JPWO2018181747A1 - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

Provided is an interlayer film for a laminated glass, which can enhance the bonding property at the time of producing the laminated glass, can increase the bending rigidity of the laminated glass at a high temperature, and can enhance the sound insulation of the laminated glass. The interlayer film for laminated glass according to the present invention is an interlayer film for laminated glass having a structure of one layer or two or more layers, and includes a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin. The glass transition temperature Tg of the component derived from the polyvinyl acetal resin contained is 80 ° C. or more, and the shear storage modulus G ′ at 70 ° C. is 5 MPa or more and 500 MPa or less, and the formula: (log (G ′ (Tg− 5))-log (G '(Tg)) / 5 The formula of the value B obtained from: (log (G' (Tg-20 ° C))-log (G '(Tg-10 ° C))) The ratio B / A to the value A obtained from / 10 is 3 or more.

Description

  The present invention relates to an interlayer film for a laminated glass used for obtaining a laminated glass. The present invention also relates to a laminated glass using the interlayer film for a laminated glass.

  Even if the laminated glass is damaged by an external impact, the amount of glass fragments scattered is small and the laminated glass is excellent in safety. For this reason, the laminated glass is widely used in automobiles, railway vehicles, aircraft, ships, buildings, and the like. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between two glass plates.

  As an example of the interlayer film for laminated glass, Patent Literature 1 listed below discloses 100 parts by weight of a polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and at least one of an alkali metal salt and an alkaline earth metal salt. Discloses a sound insulating layer containing 0.001 to 1.0 parts by weight of a metal salt and a plasticizer exceeding 30 parts by weight. This sound insulation layer can be used as an interlayer in a single layer.

  Further, Patent Literature 1 below describes a multilayer interlayer in which the sound insulation layer and another layer are stacked. Other layers to be laminated on the sound insulation layer include 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of an alkali metal salt and an alkaline earth metal salt of 0.001 to 0.001. 1.0 part by weight and a plasticizer of 30 parts by weight or less.

  Patent Document 2 listed below discloses an intermediate film that is a polymer layer having a glass transition temperature of 33 ° C. or higher. Patent Literature 2 describes that the polymer layer is disposed between glass plates having a thickness of 4.0 mm or less.

JP 2007-070200 A US2013 / 0236911A1

  In a laminated glass using a conventional interlayer film as described in Patent Documents 1 and 2, bending rigidity may be low. For this reason, for example, when a laminated glass is used as a window glass for a side door of an automobile, there is no frame for fixing the laminated glass, and bending of the laminated glass due to low rigidity of the laminated glass causes the laminated glass to have a small thickness. Opening and closing may be hindered.

  In recent years, in order to reduce the weight of laminated glass, it is required to reduce the thickness of a glass plate. In a laminated glass having an interlayer film sandwiched between two glass plates, there is a problem that it is extremely difficult to maintain sufficiently high bending rigidity when the thickness of the glass plates is reduced.

  For example, even if the thickness of the glass plate is thin, if the bending rigidity of the laminated glass can be increased due to the interlayer film, the weight of the laminated glass can be reduced. When the laminated glass is lightweight, the amount of material used for the laminated glass can be reduced, and the environmental load can be reduced. Furthermore, when a lightweight laminated glass is used for an automobile, fuel efficiency can be improved, and as a result, the environmental load can be reduced.

  Further, the laminated glass used for automobiles and the like sometimes has a considerably high temperature of about 70 ° C. Further, when the thickness of the glass plate is small, the rigidity of the interlayer film has a large effect, and the bending rigidity of the laminated glass at high temperatures tends to be low. With a conventional interlayer film, it is difficult to sufficiently increase the bending rigidity of the laminated glass at a high temperature of about 70 ° C.

  On the other hand, if the interlayer film is made relatively hard in order to increase the bending rigidity at a high temperature, the bonding property at the time of producing a laminated glass is reduced. For example, a portion where the interlayer film and the glass plate do not adhere to each other easily occurs. As a result, air bubbles remain or partial peeling occurs in the laminated glass.

  It is difficult for a conventional interlayer film to achieve both excellent laminating property at the time of producing a laminated glass and high bending rigidity at a high temperature.

  Further, it is desired that the laminated glass using the interlayer film has high sound insulation in addition to high bonding property and bending rigidity.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a laminated glass intermediate which can enhance the bonding property during the production of a laminated glass, increase the bending rigidity of the laminated glass at high temperatures, and enhance the sound insulation of the laminated glass. Is to provide a membrane. Another object of the present invention is to provide a laminated glass using the interlayer film for laminated glass.

  According to a broad aspect of the present invention, an interlayer film for laminated glass having a structure of one layer or two or more layers, including a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin, is included in the interlayer film. The glass transition temperature Tg of the component derived from the polyvinyl acetal resin is 80 ° C. or more, the shear storage modulus G ′ at 70 ° C. is 5 MPa or more and 500 MPa or less, and the formula: (log (G ′ (Tg−5 ° C.) ))-Log (G '(Tg))) / 5, the formula: (log (G' (Tg-20 ° C))-log (G '(Tg-10 ° C))) / 10 Provided is an interlayer film for laminated glass (hereinafter, sometimes referred to as an interlayer film) having a ratio B / A to a value A, which is more determined, of 3 or more.

  In a specific aspect of the intermediate film according to the present invention, the intermediate film includes a first layer including both the polyvinyl acetal resin and the second resin.

  In a specific aspect of the intermediate film according to the present invention, the second resin has a glass transition temperature of −20 ° C. or more and 0 ° C. or less.

  In a specific aspect of the intermediate film according to the present invention, the content of the second resin is 20% by weight or more based on a total of 100% by weight of the polyvinyl acetal resin and the second resin.

  In a specific aspect of the intermediate film according to the present invention, the gel fraction determined by the following formula (X) is 10% by weight or more.

Gel fraction (% by weight) = W2 / W1 × 100 Formula (X)
W1: Weight of the intermediate film before immersing the intermediate film in tetrahydrofuran at 23 ° C. W2: Weight of the intermediate film after immersion in the tetrahydrofuran at 23 ° C. and taken out and dried

  In a specific aspect of the interlayer according to the present invention, the shear storage modulus G ′ at 70 ° C. is 10 MPa or more and 500 MPa or less.

