided with the process of obtaining the intermediate film for laminated glass provided with these is provided.

  In a specific aspect of the method for producing an interlayer film for laminated glass according to the present invention, the first resin layer and the plastic layer are heated at a temperature of 65 ° C. or higher and 150 ° C. or lower by a roll-to-roll method. Thermocompression bonding under the conditions of a pressure of 0.1 kN to 5 kN and a tension of 100 N or less during conveyance.

  According to a wide aspect of the present invention, the laminated glass member includes a first laminated glass member, a second laminated glass member, and the interlayer film for laminated glass described above, and the interlayer film for laminated glass is the first laminated glass. A laminated glass is provided that is disposed between a member and the second laminated glass member.

  An interlayer film for laminated glass according to the present invention includes a plastic layer having a Young's modulus of 1 GPa or more, and a first resin layer laminated on a first surface of the plastic layer, and the first layer of the plastic layer. As the first resin layer before being laminated on the plastic layer, the second resin layer laminated on the second surface opposite to the surface of the plastic layer may or may not be provided. Since the ten-point average roughness Rz measured according to JIS B0601-1982 on the surface to be laminated is obtained using the first resin layer of 45 μm or less, the plastic layer and the resin layer in the intermediate film It is possible to improve the adhesion of the laminated glass and to improve the handleability of the laminated glass.

  The method for producing an interlayer film for laminated glass according to the present invention is a ten-point average measured in accordance with JIS B0601-1982 on a plastic layer having a Young's modulus of 1 GPa or more and a surface laminated on the plastic layer. Using the first resin layer having a roughness Rz of 45 μm or less, the first resin layer and the plastic layer are thermocompression bonded to the plastic layer and the first surface of the plastic layer. An interlayer film for laminated glass having the first resin layer laminated is obtained, or a plastic layer having a Young's modulus of 1 GPa or more and JIS B0601-1982 on the surface laminated on the plastic layer. The first resin layer having a ten-point average roughness Rz measured in conformity with 45 μm or less, and JIS B0601- on the surface laminated on the plastic layer Using the second resin layer having a ten-point average roughness Rz of 45 μm or less measured in accordance with 1982, the first resin layer, the plastic layer, and the second resin layer are thermocompression bonded. Thus, the plastic layer, the first resin layer laminated on the first surface of the plastic layer, and the second surface opposite to the first surface of the plastic layer were laminated. Since the process of obtaining the intermediate film for laminated glasses provided with a 2nd resin layer is provided, the adhesiveness of the plastic layer and resin layer in an intermediate film can be improved, and the handleability of a laminated glass can be improved.

FIG. 1 is a cross-sectional view showing an interlayer film for laminated glass according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a laminated glass using an interlayer film for laminated glass according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

(Interlayer film for laminated glass)
The interlayer film for laminated glass according to the present invention includes a plastic layer and a first resin layer laminated on the first surface of the plastic layer. The interlayer film for laminated glass according to the present invention includes or does not include the second resin layer laminated on the second surface opposite to the first surface of the plastic layer.

  Therefore, the interlayer film for laminated glass according to the present invention is the interlayer film (1) that includes the plastic layer and the first resin layer and does not include the second resin layer, or the first resin layer. And an intermediate film (2) comprising a plastic layer and a second resin layer. The interlayer film for laminated glass according to the present invention may be the interlayer film (1) or the interlayer film (2).

  The Young's modulus of the plastic layer is 1 GPa or more. The interlayer film for laminated glass according to the present invention is measured as the first resin layer before being laminated on the plastic layer in accordance with JIS B0601-1982 on the surface laminated on the plastic layer. The ten-point average roughness Rz is obtained using a first resin layer having a thickness of 45 μm or less.

  By adopting the above-described configuration in the present invention, it is possible to improve the adhesiveness between the plastic layer and the resin layer in the intermediate film and to improve the handleability of the laminated glass. Moreover, the workability at the time of manufacture of the laminated glass using an intermediate film can be improved. For example, in the production of laminated glass, when the intermediate film is transported onto a laminated glass member such as a glass plate, peeling of the adhesive interface between the plastic layer, the first resin layer, and the second resin layer occurs. In addition, because it is easy to handle, it is excellent in workability. This effect originates from the fact that when the film is subjected to a wavy movement during conveyance, if the interfacial adhesive force is low, peeling tends to occur due to the movement, but if the interfacial adhesion is high, peeling does not occur. Furthermore, by adopting the above-described configuration in the present invention, even if the laminated glass using the interlayer film is broken, it is difficult for large pieces to be generated, and the safety of the obtained laminated glass can be improved. This effect is derived from excellent impact relaxation at breakage by controlling the adhesion between layers.

  In particular, when a resin layer having a Young's modulus lower than that of the plastic layer is laminated on a plastic layer having a high Young's modulus, or when an intermediate film is disposed between laminated glass members, handling properties are poor, and This is very time consuming and tends to cause problems in handling. Furthermore, misalignment is likely to occur. Further, if the plastic layer and the resin layer are simply firmly bonded, there is a problem that when the laminated glass is broken, the fragments become large. On the other hand, by adopting the above-described configuration in the present invention, it is possible to improve workability and reduce the size of fragments.

  Moreover, in this invention, the penetration resistance of the laminated glass obtained can also be improved. Furthermore, even if the laminated glass is broken, the appearance of the laminated glass after the breakage can be improved. For example, the laminated glass is likely to be broken like a spider web, and is less likely to be broken as the laminated glass is torn. In addition, the laminated glass does not break as if it was torn, but breaks like a spider's web, making it much less likely that glass fragments will cause major damage to people, etc. Becomes even higher.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further improving the handleability of the laminated glass, the ten-point average of the surface on the side laminated on the plastic layer in the first resin layer The roughness Rz is preferably 40 μm or less, more preferably 35 μm or less, and still more preferably 30 μm or less.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further improving the handleability of the laminated glass, the ten-point average of the surface on the side laminated on the plastic layer in the second resin layer The roughness Rz is preferably 45 μm or less, more preferably 40 μm or less, still more preferably 35 μm or less, and particularly preferably 30 μm or less.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further improving the handleability of the laminated glass, the first resin is laminated in the state where the first resin layer is laminated on the plastic layer. The ten-point average roughness Rz of the surface of the layer laminated on the plastic layer is preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further enhancing the handleability of the laminated glass, the second resin is laminated in the state where the second resin layer is laminated on the plastic layer. The ten-point average roughness Rz of the surface of the layer laminated on the plastic layer is preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further improving the handleability of the laminated glass, it is laminated on the plastic layer of the first resin layer after being laminated on the plastic layer. 10-point average roughness Rz (μm) (Rz1b) of the surface on the other side of the surface of the first resin layer on the side laminated on the plastic layer before being laminated on the plastic layer The rate of change ((Rz1a−Rz1b) / Rz1a) with respect to the roughness Rz (μm) (Rz1a) is preferably 20% or more, more preferably 30% or more, and even more preferably 50% or more.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further improving the handleability of the laminated glass, it is laminated on the plastic layer of the second resin layer after being laminated on the plastic layer. 10-point average roughness Rz (μm) (Rz2b) of the surface on the other side of the surface of the second resin layer before being laminated on the plastic layer on the side laminated on the plastic layer The rate of change ((Rz2a−Rz2b) / Rz2a) with respect to the roughness Rz (μm) (Rz2a) is preferably 20% or more, more preferably 30% or more, and even more preferably 50% or more.