  In a specific aspect of the intermediate film according to the present invention, the polyvinyl acetal resin contained in the intermediate film is a polyvinyl acetoacetal resin, a polyvinyl butyral resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal resin.

  In a specific aspect of the intermediate film according to the present invention, a component derived from the polyvinyl acetal resin contained in the intermediate film has a glass transition temperature of 80 ° C or more and 120 ° C or less.

  In one specific aspect of the interlayer according to the present invention, the interlayer includes a plasticizer.

  In a specific aspect of the intermediate film according to the present invention, the thickness is 3 mm or less.

  In a specific aspect of the intermediate film according to the present invention, the intermediate film uses a first glass plate having a thickness of 1.6 mm or less, and is disposed between the first glass plate and the second glass plate. Placed and used to obtain a laminated glass.

  In one specific aspect of the intermediate film according to the present invention, the intermediate film is disposed between a first glass plate and a second glass plate, and is used for obtaining a laminated glass; The sum of the thickness of the plate and the thickness of the second glass plate is 3.5 mm or less.

  According to a broad aspect of the present invention, it includes a first laminated glass member, a second laminated glass member, and the above-described interlayer film for laminated glass, wherein the first laminated glass member and the second laminated glass are provided. A laminated glass is provided, in which the interlayer film for a laminated glass is arranged between members.

  In a specific aspect of the laminated glass according to the present invention, the first laminated glass member is a first glass plate, and the thickness of the first glass plate is 1.6 mm or less.

  In a specific aspect of the laminated glass according to the present invention, the first laminated glass member is a first glass plate, the second laminated glass member is a second glass plate, and the first glass The sum of the thickness of the plate and the thickness of the second glass plate is 3.5 mm or less.

  The interlayer film for laminated glass according to the present invention is an interlayer film for laminated glass having a structure of one layer or two or more layers. The interlayer film for a laminated glass according to the present invention includes a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin. The component derived from the polyvinyl acetal resin contained in the interlayer film for laminated glass according to the present invention has a glass transition temperature of 80 ° C or higher. In the interlayer film for laminated glass according to the present invention, the shear storage modulus G ′ at 70 ° C. is 5 MPa or more and 500 MPa or less. In the interlayer film for a laminated glass according to the present invention, the value B obtained from the formula: (log (G ′ (Tg−5 ° C.)) − Log (G ′ (Tg))) / 5 is represented by the formula: (log (G The ratio B / A to the value A calculated from '(Tg-20 ° C))-log (G' (Tg-10 ° C)) / 10 is 3 or more. Since the interlayer film for laminated glass according to the present invention has the above-described configuration, it is possible to enhance the bonding property when producing a laminated glass using the interlayer film for laminated glass according to the present invention. The bending rigidity at high temperature can be increased, and the sound insulation of the laminated glass can be enhanced.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a second embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing one example of a laminated glass using the laminated glass intermediate film shown in FIG. FIG. 4 is a cross-sectional view schematically showing one example of a laminated glass using the laminated glass intermediate film shown in FIG. FIG. 5 is a schematic diagram for explaining a method for measuring bending stiffness. FIG. 6 is a diagram illustrating the relationship between G ′ and temperature in Example 11 and Comparative Example 4.

  Hereinafter, the present invention will be described in detail.

(Interlayer for laminated glass)
The interlayer film for a laminated glass according to the present invention (hereinafter sometimes referred to as an interlayer film) has a structure of one layer or a structure of two or more layers. The intermediate film according to the present invention may have a single-layer structure, or may have a two- or more-layer structure. The intermediate film according to the present invention may have a two-layer structure, may have a two or more layer structure, may have a three-layer structure, may have a three-layer structure May be provided. The intermediate film according to the present invention includes a first layer. The intermediate film according to the present invention may be a single-layer intermediate film including only the first layer, or may be a multilayer intermediate film including the first layer and another layer.

  The intermediate film according to the present invention includes a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin. A resin other than the polyvinyl acetal resin is referred to as a second resin to distinguish it from the polyvinyl acetal resin.

  The glass transition temperature Tg of the component derived from the polyvinyl acetal resin contained in the interlayer film according to the present invention is 80 ° C. or higher.

  The shear storage modulus G ′ (70 ° C.) at 70 ° C. of the interlayer film according to the present invention is 5 MPa or more and 500 MPa or less.

  In the intermediate film according to the present invention, the value B obtained from the formula: (log (G ′ (Tg−5 ° C.)) − Log (G ′ (Tg))) / 5 is expressed by the formula: (log (G ′ (Tg) −20 ° C.))-Log (G ′ (Tg−10 ° C.))) The ratio B / A to the value A obtained from / 10 is 3 or more.

  Since the intermediate film according to the present invention has the above-described configuration, it is possible to enhance the bonding property when the laminated glass according to the present invention is manufactured. During the production of the laminated glass, the interlayer film and the laminated glass member are easily bonded. As a result, bubbles are less likely to remain in the laminated glass, and partial peeling is less likely to occur.

  Moreover, since the intermediate film according to the present invention has the above-described configuration, the bending rigidity of the laminated glass using the intermediate film according to the present invention at a high temperature can be increased. In particular, the bending rigidity at 70 ° C. can be increased. Further, the flexural rigidity at 40 ° C. and 60 ° C. can be increased. In addition, the bending rigidity of the interlayer at 20 ° C. can be increased. Further, in order to obtain a laminated glass, the interlayer film is often arranged between the first glass plate and the second glass plate. Even if the thickness of the first glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. Further, even when both the first glass plate and the second glass plate are thin, the bending rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. When the thickness of both the first glass plate and the second glass plate is large, the bending rigidity of the laminated glass is further increased.

  With a conventional interlayer, it is difficult to sufficiently increase bending rigidity over a wide temperature range including room temperature and high temperature. For example, even if the flexural rigidity at normal temperature is high, the flexural rigidity at high temperature is low, or even if the flexural rigidity at high temperature is high, the flexural rigidity at normal temperature is low. On the other hand, in the present invention, the bending rigidity can be increased over a wide temperature range (for example, 20 ° C., 40 ° C., 60 ° C., and 70 ° C.).

  In the present invention, it is possible to achieve both excellent laminating property at the time of producing a laminated glass and high bending rigidity at a high temperature.

  Furthermore, since the interlayer according to the present invention has the above-described configuration, the sound insulation of the laminated glass using the interlayer according to the present invention can be enhanced.

  Since the intermediate film contains a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin, the sound insulation is effectively increased.

  Since the glass transition temperature Tg (hereinafter, sometimes referred to as Tg) of the component derived from the polyvinyl acetal resin is 80 ° C. or higher, the bending rigidity at a high temperature is improved. From the viewpoint of further improving the bending rigidity at a high temperature, the above Tg is preferably 85 ° C. or more. From the viewpoint of further improving the bending rigidity at high temperatures, the glass transition temperature of the polyvinyl acetal resin is preferably 120 ° C or lower, more preferably 110 ° C or lower. When the intermediate film contains a plurality of polyvinyl acetal resins, it is preferable that the glass transition temperature having the highest glass transition temperature among the components derived from the polyvinyl acetal resin satisfies the above temperature.

  When the intermediate film contains an additive such as a plasticizer described below, the glass transition temperature Tg of the component derived from the polyvinyl acetal resin is the glass transition temperature of the polyvinyl acetal resin composition containing the polyvinyl acetal resin and the additive. Means temperature.

  From the viewpoint of further improving the sound insulation, the glass transition temperature of the component derived from the second resin is preferably -25 ° C or higher, more preferably -20 ° C or higher. From the viewpoint of further improving the sound insulation, the glass transition temperature of the component derived from the second resin is preferably 0 ° C or lower, more preferably -1 ° C or lower.

  When the intermediate film contains an additive such as a plasticizer to be described later, the glass transition temperature Tg of the component derived from the second resin is determined by the second resin composition containing the second resin and the additive. Means the glass transition temperature.

  As a method for measuring the glass transition temperature, immediately after storing the interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a viscoelasticity measuring device “DVA manufactured by IT Measurement Control Co., Ltd.” A method of measuring viscoelasticity using “−200”. The intermediate film was cut out at a length of 8 mm and a width of 5 mm, and the temperature was increased from −50 ° C. to 150 ° C. in a shearing mode at a rate of 3 ° C./min, and the frequency was 1 Hz and the strain was 0.08%. Preferably, the glass transition temperature is measured.

  Since the storage elastic modulus G ′ (70 ° C.) at 70 ° C. of the interlayer film is 5 MPa or more and 500 MPa or less, the bending rigidity is improved. From the viewpoint of further improving the bending rigidity, the shear storage modulus at 70 ° C. of the interlayer film is preferably 10 MPa or more. From the viewpoint of further improving the handling property, the shear storage modulus at 70 ° C. of the interlayer film is preferably 300 MPa or less.

  In the case where the interlayer is a multilayer interlayer, the shear storage modulus means a shear storage equivalent modulus. The above-mentioned shear storage equivalent elastic modulus indicates a shear storage elastic modulus when the multilayer body is regarded as a single layer. When there is no slip between the layers, for example, the shear storage equivalent modulus is measured by measuring the shear storage modulus by a general dynamic viscoelasticity measurement method with the layer configuration constituting the interlayer film as it is. Can be.

  The above-mentioned shear storage elastic modulus and the above-mentioned shear storage equivalent elastic modulus are obtained as follows.

  As a method for measuring the above-mentioned shear storage elastic modulus and the above-mentioned shear storage equivalent elastic modulus, immediately after storing the interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, it is manufactured by IT Measurement Control Co., Ltd. And a method of measuring viscoelasticity using a viscoelasticity measuring apparatus “DVA-200”. The intermediate film was cut out at a length of 8 mm and a width of 5 mm, and measured in a shearing mode at a rate of 3 ° C./min to increase the temperature from −50 ° C. to 150 ° C., and at a frequency of 1 Hz and a strain of 0.08%. Is preferred.

  The shear storage equivalent elastic modulus G '* is obtained by the following equation (A).

  G ′ * = (Σiai) / (Σiai / G′i) Expression (A)

  In the above formula (A), G'i represents the shear storage modulus of the i-th layer in the interlayer, and ai represents the thickness of the i-th layer in the interlayer. Σi means that the sum of the numerical values of the i-th layer is calculated.

  In the above intermediate film, the value B obtained from the formula: (log (G ′ (Tg−5 ° C.)) − Log (G ′ (Tg))) / 5 is expressed by the following formula: (log (G ′ (Tg−20 ° C.)) ))-Log (G ′ (Tg−10 ° C.))) Since the ratio B / A to the value A obtained from / 10 is 3 or more, the bending stiffness and bonding property at high temperatures are improved. The ratio B / A is preferably 3.5 or more from the viewpoint of further improving the bending rigidity and the bonding property at a high temperature. The ratio B / A may be 30 or less.

  When the intermediate film contains an additive such as a plasticizer described below, the glass transition temperature Tg of the component derived from the second resin is the second resin containing the second resin and the additive. It means the glass transition temperature of the composition. The value A means a change in G 'from Tg-20C to Tg-10C, and the value B means a change in G' from Tg-5C to Tg. The value of the ratio B / A increases as the value A decreases or the value B increases.

  When the intermediate film contains an additive such as a plasticizer described below, the glass transition temperature Tg of the component derived from the second resin is the second resin containing the second resin and the additive. It means the glass transition temperature of the composition.

  In order to make the ratio B / A fall within the above range, a method of crosslinking a polyvinyl acetal resin, a method of crosslinking a second resin, a method of crosslinking a polyvinyl acetal resin and a second resin, and A method of blending a filler and the like can be given.

  The value A and the value B are obtained as follows.

  As a method for measuring the above-mentioned values A and B, immediately after storing the interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a viscoelasticity measuring device manufactured by IT Measurement Control Co., Ltd. A method of measuring viscoelasticity using “DVA-200” is exemplified. The intermediate film was cut out at a length of 8 mm and a width of 5 mm, and measured in a shearing mode at a rate of 3 ° C./min to increase the temperature from −50 ° C. to 150 ° C., and at a frequency of 1 Hz and a strain of 0.08%. Is preferred.