  From the viewpoint of further improving the adhesiveness between the plastic layer and the resin layer and further improving the handleability of the laminated glass, the Young's modulus of the plastic layer may be higher than the Young's modulus of the first resin layer. preferable. From the viewpoint of further improving the adhesion between the plastic layer and the resin layer, and further enhancing the handleability of the laminated glass, when the intermediate film includes the second resin layer, the Young's modulus of the plastic layer is: The Young's modulus of the second resin layer is preferably higher.

  The interlayer film for laminated glass according to the present invention preferably includes the second resin layer. In the case where the intermediate film includes the second layer, the workability at the time of producing the laminated glass can be further increased, and the fragments when the laminated glass is broken can be effectively reduced.

  From the viewpoint of further improving the workability during the production of the laminated glass and effectively reducing the fragments when the laminated glass is broken, the Young's modulus of the plastic layer is preferably 1.5 GPa or more, more preferably 2 GPa. That's it. The Young's modulus is preferably 10 GPa or less.

  In general, the Young's modulus of a resin layer containing a polyvinyl acetal resin and a plasticizer is less than 1 GPa, specifically 0.8 GPa or less. Therefore, in general, the plastic layer having a Young's modulus of 1 GPa or more is different from a resin layer containing a polyvinyl acetal resin and a plasticizer. The Young's modulus of the first resin layer is preferably less than 1 GPa, more preferably 0.8 GPa or less. The Young's modulus of the second resin layer is preferably less than 1 GPa, more preferably 0.8 GPa or less.

  From the viewpoint of further improving the workability at the time of producing the laminated glass and effectively reducing the fragments when the laminated glass is broken, the Young's modulus of the plastic layer is determined by the first resin layer and the second resin layer. Each Young's modulus of the resin layer is preferably more than 1.25 times, more preferably 2 times or more, further preferably 4 times or more, preferably 50 times or less, more preferably 10 times or less.

  The Young's modulus of the plastic layer, the first resin layer, and the second resin layer is measured as follows.

  A strain-stress curve is obtained at 23 ° C. by a tensile test according to JIS K7127. The Young's modulus is indicated by the slope of the linear portion of the obtained strain-stress curve.

  From the viewpoint of further improving the workability during the production of the laminated glass and effectively reducing the fragments when the laminated glass is broken, the adhesive force between the plastic layer and the first resin layer, and the plastic layer And the second resin layer are preferably 1 N / 50 mm or more, more preferably 2 N / 50 mm or more, still more preferably 3 N / 50 mm or more, preferably 20 N / 50 mm or less, more preferably 15 N / 50 mm. Hereinafter, it is more preferably 10 N / 50 mm or less. When the adhesive force is not less than the lower limit, the adhesion between the interface between the plastic layer and the first resin layer and the interface between the plastic layer and the second resin layer is further improved. When the adhesive strength is less than or equal to the above upper limit, large laminated glass fragments are less likely to be produced during a penetration resistance test of the laminated glass, and the safety is further improved.

  The adhesive force between the plastic layer and the first resin layer and the adhesive force between the plastic layer and the second resin layer are measured as follows.

  In accordance with JIS K6854-2, the adhesive force is measured at 23 ° C. at a speed of 500 mm / min using a Tensilon universal material testing machine (“RTM-500” manufactured by Orientec Co., Ltd.).

  In the interlayer film for laminated glass according to the present invention, the plastic layer and the first resin layer have a heating temperature of 65 ° C. or higher and 150 ° C. or lower, and a pressure during pressure bonding of 0.1 kN or higher and 5 kN by roll-to-roll method. It is preferable that thermocompression bonding is performed under the following conditions and a tension of 100 N or less during conveyance. By producing the intermediate film by such thermocompression bonding, the adhesive force between the plastic layer and the first resin layer can be controlled within a suitable range.

  In the interlayer film for laminated glass according to the present invention, the first resin layer, the plastic layer, and the second resin layer are heated at a temperature of 65 ° C. or higher and 150 ° C. or lower by a roll-to-roll method. It is preferable that thermocompression bonding is performed under conditions of a pressure of 0.1 kN or more and 5 kN or less and a tension of 100 N or less during conveyance. By producing the intermediate film by such thermocompression bonding, the adhesive force between the plastic layer and the first resin layer and the adhesive force between the plastic layer and the second resin layer are controlled within a suitable range. it can.

  The interlayer film for laminated glass according to the present invention heats the first resin layer, disposes the first resin layer on the surface of the plastic layer, and uses the heated press roll, It can also be obtained by a laminating press that passes and maintains the heating temperature of the layer. The interlayer film for laminated glass according to the present invention heats the first resin layer and the second resin layer, and disposes the first resin layer and the second resin layer on the surface of the plastic layer. Further, it can also be obtained by a laminating press in which pressure is applied by using a heated press roll so as to maintain the heating temperature of the first resin layer and the second resin layer.

  In an intermediate film that includes the first resin layer and does not include the second resin layer, the heating temperature indicates the heating temperature of the first resin layer. In the intermediate film including the first resin layer and the second resin layer, the heating temperature indicates the heating temperature of the first resin layer and the second resin layer. However, if the heating temperatures of the first resin layer and the second resin layer are within the above ranges, the heating temperatures of the first resin layer and the second resin layer are the same. It may be different.

  Specifically, the interlayer film for laminated glass according to the present invention may have the following structure.

  In FIG. 1, the intermediate film for laminated glasses used for the laminated glass which concerns on one Embodiment of this invention is typically shown with sectional drawing.