  From the viewpoint of further increasing the bending stiffness, the gel fraction of the above intermediate film, which is determined by the following formula (X), is preferably 10% by weight or more. From the viewpoint of further improving the penetration resistance, the gel fraction of the above intermediate film determined by the following formula (X) is preferably 10% by weight or more, and more preferably 80% by weight or less. When the gel fraction is 10% by weight or more, the effect of improving the bending rigidity and the penetration resistance increases. When the gel fraction is 80% by weight or less, the penetration resistance is considerably increased. From the viewpoint of further increasing bending rigidity and penetration resistance, the gel fraction is more preferably 30% by weight or more. From the viewpoint of further improving the penetration resistance, the gel fraction is more preferably 50% by weight or less.

Gel fraction (% by weight) = W2 / W1 × 100 Formula (X)
W1: Weight of the intermediate film before immersing the intermediate film in tetrahydrofuran at 23 ° C. W2: Weight of the intermediate film after immersion in the tetrahydrofuran at 23 ° C. and taken out and dried

  From the viewpoint of further increasing bending rigidity and penetration resistance, the intermediate film preferably includes a first layer containing both the polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin.

  From the viewpoint of further increasing the bending stiffness and the penetration resistance, the intermediate film preferably has a phase separation structure. It is considered that one of the factors that exerts these effects is that energy distribution smoothly proceeds due to the phase separation structure.

  The phase separation structure is preferably a bicontinuous structure or a sea-island structure. The phase separation structure may be a bicontinuous structure or a sea-island structure. It is preferable that the polyvinyl acetal resin and the second resin are included in different phases. In the case of a sea-island structure, the polyvinyl acetal resin may be a sea portion, and the second resin may be an island portion, wherein the second resin is a sea portion and the polyvinyl acetal resin is an island portion. You may. In the phase separation structure, the polyvinyl acetal resin may be continuous (having a continuous structure), and the second resin may be continuous (having a continuous structure). Well), the polyvinyl acetal resin and the second resin may form a co-continuous structure. In the phase separation structure, the polyvinyl acetal resin may be present in a network, and the second resin may be present in a network. From the viewpoint of excellent effects of the present invention, it is preferable that the polyvinyl acetal resin and the second resin have a sea-island structure or a bicontinuous structure. That is, in the phase separation structure, it is preferable that the polyvinyl acetal resin and the second resin form a sea-island structure or a bicontinuous structure.

  In the phase-separated structure, the average of the diameters of the islands is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, particularly preferably 30 nm or more, preferably 13 μm or less, more preferably 10 μm or less, and still more preferably. Is 2 μm or less, particularly preferably 1 μm or less. The diameter of each island indicates the maximum diameter, and the average of the diameters of the islands is obtained by averaging the diameters (maximum diameters) of the plurality of islands.

  The intermediate film may have a structure of two or more layers, and may include a second layer in addition to the first layer. Preferably, the intermediate film further includes a second layer. When the intermediate film includes the second layer, the second layer is disposed on the first surface side of the first layer.

  The intermediate film may have a structure of three or more layers, and may include a third layer in addition to the first layer and the second layer. It is preferable that the intermediate film further includes a third layer. When the intermediate film includes the second layer and the third layer, the third layer is disposed on a second surface side of the first layer opposite to the first surface. You.

  The surface of the second layer opposite to the first layer is preferably a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the second layer is preferably 1.6 mm or less, more preferably 1.3 mm or less. The second surface opposite to the first surface (the surface on the second layer side) of the first layer may be a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the first layer is preferably 1.6 mm or less, more preferably 1.3 mm or less. It is preferable that the surface of the third layer opposite to the first layer is a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the third layer is preferably 1.6 mm or less, more preferably 1.3 mm or less.

  The intermediate film is disposed between the first glass plate and the second glass plate, and is suitably used for obtaining a laminated glass. Since the flexural rigidity can be sufficiently increased due to the interlayer, the total of the thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, more preferably 3 mm. It is as follows. The intermediate film is disposed between the first glass plate and the second glass plate, and is suitably used for obtaining a laminated glass. Since the bending stiffness can be sufficiently increased due to the intermediate film, the intermediate film is formed by using a first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). It is disposed between the first glass plate and the second glass plate and is suitably used for obtaining a laminated glass. The intermediate film includes a first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less) and a second glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). It is used between the said 1st glass plate and the said 2nd glass plate, and is used more suitably for obtaining laminated glass. Also in this case, the bending rigidity can be sufficiently increased due to the intermediate film.

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

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

  The intermediate film 11 shown in FIG. 1 is a multilayer intermediate film having a structure of two or more layers. The intermediate film 11 is used to obtain a laminated glass. The interlayer 11 is an interlayer for laminated glass. The intermediate film 11 includes a first layer 1, a second layer 2, and a third layer 3. The second layer 2 is disposed on the first surface 1a of the first layer 1 and is laminated. The third layer 3 is disposed on the second surface 1b of the first layer 1 opposite to the first surface 1a, and is laminated. The first layer 1 is an intermediate layer. Each of the second layer 2 and the third layer 3 is a protective layer, and is a surface layer in the present embodiment. The first layer 1 is disposed between the second layer 2 and the third layer 3 and is sandwiched therebetween. Therefore, the intermediate film 11 has a multilayer structure (second layer 2 / first layer 1 / third layer 3) in which the second layer 2, the first layer 1, and the third layer 3 are stacked in this order. Layer 3).

  Note that other layers may be disposed between the second layer 2 and the first layer 1 and between the first layer 1 and the third layer 3, respectively. It is preferable that the second layer 2 and the first layer 1 and the first layer 1 and the third layer 3 are each directly laminated. As another layer, a layer containing polyethylene terephthalate or the like can be mentioned.

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

  The intermediate film 11A shown in FIG. 2 is a single-layer intermediate film having a one-layer structure. The intermediate film 11A is a first layer. The intermediate film 11A is used to obtain a laminated glass. The intermediate film 11A is an intermediate film for laminated glass.

  Hereinafter, the details of the first layer, the second layer, and the third layer constituting the intermediate film according to the present invention, and the first layer, the second layer, and the third layer will be described. The details of each component included will be described.

(resin)
The intermediate film includes a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin. It is preferable that each of the first layer, the second layer, and the third layer contains a polyvinyl acetal resin. It is preferable that the first layer, the second layer, and the third layer each include a second resin other than the polyvinyl acetal resin. As the polyvinyl acetal resin, only one kind may be used, or two or more kinds may be used in combination. As the second resin, only one kind may be used, or two or more kinds may be used in combination.

  In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the polyvinyl acetal resin is preferably 20% by weight or more, more preferably 25% by weight or more, and still more preferably 30% by weight or more. It is particularly preferably at least 35% by weight, preferably less than 100% by weight. When the content of the polyvinyl acetal resin is equal to or more than the lower limit, the bending rigidity is effectively increased. In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the polyvinyl acetal resin may be 90% by weight or less, 80% by weight or less, or 75% by weight. Or less, 70% by weight or less, or 65% by weight or less.

  From the viewpoint of effectively increasing the affinity between the resin component and the plasticizer and effectively increasing the penetration resistance, the polyvinyl acetal resin is a polyvinyl acetoacetal resin, a polyvinyl butyral resin, a polyvinyl benzyl acetal resin or a polyvinyl cumin acetal. It is preferably a resin. From the viewpoint of further increasing the bending stiffness at 40 ° C., 60 ° C., and 70 ° C., the polyvinyl acetal resin is preferably a polyvinyl acetoacetal resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal resin. In particular, from the viewpoint of further increasing the bending stiffness at 60 ° C. and 70 ° C., the polyvinyl acetal resin is preferably a polyvinyl benzyl acetal resin or a polyvinyl cumin acetal resin. In the present specification, the polyvinyl acetal resin includes an acetoacetalized resin, a benzylacetalized resin, and a cuminacetalized resin.

  From the viewpoint of effectively increasing the bending rigidity and the sound insulation, the interlayer film includes a second resin other than the polyvinyl acetal resin. From the viewpoint of effectively increasing bending rigidity and sound insulation, the first layer, the second layer, and the third layer each preferably include a second resin other than the polyvinyl acetal resin. Examples of the second resin include a thermosetting resin and a thermoplastic resin. The intermediate film preferably contains a thermoplastic resin (a second thermoplastic resin other than the polyvinyl acetal resin) as the second resin. A thermoplastic resin other than the polyvinyl acetal resin may be referred to as a second thermoplastic resin to be distinguished from the polyvinyl acetal resin. As the second resin, only one kind may be used, or two or more kinds may be used in combination.

  From the viewpoint of effectively increasing the bending rigidity and the sound insulation, the interlayer film preferably contains a resin that is incompatible with the polyvinyl acetal resin as the second resin. From the viewpoint of effectively increasing bending rigidity and sound insulation, the interlayer film preferably contains a polyolefin resin, an acrylic polymer, a urethane polymer, a silicone polymer, a rubber, or a vinyl acetate polymer. From the viewpoint of effectively increasing the bending stiffness and the sound insulation, it is more preferable that the interlayer film contains an acrylic polymer that easily balances the performance.

  The acrylic polymer is preferably a polymer of a polymerizable component containing a (meth) acrylate. The acrylic polymer is preferably a poly (meth) acrylate.

  The poly (meth) acrylate is not particularly limited. Examples of the poly (meth) acrylate include poly (methyl) acrylate, poly (ethyl) acrylate, n-propyl poly (meth) acrylate, i-propyl poly (meth) acrylate, and poly (meth) acrylate. N-butyl (meth) acrylate, i-butyl poly (meth) acrylate, t-butyl poly (meth) acrylate, 2-ethylhexyl poly (meth) acrylate, 2-hydroxyethyl poly (meth) acrylate, 2-hydroxypropyl poly (meth) acrylate, 4-hydroxybutyl poly (meth) acrylate, glycidyl poly (meth) acrylate, octyl poly (meth) acrylate, propyl poly (meth) acrylate, poly (meth) 2-ethyloctyl acrylate, nonyl poly (meth) acrylate, isononyl poly (meth) acrylate, Decyl (meth) acrylate, isodecyl poly (meth) acrylate, lauryl poly (meth) acrylate, isotetradecyl poly (meth) acrylate, cyclohexyl poly (meth) acrylate, isobornyl poly (meth) acrylate, And polybenzyl (meth) acrylate. Further, (meth) acrylic acid having a polar group and (meth) acrylic acid ester include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and Glycidyl (meth) acrylate and the like can be mentioned. In the dynamic viscoelasticity spectrum, the temperature at which the maximum value of tan δ is attained can be easily controlled within an appropriate range. Therefore, polyacrylate is preferred, and polyethyl acrylate, poly-n-butyl acrylate, and polyacryl are preferred. 2-ethylhexyl acid or octyl polyacrylate is more preferred. By using these preferred poly (meth) acrylates, the balance between the productivity of the interlayer and the properties of the interlayer is further improved. Only one kind of the poly (meth) acrylate may be used, or two or more kinds may be used in combination.

  In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the second resin other than the polyvinyl acetal resin is preferably 20% by weight or more, more preferably 25% by weight or more, and still more preferably 30% by weight or more. % Or more, particularly preferably 35% or more, and preferably less than 100% by weight. When the content of the second resin is equal to or more than the lower limit, the bending rigidity, the bonding property, and the sound insulation property are effectively increased. In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the second resin is preferably 90% by weight or less, more preferably 80% by weight or less, and further preferably 75% by weight or less. It is particularly preferably at most 70% by weight, most preferably at most 65% by weight. When the content of the second resin is equal to or less than the upper limit, the bending rigidity, the bonding property, and the sound insulation property are effectively increased.