  The intermediate film 1 shown in FIG. 1 is a multilayer intermediate film. The intermediate film 1 is used to obtain a laminated glass. The intermediate film 1 is an intermediate film for laminated glass. The intermediate film 1 is formed on the plastic layer 2, the first resin layer 3 laminated on the first surface 2a of the plastic layer 2, and the second surface 2b opposite to the first surface 2a of the plastic layer 2. And a laminated second resin layer 4. The plastic layer 2 and the first resin layer 3 and the plastic layer 2 and the second resin layer 4 are directly laminated, respectively. The plastic layer 2 is an intermediate layer. The first resin layer 3 and the second resin layer 4 are surface layers in the present embodiment. The plastic layer 2 is disposed between the first resin layer 3 and the second resin layer 4. The plastic layer 2 is sandwiched between the first resin layer 3 and the second resin layer 4. Therefore, the intermediate film 1 has a multilayer structure in which the first resin layer 3, the plastic layer 2, and the second resin layer 4 are laminated in this order. Note that an intermediate film in which the first resin layer and the plastic layer 2 are stacked may be obtained without stacking the second resin layer 4.

(Blend component of plastic layer)
[Thermoplastic resin]
The plastic layer includes a thermoplastic resin. Examples of the thermoplastic resin contained in the plastic layer include chain polyolefins such as polyethylene, polypropylene, poly (4-methylpentene-1), and polyacetal; ring-opening metathesis polymers or addition polymers of norbornenes, norbornenes and others Polyolefins such as addition copolymers with olefins; biodegradable polymers such as polylactic acid and polybutyl succinate; polyamides such as nylon 6, nylon 11, nylon 12 and nylon 66; aramids; polymethyl methacrylate , Polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene copolymer polymethyl methacrylate, polycarbonate, polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene Polyester such as len-2,6-naphthalate; polyethersulfone; polyetheretherketone; modified polyphenylene ether; polyphenylene sulfide; polyetherimide; polyimide; polyarylate; tetrafluoroethylene resin; Fluorinated ethylene chloride resin; Tetrafluoroethylene-6 fluorinated propylene copolymer; Polyvinylidene fluoride and the like. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the workability during the production of the laminated glass and effectively reducing the fragments when the laminated glass is broken, it is preferable that the thermoplastic resin contained in the plastic layer is polyethylene terephthalate.

  In order to effectively increase the Young's modulus, the plastic layer preferably contains a thermoplastic resin other than the polyvinyl acetal resin, and preferably does not contain the polyvinyl acetal resin. When the plastic layer contains a polyvinyl acetal resin, the content of the polyvinyl acetal resin is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less in 100% by weight of the plastic layer. It is.

  In order to effectively increase the Young's modulus, the plastic layer preferably does not contain a plasticizer. When the plastic layer contains a plasticizer, the content of the plasticizer is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less in 100% by weight of the plastic layer. .

[Other ingredients]
The plastic layer preferably contains an ultraviolet shielding agent, and preferably contains an antioxidant. In addition, the kind of ultraviolet shielding agent and antioxidant which can be used for the said plastic layer is the same as that of the ultraviolet shielding agent and antioxidant which can be used for the 1st resin layer and 2nd resin layer which are mentioned later. .

  The plastic layer may contain additives such as a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion adjusting agent, a moisture-resistant agent, and a fluorescent brightening agent as necessary. As for these additives, only 1 type may be used and 2 or more types may be used together.

(Composition components of the first resin layer and the second resin layer)
[Thermoplastic resin]
Each of the first resin layer and the second resin layer preferably includes a thermoplastic resin. The thermoplastic resin is not particularly limited. A conventionally well-known thermoplastic resin can be used as said thermoplastic resin. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together. The thermoplastic resin in the first resin layer and the thermoplastic resin in the second resin layer may be the same or different.

  Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin. Thermoplastic resins other than these may be used.

  The thermoplastic resin is preferably a polyvinyl acetal resin. By the combined use of the polyvinyl acetal resin and the plasticizer, the adhesion of the first resin layer and the second resin layer to other layers such as a laminated glass member and a plastic layer is further increased.

  The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol can be produced, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is generally in the range of 70 to 99.8 mol%.

  The average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, preferably 5000 or less, more preferably 4000 or less, still more preferably 3500 or less, particularly preferably 3000 or less, and most preferably 2500 or less. . When the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the average degree of polymerization is not more than the above upper limit, the intermediate film can be easily molded. The average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.

  The number of carbon atoms of the acetal group contained in the polyvinyl acetal resin is not particularly limited. The aldehyde used when manufacturing the said polyvinyl acetal resin is not specifically limited. The carbon number of the acetal group in the polyvinyl acetal resin is preferably 3 or 4. When the carbon number of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the intermediate film is sufficiently low.

  The aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among these, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable, and n-butyraldehyde is still more preferable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

  The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 18 mol% or more, still more preferably 20 mol% or more, particularly preferably 28 mol% or more, preferably 40 mol. % Or less, more preferably 35 mol% or less, still more preferably 32 mol% or less. When the hydroxyl group content is at least the above lower limit, the adhesive strength of the interlayer film is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.

  The hydroxyl group content of the polyvinyl acetal resin is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which the hydroxyl group is bonded by the total amount of ethylene groups in the main chain, as a percentage. The amount of the ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring according to JIS K6726 “Testing method for polyvinyl alcohol”.

  The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.5 mol% or more, preferably 30 mol% or less. More preferably, it is 25 mol% or less, more preferably 20 mol% or less, particularly preferably 15 mol% or less, and most preferably 3 mol% or less. When the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased. When the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass is increased.

  The degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, It is a value indicating the mole fraction obtained by dividing by the percentage. The amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.

  The degree of acetalization of the polyvinyl acetal resin (in the case of polyvinyl butyral resin, the degree of butyralization) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, more preferably 75 mol%. Hereinafter, it is 70 mol% or less more preferably. When the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.

  The degree of acetalization is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, as a percentage.

  The degree of acetalization can be calculated by a method based on JIS K6728 “Testing method for polyvinyl butyral”.

  The hydroxyl group content (hydroxyl group amount), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from results measured by a method based on JIS K6728 “Testing methods for polyvinyl butyral”. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl content), the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It is preferable to calculate from the results measured by.

[Plasticizer]
The first resin layer preferably contains a plasticizer. The second resin layer preferably contains a plasticizer. In the case where the thermoplastic resin in the first resin layer and the second resin layer is a polyvinyl acetal resin, it is particularly preferable that the first resin layer and the second resin layer each contain a plasticizer. . By using the plasticizer, the adhesive force between the first resin layer and the second resin layer is further increased.

  The plasticizer is not particularly limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphate plasticizers such as organic phosphate plasticizers and organic phosphorous acid plasticizers. It is done. Of these, organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.

  The monobasic organic acid ester is not particularly limited. For example, a glycol ester obtained by reaction of glycol with a monobasic organic acid, and triethylene glycol or tripropylene glycol with a monobasic organic acid. Examples include esters. Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.

  The polybasic organic acid ester is not particularly limited, and examples thereof include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.

  The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di 2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl hexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, adipine Examples include a mixture of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, alkyd oil-modified sebacic acid, and a mixture of phosphate ester and adipate. Organic ester plasticizers other than these may be used.

  The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

  The plasticizer is preferably a diester plasticizer represented by the following formula (1).

  In the above formula (1), R1 and R2 each represent an organic group having 2 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10. . R1 and R2 in the formula (1) are each preferably an organic group having 5 to 10 carbon atoms, and more preferably an organic group having 6 to 10 carbon atoms.

  The plasticizer preferably contains at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH). More preferably, it contains 2-ethylhexanoate.

  The content of the plasticizer is not particularly limited. In the first resin layer and the second resin layer, the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin is preferably 25 parts by weight or more, more preferably 30 parts by weight or more. The amount is preferably 35 parts by weight or more, preferably 75 parts by weight or less, more preferably 60 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 40 parts by weight or less. When the content of the plasticizer is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the content of the plasticizer is not more than the above upper limit, the transparency of the interlayer film is further enhanced.

[Heat shielding compound]
Component X:
Each of the first resin layer and the second resin layer preferably includes a heat shielding compound. Preferably, each of the first resin layer and the second resin layer includes at least one component X of a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound. Each of the first resin layer and the second resin layer includes at least one component X of a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound, or includes heat shielding particles described later. preferable. The component X is a heat shielding compound. By using the component X in at least one layer of the entire intermediate film, infrared rays (heat rays) can be effectively blocked.

  The component X is not particularly limited. As component X, conventionally known phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds can be used. As for the said component X, only 1 type may be used and 2 or more types may be used together.

  Examples of the component X include phthalocyanine, a derivative of phthalocyanine, naphthalocyanine, a derivative of naphthalocyanine, anthracyanine, an anthracocyanine derivative, and the like. The phthalocyanine compound and the phthalocyanine derivative preferably each have a phthalocyanine skeleton. The naphthalocyanine compound and the naphthalocyanine derivative preferably each have a naphthalocyanine skeleton. It is preferable that each of the anthocyanin compound and the derivative of the anthracyanine has an anthracyanine skeleton.

  From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X is preferably at least one selected from the group consisting of phthalocyanine, phthalocyanine derivatives, naphthalocyanine, and naphthalocyanine derivatives. More preferably, it is at least one of phthalocyanine and phthalocyanine derivatives.

  From the viewpoint of effectively increasing the heat shielding property and maintaining the visible light transmittance at a higher level over a long period of time, the component X preferably contains a vanadium atom or a copper atom. The component X preferably contains a vanadium atom, and preferably contains a copper atom. The component X is more preferably at least one of a phthalocyanine containing a vanadium atom or a copper atom and a phthalocyanine derivative containing a vanadium atom or a copper atom. From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X preferably has a structural unit in which an oxygen atom is bonded to a vanadium atom.

  When the first resin layer or the second resin layer contains the component X, each content of the component X is preferably in 100% by weight of the first resin layer and the second resin layer. Is 0.001 wt% or more, more preferably 0.005 wt% or more, still more preferably 0.01 wt% or more, particularly preferably 0.02 wt% or more, preferably 0.2 wt% or less, more preferably It is 0.1% by weight or less, more preferably 0.05% by weight or less, and particularly preferably 0.04% by weight or less. When the content of the component X in the first resin layer and the second resin layer is not less than the lower limit and not more than the upper limit, the heat shielding property is sufficiently high, and the visible light transmittance is sufficiently high. Become. For example, the visible light transmittance can be 70% or more.

Thermal barrier particles:
Each of the first resin layer and the second resin layer preferably includes heat shielding particles. The heat shielding particles are heat shielding compounds. Infrared rays (heat rays) can be effectively blocked by using a heat-shielding compound in at least one layer of the entire intermediate film.

  From the viewpoint of further improving the heat shielding property of the laminated glass, the heat shielding particles are more preferably metal oxide particles. The heat shielding particles are preferably particles (metal oxide particles) formed of a metal oxide. As for the said heat-shielding particle, only 1 type may be used and 2 or more types may be used together.

  Infrared rays having a wavelength longer than 780 nm longer than visible light have a smaller amount of energy than ultraviolet rays. However, infrared rays have a large thermal effect, and once infrared rays are absorbed by a substance, they are released as heat. For this reason, infrared rays are generally called heat rays. By using the heat shielding particles, infrared rays (heat rays) can be effectively blocked. The heat shielding particles mean particles that can absorb infrared rays.

Specific examples of the heat shielding particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles (IZO particles). ), Aluminum doped zinc oxide particles (AZO particles), niobium doped titanium oxide particles, sodium doped tungsten oxide particles, cesium doped tungsten oxide particles, thallium doped tungsten oxide particles, rubidium doped tungsten oxide particles, tin doped indium oxide particles (ITO particles) And metal oxide particles such as tin-doped zinc oxide particles and silicon-doped zinc oxide particles, and lanthanum hexaboride (LaB ₆ ) particles. Heat shielding particles other than these may be used. Among these, metal oxide particles are preferable because of their high heat ray shielding function, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferable, and ITO particles or tungsten oxide particles are particularly preferable. In particular, tin-doped indium oxide particles (ITO particles) are preferable, and tungsten oxide particles are also preferable because they have a high heat ray shielding function and are easily available.

  The tungsten oxide particles are generally represented by the following formula (X1) or the following formula (X2). In the intermediate film, tungsten oxide particles represented by the following formula (X1) or the following formula (X2) are preferably used.

W _y O _z Formula (X1)
In the above formula (X1), W represents tungsten, O represents oxygen, and y and z satisfy 2.0 <z / y <3.0.

M _x W _y O _z Formula (X2)
In the above formula (X2), M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu , Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta And at least one element selected from the group consisting of Re, W represents tungsten, O represents oxygen, and x, y, and z represent 0.001 ≦ x / y ≦ 1, and 2.0 <z / y ≦ 3.0 is satisfied.

  From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the tungsten oxide particles are preferably metal-doped tungsten oxide particles. The “tungsten oxide particles” include metal-doped tungsten oxide particles. Specific examples of the metal-doped tungsten oxide particles include sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, and rubidium-doped tungsten oxide particles.

From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, cesium-doped tungsten oxide particles are particularly preferable. From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the cesium-doped tungsten oxide particles are preferably tungsten oxide particles represented by the formula: Cs _0.33 WO ₃ .

  The average particle diameter of the heat shielding particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.1 μm or less, more preferably 0.05 μm or less. When the average particle size is not less than the above lower limit, the heat ray shielding property is sufficiently increased. When the average particle size is not more than the above upper limit, the dispersibility of the heat shielding particles is increased.

  The “average particle diameter” indicates a volume average particle diameter. The average particle diameter can be measured using a particle size distribution measuring apparatus (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.