  In a total of 100% by weight of the polyvinyl acetal resin and the acrylic polymer, the content of the acrylic polymer is preferably 20% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more, and particularly preferably. It is at least 35% by weight, preferably less than 100% by weight. When the content of the acrylic polymer is not less than the lower limit, the bending rigidity is effectively increased. In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the acrylic polymer is preferably 90% by weight or less, more preferably 80% by weight or less, further preferably 75% by weight or less, It is particularly preferably at most 70% by weight, most preferably at most 65% by weight. When the content of the acrylic polymer is equal to or less than the upper limit, the bending rigidity, the bonding property, and the sound insulating property are effectively increased.

  It is preferable that the second resin has a crosslinked structure or that the polyvinyl acetal resin and the second resin are crosslinked. The intermediate film may include the polyvinyl acetal resin and the second resin as a crosslinked product in which the polyvinyl acetal resin and the second resin are crosslinked. The thermoplastic resin may have a crosslinked structure. By the above crosslinked structure, the shear storage modulus can be controlled, and an interlayer having both excellent flexibility and high strength can be produced.

  Examples of the method for crosslinking the resin include the following methods. A method in which functional groups that react with each other are introduced into a polymer structure of a resin to form crosslinks. A method of crosslinking using a crosslinking agent having two or more functional groups that react with a functional group present in a polymer structure of a resin. A method of crosslinking a polymer using a radical generator having a hydrogen abstracting ability such as a peroxide. A method of crosslinking by electron beam irradiation. Since the shear storage modulus can be easily controlled and the productivity of the interlayer increases, it is preferable to introduce crosslinkable functional groups into the polymer structure of the resin and form a crosslink.

  When the intermediate film contains a crosslinked product of the polyvinyl acetal resin and the second resin, the glass transition temperature of the polyvinyl acetal resin is the glass transition temperature of a component derived from the polyvinyl acetal resin in the crosslinked product. And the glass transition temperature of the second resin indicates a glass transition temperature of a component derived from the second resin in the crosslinked product.

  The first layer (including a single-layer intermediate film) preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (1)). The first layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)) as the thermoplastic resin (1). When the intermediate film is a single-layer intermediate film including only the first layer, the intermediate film includes the polyvinyl acetal resin (1). The second layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (2)). The second layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (2)) as the thermoplastic resin (2). The third layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (3)). The third layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (3)) as the thermoplastic resin (3). The polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different. It is preferable that the polyvinyl acetal resin (1) is different from the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) because the sound insulating property is further improved. The thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be the same or different. Each of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be used alone or in combination of two or more. Each of the thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be used alone or in combination of two or more.

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

  The polyvinyl acetal resin is preferably an acetalized product of polyvinyl alcohol. The polyvinyl alcohol is obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is generally 70 to 99.9 mol%.

  The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, even more preferably 1500 or more, further preferably 1600 or more, particularly preferably 2600 or more, and most preferably 2700 or more, and preferably It is 5000 or less, more preferably 4000 or less, and still more preferably 3500 or less. When the average degree of polymerization is not less than the lower limit, the penetration resistance and bending rigidity of the laminated glass are further increased. When the average degree of polymerization is equal to or less than the upper limit, molding of the interlayer film becomes easy.

  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 in the polyvinyl acetal resin is preferably 2 to 10, and more preferably 2, 7 or 10 from the viewpoint of effectively increasing the flexural rigidity at high temperatures. Further, the number of carbon atoms of the acetal group in the polyvinyl acetal resin is preferably 2 or 4, and in this case, the production of the polyvinyl acetal resin is efficient.

  Generally, an aldehyde having 1 to 10 carbon atoms is suitably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, Examples include n-nonyl aldehyde, n-decyl aldehyde, cumin aldehyde, and benzaldehyde. Acetaldehyde, n-butyraldehyde, isobutyraldehyde, cuminaldehyde or benzaldehyde is preferred, and acetaldehyde, n-butyraldehyde, isobutyraldehyde, cuminaldehyde or benzaldehyde is more preferred. Acetaldehyde, n-butyraldehyde, cuminaldehyde or benzaldehyde are more preferred. As the aldehyde, only one kind may be used, or two or more kinds may be used in combination.

  When the polyvinyl acetal resin (1) is used as a part of a single-layer intermediate film, the content of hydroxyl groups (the amount of hydroxyl groups) of the polyvinyl acetal resin (1) is preferably in the following range. The hydroxyl group content (hydroxyl amount) of the polyvinyl acetal resin (1) is preferably 25 mol% or more, more preferably 28 mol% or more, more preferably 30 mol% or more, and still more preferably 31.5 mol%. It is more preferably at least 32 mol%, particularly preferably at least 33 mol%. The content of hydroxyl groups (amount of hydroxyl groups) in the polyvinyl acetal resin (1) is preferably 45 mol% or less, more preferably 43 mol% or less, and further preferably 41 mol% or less. When the content of the hydroxyl group is not less than the lower limit, the bending rigidity is further increased, and the adhesive strength of the interlayer is further increased. When the content of the hydroxyl group is equal to or less than the upper limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated.

  When the polyvinyl acetal resin (1) is used as a part of a multilayer interlayer, the content of hydroxyl groups (the amount of hydroxyl groups) of the polyvinyl acetal resin (1) is preferably in the following range. The hydroxyl group content (hydroxyl amount) of the polyvinyl acetal resin (1) is preferably at least 17 mol%, more preferably at least 20 mol%, further preferably at least 22 mol%, preferably at most 45 mol%, more preferably Is at most 43 mol%, more preferably at most 41 mol%. When the content of the hydroxyl group is not less than the lower limit, the bending rigidity is further increased, and the adhesive strength of the interlayer is further increased. When the content of the hydroxyl group is equal to or less than the upper limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated. In particular, when the hydroxyl group content of the polyvinyl acetal resin (1) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and when it is 45 mol% or less, the sound insulation of the laminated glass is further enhanced. . Further, the laminated glass using the interlayer film in which the content of hydroxyl groups in the polyvinyl acetal resin (1) is 28 mol% or less tends to have low flexural rigidity. Can be improved.