  When the first resin layer or the second resin layer contains the heat shielding particles, each content of the heat shielding particles is preferably 100% by weight of the first resin layer and the second resin layer. Is 0.01 wt% or more, more preferably 0.1 wt% or more, still more preferably 1 wt% or more, particularly preferably 1.5 wt% or more, preferably 6 wt% or less, more preferably 5.5 wt%. % Or less, more preferably 4% by weight or less, particularly preferably 3.5% by weight or less, and most preferably 3.0% by weight or less. When the content of the heat shielding particles is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high.

When the first resin layer or the second resin layer contains the heat shielding particles, the first resin layer and the second resin layer contain 0.1 to 12 g / m ^{2 of the} heat shielding particles. It is preferable to contain in the ratio. When the ratio of the heat shielding particles is within the above range, the heat shielding property is sufficiently high, and the visible light transmittance is sufficiently high. The proportion of the heat shielding particles is preferably 0.5 g / m ² or more, more preferably 0.8 g / m ² or more, still more preferably 1.5 g / m ² or more, particularly preferably 3 g / m ² or more, preferably Is 11 g / m ² or less, more preferably 10 g / m ² or less, still more preferably 9 g / m ² or less, and particularly preferably 7 g / m ² or less. When the ratio is equal to or higher than the lower limit, the heat shielding property is further enhanced. The said visible light transmittance becomes it still higher that the said ratio is below the said upper limit.

[Ultraviolet shielding agent]
The first resin layer preferably contains an ultraviolet shielding agent. The second resin layer preferably contains an ultraviolet shielding agent. More preferably, both the first resin layer and the second resin layer contain an ultraviolet shielding agent. By using the ultraviolet shielding agent, even if the interlayer film and the laminated glass are used for a long period of time, the visible light transmittance is more unlikely to decrease. As for this ultraviolet shielding agent, only 1 type may be used and 2 or more types may be used together.

  The ultraviolet shielding agent includes an ultraviolet absorber. The ultraviolet shielding agent is preferably an ultraviolet absorber.

  Conventionally known general UV screening agents are, for example, metal UV screening agents, metal oxide UV screening agents, benzotriazole UV screening agents (benzotriazole compounds), and benzophenone UV screening agents (benzophenone). Compound), triazine-based UV screening agent (triazine compound), malonic acid ester-based UV screening agent (malonic acid ester compound), oxalic acid anilide-based UV screening agent (oxalic acid anilide compound) and benzoate-based UV screening agent (benzoate compound) Etc.

  Examples of the metallic ultraviolet shielding agent include platinum particles, particles in which the surface of the platinum particles is coated with silica, palladium particles, particles in which the surface of the palladium particles is coated with silica, and the like. The ultraviolet shielding agent is preferably not a heat shielding particle.

  Examples of the metal oxide ultraviolet shielding agent include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface may be coat | covered as said metal oxide type ultraviolet-ray shielding agent. Examples of the coating material on the surface of the metal oxide ultraviolet shielding agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.

  Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has a band gap energy of 5.0 eV or more, for example.

  Examples of the benzotriazole-based ultraviolet shielding agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole ("Tinvin 320" manufactured by BASF), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF " Tinuvin 326 ") and 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (" Tinvin 328 "manufactured by BASF) and the like. The benzotriazole-based ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet shielding agent containing a halogen atom, and more preferably a benzotriazole-based ultraviolet shielding agent containing a chlorine atom, because of its excellent ability to absorb ultraviolet rays. .

  Examples of the benzophenone-based ultraviolet shielding agent include octabenzone (“Chimasorb 81” manufactured by BASF).

  Examples of the triazine-based ultraviolet shielding agent include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (“Tinuvin 1577FF” manufactured by BASF Corporation). ) And the like.

  Examples of the malonic ester-based ultraviolet screening agent include 2- (p-methoxybenzylidene) malonic acid dimethyl, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene) -bis. (1,2,2,6,6-pentamethyl-4-piperidinyl) malonate and the like.

  As a commercial item of the said malonic acid ester type | system | group ultraviolet shielding agent, Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all are the Clariant company make) are mentioned.

  Examples of the oxalic acid anilide-based ultraviolet shielding agent include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl) -N ′. Oxalic acid diamides having an aryl group substituted on a nitrogen atom, such as-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("Sanduvor VSU" manufactured by Clariant) Can be mentioned.

  Examples of the benzoate-based ultraviolet shielding agent include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (“Tinvin 120” manufactured by BASF).

  In order to suppress a decrease in visible light transmittance of the interlayer film and the laminated glass after aging, the ultraviolet shielding agent is 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5- It is preferably chlorobenzotriazole (“Tinvin 326” manufactured by BASF) or 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinvin 328” manufactured by BASF). It may be (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole.

  When the first resin layer and the second resin layer contain the ultraviolet shielding agent, each content of the ultraviolet shielding agent in 100% by weight of the first resin layer and the second resin layer is as follows: Preferably 0.1% by weight or more, more preferably 0.2% by weight or more, still more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably 2.5% by weight or less, more preferably Is 2% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is not less than the above lower limit and not more than the above upper limit, a decrease in visible light transmittance after time is further suppressed. In particular, when the content of the ultraviolet shielding agent is 0.2% by weight or more in 100% by weight of the first resin layer and the second resin layer, visible light transmission after aging of the interlayer film and the laminated glass is achieved. The reduction in rate can be remarkably suppressed.

[Antioxidant]
The first resin layer preferably contains an antioxidant. The second resin layer preferably contains an antioxidant. It is preferable that both the first resin layer and the second resin layer contain an antioxidant. As for this antioxidant, only 1 type may be used and 2 or more types may be used together.

  Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. The phenolic antioxidant is an antioxidant having a phenol skeleton. The sulfur-based antioxidant is an antioxidant containing a sulfur atom. The phosphorus antioxidant is an antioxidant containing a phosphorus atom.

  The antioxidant is preferably a phenolic antioxidant or a phosphorus antioxidant.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, and stearyl. -Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl- 6-t-butylphenol), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-tert-butylphenyl) Butane, tetrakis [methylene-3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydro) Loxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,3′- and t-butylphenol) butyric acid glycol ester and bis (3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene). One or more of these antioxidants are preferably used.

  Examples of the phosphorus antioxidant include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphos. Phyto, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, tris (2,4-di-t -Butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, and the like. One or more of these antioxidants are preferably used.

  Examples of commercially available antioxidants include “IRGANOX 245” manufactured by BASF, “IRGAFOS 168” manufactured by BASF, “IRGAFOS 38” manufactured by BASF, “Smilizer BHT” manufactured by Sumitomo Chemical, and “ Irganox 1010 "and the like.

  When the first resin layer and the second resin layer contain the antioxidant, each content of the antioxidant in 100% by weight of the first resin layer and the second resin layer is as follows: Preferably it is 0.1 weight% or more, Preferably it is 2 weight% or less, More preferably, it is 1.8 weight% or less. When the content of the antioxidant is not less than the above lower limit, the high visible light transmittance of the interlayer film and the laminated glass is maintained for a longer period of time. When the content of the antioxidant is not more than the above upper limit, an excessive antioxidant is hardly generated to obtain the addition effect.

[Other ingredients]
Each of the first resin layer and the second resin layer may be a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, a fluorescent brightening agent, or the like, if necessary. An additive may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.

(Other details of interlayer film for laminated glass)
It is preferable that the said intermediate film for laminated glasses is arrange | positioned and used between a 1st laminated glass member and a 2nd laminated glass member.

  The thickness of the interlayer film for laminated glass is not particularly limited. From the viewpoint of practical use and from the viewpoint of sufficiently increasing the heat shielding property, the thickness of the intermediate film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably 1.5 mm or less. is there. When the thickness of the intermediate film is not less than the above lower limit, the penetration resistance of the laminated glass is increased.

  The thickness of the plastic layer is preferably 5 μm or more, more preferably 30 μm or more, preferably 300 μm or less, more preferably 150 μm or less. When the thickness of the plastic layer is equal to or more than the lower limit, the Young's modulus of the plastic layer is effectively increased, the workability at the time of producing the laminated glass is further increased, and the fragments when the laminated glass is broken are further increased. Even smaller. When the thickness of the plastic layer is less than or equal to the upper limit, the thicknesses of the first resin layer and the second resin layer can be relatively increased, and the first resin layer and the second resin are relatively thick. The performance derived from the layer can be further exhibited.

  The thicknesses of the first resin layer and the second resin layer are each preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.25 mm or more, particularly preferably 0.3 mm or more, preferably Is 1.0 mm or less, more preferably 0.6 mm or less, even more preferably 0.5 mm or less, still more preferably 0.45 mm or less, and particularly preferably 0.4 mm or less. When the thickness of the first resin layer and the second resin layer is equal to or greater than the lower limit, the penetration resistance of the laminated glass is further enhanced. When the thickness of the first resin layer and the second resin layer is not more than the upper limit, the transparency of the laminated glass is further increased.

(Method for producing interlayer film for laminated glass)
The method for producing an interlayer film for laminated glass according to the present invention is a ten-point average measured in accordance with JIS B0601-1982 on a plastic layer having a Young's modulus of 1 GPa or more and a surface laminated on the plastic layer. Using the first resin layer having a roughness Rz of 45 μm or less, the first resin layer and the plastic layer are thermocompression bonded to the plastic layer and the first surface of the plastic layer. An interlayer film for laminated glass having the first resin layer laminated is obtained, or a plastic layer having a Young's modulus of 1 GPa or more and JIS B0601-1982 on the surface laminated on the plastic layer. The first resin layer having a ten-point average roughness Rz measured in conformity with 45 μm or less, and JIS B0601-1 on the surface laminated on the plastic layer The first resin layer, the plastic layer, and the second resin layer are thermocompression bonded using a second resin layer having a ten-point average roughness Rz of 45 μm or less measured in accordance with 982 Thus, the plastic layer, the first resin layer laminated on the first surface of the plastic layer, and the second surface opposite to the first surface of the plastic layer were laminated. A step of obtaining an interlayer film for laminated glass comprising a second resin layer.

  A preferable method for producing an interlayer film for laminated glass according to the present invention is such that the plastic layer and the first resin layer are heated at a temperature of 65 ° C. or higher and 150 ° C. or lower and a pressure of 0. For laminated glass comprising the plastic layer and the first resin layer laminated on the first surface of the plastic layer by thermocompression bonding under a condition of 1 kN or more and 5 kN or less and a tension during transportation of 100 N or less. An intermediate film is obtained, or the plastic layer, the first resin layer, and the second resin layer are heated to 65 ° C. or higher and 150 ° C. or lower with a pressure of 0. The plastic layer and the first resin layer laminated on the first surface of the plastic layer by thermocompression bonding under conditions of 1 kN or more and 5 kN and a tension during transportation of 100 N or less , And the first surface of the plastic layer comprises a step of obtaining a interlayer film for a laminated glass comprising a second resin layer laminated to the opposite second surface.

  The Young's modulus of the plastic layer is 1 GPa or more. In the method for producing an interlayer film for laminated glass according to the present invention, the Young's modulus of the plastic layer is preferably higher than the Young's modulus of the first resin layer. The adhesive force between the plastic layer and the first resin layer measured in accordance with JIS K6854-2 is preferably 1 N / 50 mm or more, preferably 20 N / 50 mm or less.

  When the intermediate film includes the second resin layer, the Young's modulus of the plastic layer is preferably higher than the Young's modulus of the second resin layer. When the intermediate film includes the second resin layer, the adhesive force between the plastic layer and the second resin layer measured according to JIS K6854-2 is preferably 1 N / 50 mm or more, preferably 20 N / 50 mm or less.

  By the way, a plastic layer containing polyethylene terephthalate or the like is disposed on one surface of the resin layer or between two resin layers, and a laminated glass member such as a glass plate is disposed on the outer surface of the two resin layers. Thus, it is conceivable to perform autoclaving when obtaining a laminated glass. However, when autoclaving is performed, the handleability of the interlayer film is poor, and it takes a lot of time to laminate, and problems are likely to occur in handling. On the other hand, by adopting the above-described configuration of the method for producing an interlayer film for laminated glass according to the present invention, workability can be improved and fragments can be reduced.

  In addition, when obtaining an intermediate film provided with the first resin layer, the plastic layer, and the second resin layer, three layers may be laminated at one time, and the remaining layers after the two layers are laminated. You may laminate.

  The heating temperature is preferably 65 ° C or higher, preferably 150 ° C or lower. When the heating temperature is equal to or higher than the lower limit, the adhesion of the first resin layer and the second resin layer to the plastic layer is further improved. When the heating temperature is equal to or lower than the upper limit, softening of the first resin layer and the second resin layer is suppressed, and the suitability for lamination is further improved.

  The pressure during the pressure bonding is preferably 0.1 kN or more, preferably 5 kN or less. When the pressure at the time of the pressure bonding is equal to or higher than the lower limit, the adhesion of the first resin layer and the second resin layer to the plastic layer is further improved. When the pressure at the time of the pressure bonding is not more than the above upper limit, the occurrence of laminating wrinkles is suppressed and the suitability for laminating is further improved.