  The content of each hydroxyl group in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, more preferably 30 mol% or more, and still more preferably. It is at least 31.5 mol%, more preferably at least 32 mol%, particularly preferably at least 33 mol%. The content of hydroxyl groups in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 45 mol% or less, more preferably 43 mol% or less, and further preferably 41 mol% or less. When the content of the hydroxyl group is not less than the lower limit, the bending rigidity is further increased, and the adhesive strength of the interlayer is further increased. When the content of the hydroxyl group is equal to or less than the upper limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated.

  The hydroxyl group content of the polyvinyl acetal resin is a value obtained by dividing the amount of ethylene groups to which the hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, and is expressed as a percentage. The amount of the ethylene group to which the hydroxyl group is bonded can be measured, for example, in accordance with JIS K6728 “Testing method for polyvinyl butyral”.

  The degree of acetylation (the amount of acetyl group) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, and further preferably 9 mol% or more. It is at least mol%, preferably at most 30 mol%, more preferably at most 25 mol%, even more preferably at most 24 mol%. When the degree of acetylation is equal to or more than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer or other thermoplastic resin is increased, and the sound insulation and the penetration resistance are further improved. When the acetylation degree is equal to or less than the upper limit, the interlayer film and the laminated glass have high moisture resistance. In particular, when the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol% or more and 25 mol% or less, the penetration resistance is further improved.

  The degree of acetylation of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably at least 0.01 mol%, more preferably at least 0.5 mol%, and preferably at most 10 mol%, more preferably Is not more than 2 mol%. When the acetylation degree is equal to or more than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the acetylation degree is equal to or less than the upper limit, the interlayer film and the laminated glass have high moisture resistance.

  The degree of acetylation is a value expressed as a percentage in terms of a mole fraction obtained by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain. The amount of the ethylene group to which the acetyl group is bonded can be measured, for example, in accordance with JIS K6728 “Testing method for polyvinyl butyral”.

  The degree of acetalization (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (1) is preferably at least 47 mol%, more preferably at least 50 mol%, further preferably at least 68 mol%, preferably at least 68 mol%. It is at most 85 mol%, more preferably at most 80 mol%, even more preferably at most 75 mol%. When the acetalization degree is equal to or more than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing a polyvinyl acetal resin becomes short.

  The degree of acetalization (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably at least 55 mol%, more preferably at least 57 mol%, preferably Is at most 75 mol%, more preferably at most 71 mol%. When the acetalization degree is equal to or more than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing a polyvinyl acetal resin becomes short.

  The degree of acetalization is determined as follows. First, a value is obtained by subtracting the amount of ethylene groups to which hydroxyl groups are bonded and the amount of ethylene groups to which acetyl groups are bonded from the total amount of ethylene groups in the main chain. The obtained value is divided by the total amount of ethylene groups in the main chain to determine the mole fraction. The value of this mole fraction expressed as a percentage is the degree of acetalization.

  The hydroxyl content (hydroxyl content), acetalization degree (butyralization degree) and acetylation degree are preferably calculated from the results measured by a method based on JIS K6728 "Testing method for polyvinyl butyral". However, measurement according to ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl content (hydroxyl group content), the acetalization degree (butyralization degree) and the acetylation degree are determined according to JIS K6728 "Polyvinyl butyral test method". Can be calculated from the results measured by

(Plasticizer)
The intermediate film preferably contains a plasticizer. The first layer (including a single-layer intermediate film) preferably contains a plasticizer (hereinafter sometimes referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter sometimes referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (3)). By the use of a plasticizer, and by using a polyvinyl acetal resin and a plasticizer in combination, the penetration resistance is more excellent, and the adhesive force of the layer containing the polyvinyl acetal resin and the plasticizer to a laminated glass member or another layer is appropriately high. Become. The plasticizer is not particularly limited. The plasticizer (1), the plasticizer (2), and the plasticizer (3) may be the same or different. Each of the plasticizer (1), the plasticizer (2) and the plasticizer (3) may be used alone or in combination of two or more.

  Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. . Organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.

  Examples of the monobasic organic acid ester include a glycol ester obtained by reacting a glycol with a monobasic organic acid. 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, heptyl acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decyl acid.

  Examples of the polybasic organic acid ester 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.

  Examples of the organic ester plasticizer include triethylene glycol di-2-ethyl propanoate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl hexanoate, 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 Xanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicaprylate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate Dibutyl maleate, bis (2-butoxyethyl) adipate, dibutyl adipate, diisobutyl adipate, 2,2-butoxyethoxyethyl adipate, glycol benzoate, 1,3-butylene glycol polyester adipate, adipic acid Dihexyl, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisode adipate Le, Hepuchirunoniru adipic acid, tributyl citrate, acetyl tributyl citrate, diethyl carbonate, dibutyl sebacate, oil-modified sebacic alkyds, and mixtures of phosphoric acid esters and adipic acid esters. Organic ester plasticizers other than these may be used. Other adipates other than the above-mentioned adipates may be used.

  Examples of the organic phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, tricresyl phosphate, and triisopropyl phosphate.

  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 above 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 triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH) or triethylene glycol di-2-ethyl propanoate. . The plasticizer more preferably contains triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and further preferably contains triethylene glycol di-2-ethylhexanoate. preferable.

  In the second layer, 100 parts by weight of the thermoplastic resin (2) (or 100 parts by weight of the polyvinyl acetal resin (2) when the thermoplastic resin (2) is the polyvinyl acetal resin (2)). Let content of agent (2) be content (2). In the third layer, 100 parts by weight of the thermoplastic resin (3) (or 100 parts by weight of the polyvinyl acetal resin (3) when the thermoplastic resin (3) is the polyvinyl acetal resin (3)). Let content of agent (3) be content (3). The content (2) and the content (3) are preferably at least 10 parts by weight, more preferably at least 15 parts by weight, preferably at most 40 parts by weight, more preferably at most 35 parts by weight, and further preferably at most 32 parts by weight. It is at most 30 parts by weight, particularly preferably at most 30 parts by weight. When the content (2) and the content (3) are equal to or larger than the lower limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated. When the content (2) and the content (3) are equal to or less than the upper limit, the bending rigidity is further increased.