  The tension during the conveyance is preferably 10N or more, and preferably 200N or less. When the tension at the time of conveyance is equal to or more than the lower limit, sagging at the time of conveyance of the first resin layer, the second resin layer, and the plastic layer during the lamination process is suppressed, or wrinkles at the time of bonding are suppressed. Thus, the suitability for lamination becomes even better. When the tension at the time of conveyance is not more than the above upper limit, the stretching of the first resin layer and the second resin layer is suppressed, and the laminating suitability is further improved by suppressing the change in the film width. .

  Moreover, a conventionally well-known method can be used as a manufacturing method of the said plastic layer, said 1st resin layer, and said 2nd resin layer. For example, the manufacturing method etc. which knead | mix each component mentioned above and shape | mold each layer are mentioned. Since it is suitable for continuous production, an extrusion method is preferred.

  The kneading method is not particularly limited. Examples of this method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, or the like. Especially, since it is suitable for continuous production, a method using an extruder is preferable, and a method using a twin screw extruder is more preferable.

  Since the production efficiency of the intermediate film is excellent, the first resin layer and the second resin layer preferably contain the same polyvinyl acetal resin, and contain the same polyvinyl acetal resin and the same plasticizer. Is more preferable, and it is further preferable that the same resin composition is used.

(Laminated glass)
The laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and the interlayer film for laminated glass described above. The interlayer film for laminated glass is disposed between the first laminated glass member and the second laminated glass member. The first laminated glass member is disposed outside the first resin layer in the intermediate film. The second laminated glass member is disposed outside the second resin layer in the intermediate film. In addition, when the intermediate film does not include the second resin layer, a second laminated glass constituent member may be laminated on the surface of the plastic layer opposite to the first resin layer.

  In FIG. 2, an example of the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is shown with sectional drawing.

  A laminated glass 11 shown in FIG. 2 includes an intermediate film 1, a first laminated glass member 21, and a second laminated glass member 22. The interlayer film 1 is sandwiched between a first laminated glass member 21 and a second laminated glass member 22. A first laminated glass member 21 is laminated on the first surface 1 a of the intermediate film 1. A second laminated glass member 22 is laminated on a second surface 1 b opposite to the first surface 1 a of the intermediate film 1. A first laminated glass member 21 is laminated on the outer surface 3 a of the first resin layer 3 in the intermediate film 1. A second laminated glass member 22 is laminated on the outer surface 4 a of the second resin layer 4 in the intermediate film 1.

  Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. The laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate 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. The first laminated glass member and the second laminated glass member are respectively a glass plate or a PET (polyethylene terephthalate) film, and the intermediate film is the first laminated glass member and the second laminated glass member. It is preferable that at least one glass plate is included. It is particularly preferable that both the first laminated glass member and the second laminated glass member are glass plates.

  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, mesh plate glass, wire plate glass, and green 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.

  Although each thickness of the said 1st laminated glass member and the said 2nd laminated glass member is not specifically limited, Preferably it is 1 mm or more, Preferably it is 5 mm or less. When the laminated glass member is a glass plate, the thickness of the glass plate is preferably 1 mm or more, and preferably 5 mm or less. When the laminated glass 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 manufacturing method of the said laminated glass is not specifically limited. For example, the intermediate film is sandwiched between the first and second laminated glass members, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, so that the first laminated glass member and the middle The air remaining between the film and the second laminated glass member and the intermediate film 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, a laminated glass can be obtained.

  The laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The laminated glass is preferably laminated glass for buildings or vehicles, and more preferably laminated glass for vehicles. The laminated glass can be used for other purposes. The laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like. Since the heat shielding property is high and the visible light transmittance is high, the laminated glass is suitably used for automobiles.

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

(Material of first resin layer and second resin layer)
Thermoplastic resin:
Polyvinyl butyral resin (PVB1) (hydroxyl content 22 mol%, acetylation degree 13 mol%, butyral degree 65 mol%, average polymerization degree 2300)

Plasticizer:
3GO (triethylene glycol di-2-ethylhexanoate)

Other ingredients:
BHT (Antioxidant, 2,6-di-t-butyl-p-cresol)
T-326 (UV shielding agent, 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, “Tinuvin 326” manufactured by BASF)

(Resin layer)
Resin layer A (first resin layer)
For 100 parts by weight of polyvinyl butyral resin (PVB1), 40 parts by weight of a plasticizer (3GO), 0.5 parts by weight of an ultraviolet shielding agent (T-326), and 0.5 parts by weight of an antioxidant (BHT) The mixture was added and sufficiently kneaded with a mixing roll to obtain a composition. The obtained composition was extruded by an extruder to obtain a single resin layer having a thickness of 380 μm. Moreover, the surface of the resin layer on the side laminated with the plastic layer is embossed, and the ten-point average roughness Rz measured according to JIS B0601-1982 of the embossed surface is 35 μm. Got.

Resin layer B (first resin layer)
Resin layer B was obtained in the same manner as resin layer A, except that the ten-point average roughness Rz of the surface of the resin layer on the side laminated with the plastic layer was changed to 45 μm.

Resin layer X (first resin layer)
Resin layer X was obtained in the same manner as resin layer A, except that the ten-point average roughness Rz of the surface of the resin layer laminated on the plastic layer was changed to 55 μm.

Resin layer (second resin layer)
For 100 parts by weight of polyvinyl butyral resin (PVB1), 40 parts by weight of a plasticizer (3GO), 0.5 parts by weight of an ultraviolet shielding agent (T-326), and 0.5 parts by weight of an antioxidant (BHT) The mixture was added and sufficiently kneaded with a mixing roll to obtain a composition. The obtained composition was extruded by an extruder to obtain a single resin layer having a thickness of 380 μm. Further, a second surface having a ten-point average roughness Rz of 35 μm measured on the surface of the embossed surface according to JIS B0601-1982 by embossing the surface of the resin layer that is laminated on the plastic layer. A resin layer was obtained.

(Plastic layer)
Plastic layer A (polyethylene terephthalate film, “U34 Lumirror” manufactured by Toray Industries, Inc., thickness 100 μm)

(Examples 1 to 4 and Comparative Examples 1 and 2)
(1) Production of Intermediate Film In Examples 1 to 4 and Comparative Examples 1 and 2, an intermediate film having a two-layer structure is formed by laminating a plastic layer and a first resin layer of the type shown in Table 1 below. Produced.

  Using a thermocompression laminator (“MRK-650Y type” manufactured by MCK Co., Ltd.), heat-compression is performed by a roll-to-roll method at the heating temperature, pressure during crimping, and tension during conveyance shown in Table 1 below. went.

(2) Production of laminated glass The obtained intermediate film was cut into a size of 30 cm in length and 30 cm in width. Also, two clear glasses (length 30 cm × width 30 cm × thickness 2.5 mm) were prepared. The intermediate film and the second resin layer obtained are sandwiched between the two clear glasses in the order of the first resin layer, the plastic layer, and the second resin layer, and 30 ° C. at 30 ° C. with a vacuum laminator. The laminate was obtained by holding for a minute and vacuum pressing. In the laminated body, the intermediate film portion protruding from the glass plate was cut off to obtain a laminated glass. The ten-point average roughness Rz of the second resin layer on the plastic layer side was 35 μm.

(Evaluation)
(1) Young's modulus Each Young's modulus of the plastic layer and the first resin layer was measured as follows.

  A strain-stress curve was obtained at 23 ° C. by a tensile test based on JIS K7127. The Young's modulus indicated by the slope of the linear portion of the obtained strain-stress curve was evaluated.

(2) Laminating property After laminating the first resin layer, it was evaluated by visually observing the laminated state of the first resin layer. The laminate property was judged according to the following criteria.

[Judgment criteria for laminating properties]
○: When visually observed, there is no appearance defect due to wrinkles. ×: When visually observed, there is an appearance defect due to wrinkles.

(3) Ten-point average roughness Rz on the plastic layer side of the first resin layer after lamination
The first resin layer and the plastic layer after lamination were stored in an environment at 23 ° C. for 2 hours. After storage, the first resin layer was peeled from the plastic layer at 23 ° C. at a speed of 200 mm / min using a Tensilon universal material testing machine (Orientec “RTM-500”). Ten-point average roughness Rz (Rz1b) of the first resin layer on the plastic layer side was measured in accordance with JIS B0601-1982.

(4) Adhesive force Regarding the adhesive force between the plastic layer and the first resin layer, in accordance with JIS K6854-2, using a Tensilon universal material testing machine ("RTM-500" manufactured by Orientec Co., Ltd.) The adhesive force was measured at 23 ° C. and a speed of 500 mm / min.

(5) Handling property The obtained intermediate film was cut into a size of 100 cm × 100 cm. The handleability was evaluated by holding both ends of the cut intermediate film repeatedly and repeatedly contacting 30 times so that the surface and the back surface of the intermediate film contact each other alternately on the desk. The handleability was judged according to the following criteria.

[Handling criteria]
◯: state in which no separation between the first resin layer and the plastic layer has occurred after the test Δ: state in which separation of the first resin layer and the plastic layer has been confirmed after less than 10 mm after the test ×: first after the test The state where peeling of the resin layer and the plastic layer was confirmed at the edge of 10 mm or more

  Details and results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Intermediate film 1a ... 1st surface 1b ... 2nd surface 2 ... Plastic layer 2a ... 1st surface 2b ... 2nd surface 3 ... 1st resin layer 3a ... Outer surface 4 ... 2nd resin Layer 4a ... outer surface 11 ... laminated glass 21 ... first laminated glass member 22 ... second laminated glass member

Claims (13)

Comprising a plastic layer having a Young's modulus of 1 GPa or more and a first resin layer laminated on the first surface of the plastic layer;
With or without a second resin layer laminated on a second surface opposite to the first surface of the plastic layer;
The first resin layer includes a polyvinyl acetal resin,
As the first resin layer before being laminated on the plastic layer, the ten-point average roughness Rz measured in accordance with JIS B0601-1982 on the surface laminated on the plastic layer is 45 μm or less. An interlayer film for laminated glass obtained using the first resin layer. Young's modulus of the plastic layer is higher than Young's modulus of the first resin layer,
The interlayer film for laminated glass according to claim 1, wherein when the interlayer film includes the second resin layer, the Young's modulus of the plastic layer is higher than the Young's modulus of the second resin layer.   When the intermediate film includes the second resin layer, the second resin layer before being laminated to the plastic layer is compliant with JIS B0601-1982 on the surface laminated on the plastic layer. The interlayer film for laminated glass according to claim 1 or 2, obtained by using a second resin layer having a measured ten-point average roughness Rz of 45 µm or less. It said first resin layer comprises a soluble塑agent,
The interlayer film for laminated glass according to any one of claims 1 to 3, wherein when the interlayer film includes the second resin layer, the second resin layer includes a polyvinyl acetal resin and a plasticizer. . The interlayer film for laminated glass according to any one of claims 1 to 4 , comprising the second resin layer. The interlayer film for laminated glass according to any one of claims 1 to 5 , wherein the first resin layer contains an ultraviolet shielding agent. Comprising the second resin layer;
The interlayer film for laminated glass according to any one of claims 1 to 6 , wherein the second resin layer contains an ultraviolet shielding agent. The interlayer film for laminated glass according to any one of claims 1 to 7 , wherein the first resin layer contains an antioxidant. Comprising the second resin layer;
The interlayer film for laminated glass according to any one of claims 1 to 8 , wherein the second resin layer contains an antioxidant. A plastic layer Young's modulus is not less than 1 GPa, the ten-point average roughness Rz is measured according to JIS B0601-1982 of the surface of the side to be laminated on the plastic layer is Ri der less 45 [mu] m, and polyvinyl acetal resin by using the first resin layer including the first resin layer and the plastic layer by thermocompression bonding, and the plastic layer, wherein the first laminated on the first surface of the plastic layer An interlayer film for laminated glass comprising a resin layer of
A plastic layer Young's modulus is not less than 1 GPa, the ten-point average roughness Rz is measured according to JIS B0601-1982 of the surface of the side to be laminated on the plastic layer is Ri der less 45 [mu] m, and polyvinyl acetal resin And a second resin layer having a ten-point average roughness Rz measured in accordance with JIS B0601-1982 of the surface laminated on the plastic layer of 45 μm or less. The first resin layer and the first resin layer laminated on the first surface of the plastic layer by thermocompression bonding the first resin layer, the plastic layer, and the second resin layer. And a step of obtaining an interlayer film for laminated glass comprising a second resin layer laminated on a second surface opposite to the first surface of the plastic layer. Production method of the intermediate layer. The first resin layer and the plastic layer are heated to 65 ° C. or higher and 150 ° C. or lower by a roll-to-roll method, under pressure of 0.1 kN or higher and 5 kN or lower during pressure bonding, and under a tension of 100 N or lower during conveyance. The manufacturing method of the intermediate film for laminated glasses of Claim 10 which thermocompression-bonds. A first laminated glass member;
A second laminated glass member;
The interlayer film for laminated glass according to any one of claims 1 to 9 ,
Laminated glass in which the interlayer film for laminated glass is disposed between the first laminated glass member and the second laminated glass member. A step of obtaining an interlayer film for laminated glass by the method for producing an interlayer film for laminated glass according to claim 10 or 11,
Between the first laminated glass member and the second laminated glass member, by placing the laminated glass interlayer film for a first laminated glass member, and a second laminated glass member, for the laminated glass and a step of obtaining a laminated glass Ru and an intermediate layer, the combined manufacturing method of a glass.

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