  In the first layer, 100 parts by weight of the thermoplastic resin (1) (or 100 parts by weight of the polyvinyl acetal resin (1) when the thermoplastic resin (1) is the polyvinyl acetal resin (1)). Let content of agent (1) be content (1). The content (1) is preferably at least 1 part by weight, more preferably at least 2 parts by weight, still more preferably at least 3 parts by weight, further preferably at least 5 parts by weight, preferably at most 90 parts by weight, more preferably at most 90 parts by weight. It is at most 85 parts by weight, more preferably at most 80 parts by weight. When the content (1) is equal to or more than the lower limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated. When the content (1) is equal to or less than the upper limit, the penetration resistance of the laminated glass is further increased. The content (1) may be 50 parts by weight or more, 55 parts by weight or more, or 60 parts by weight or more. The content (1) may be 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

(Heat shielding material)
The intermediate film preferably contains a heat-shielding substance (heat-shielding compound). It is preferable that the first layer contains a heat shielding material. The second layer preferably contains a heat-shielding substance. The third layer preferably contains a heat-shielding substance. The heat-insulating substance may be used alone, or two or more kinds may be used in combination.

  The heat-shielding substance preferably contains at least one component X of a phthalocyanine compound, a naphthalocyanine compound and an anthocyanin compound, or contains heat-insulating particles. In this case, both the component X and the heat shielding particles may be included.

Component X:
The intermediate film preferably contains at least one component X among a phthalocyanine compound, a naphthalocyanine compound, and an anthocyanin compound. The first layer preferably contains the component X. The second layer preferably contains the component X. The third layer preferably contains the component X. The component X is a heat-shielding substance. As the component X, only one type may be used, or two or more types may be used in combination.

  The component X is not particularly limited. As the component X, conventionally known phthalocyanine compounds, naphthalocyanine compounds, and anthocyanin compounds can be used.

  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, a phthalocyanine derivative, naphthalocyanine, and a naphthalocyanine derivative. And more preferably at least one of phthalocyanine and a derivative of phthalocyanine.

  The component X preferably contains a vanadium atom or a copper atom from the viewpoint of effectively increasing the heat shielding property and maintaining the visible light transmittance at a higher level for a long period of time. The component X preferably contains a vanadium atom, and more 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.

  In 100% by weight of the layer containing the component X (first layer, second layer or third layer), the content of the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight or more. % By weight, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more. The content of the component X in 100% by weight of the layer containing the component X (the first layer, the second layer, or the third layer) is preferably 0.2% by weight or less, more preferably 0.1% by weight or less. % By weight, more preferably 0.05% by weight or less, particularly preferably 0.04% by weight or less. When the content of the component X is equal to or higher than the lower limit and equal to or lower than the upper limit, the heat shielding property becomes sufficiently high and the visible light transmittance becomes sufficiently high. For example, the visible light transmittance can be set to 70% or more.

Thermal barrier particles:
It is preferable that the intermediate film contains heat shielding particles. It is preferable that the first layer (including a single-layer intermediate film) contains the heat shielding particles. The second layer preferably contains the heat shielding particles. The third layer preferably contains the heat shielding particles. The heat shielding particles are a heat shielding material. By using the heat shielding particles, infrared rays (heat rays) can be effectively blocked. Only one kind of the heat shielding particles may be used, or two or more kinds thereof may be used in combination.

  From the viewpoint of further increasing the heat shielding properties 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.

  Infrared light having a wavelength of 780 nm or more longer than visible light has a smaller energy amount than ultraviolet light. However, infrared rays have a large thermal effect, and are emitted as heat when infrared rays are absorbed by a substance. For this reason, infrared rays are generally called heat rays. By using the above-mentioned heat shielding particles, infrared rays (heat rays) can be effectively blocked. Note that the heat shielding particles mean particles that can absorb infrared rays.

Specific examples of the thermal barrier 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. Other heat shielding particles may be used. Metal oxide particles are preferred because they have a high heat ray shielding function, and ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferred, and ITO particles or tungsten oxide particles are particularly preferred. 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.

  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.

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. 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 size 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, and more preferably 0.05 μm or less. When the average particle diameter is equal to or more than the above lower limit, the heat ray shielding property is sufficiently high. When the average particle diameter is equal to or less than the upper limit, the dispersibility of the heat shielding particles increases.

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

  In 100% by weight of the layer containing the heat shielding particles (first layer, second layer or third layer), the content of the heat shielding particles is preferably at least 0.01% by weight, more preferably 0% by weight. 0.1% by weight or more, more preferably 1% by weight or more, particularly preferably 1.5% by weight or more. In 100% by weight of the layer containing the heat shielding particles (first layer, second layer or third layer), the content of the heat shielding particles is preferably 6% by weight or less, more preferably 5.5%. % By weight, more preferably 4% by weight or less, particularly preferably 3.5% by weight or less, most preferably 3% by weight or less. When the content of the heat shielding particles is equal to or more than the lower limit and equal to or less than the upper limit, the heat shielding property is sufficiently increased, and the visible light transmittance is sufficiently increased.

(Metal salt)
The intermediate film preferably contains at least one metal salt of an alkali metal salt, an alkaline earth metal salt and a magnesium salt (hereinafter sometimes referred to as a metal salt M). The first layer preferably contains the metal salt M. The second layer preferably contains the metal salt M. The third layer preferably contains the metal salt M. By using the metal salt M, it becomes easy to control the adhesiveness between the interlayer and the laminated glass member or the adhesiveness between the layers in the interlayer. As the metal salt M, only one kind may be used, or two or more kinds may be used in combination.

  The metal salt M preferably contains at least one metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba. The metal salt contained in the intermediate film preferably contains at least one metal of K and Mg.

  The metal salt M is an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt of an organic acid having 2 to 16 carbon atoms. Is more preferable, and a magnesium carboxylate having 2 to 16 carbon atoms or a potassium carboxylate having 2 to 16 carbon atoms is further preferable.

  Examples of the magnesium carboxylate having 2 to 16 carbon atoms and the potassium carboxylate having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, and 2-ethylbutanoic acid. Potassium, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like.

  The total content of Mg and K in the layer containing the metal salt M (first layer, second layer, or third layer) is preferably 5 ppm or more, more preferably 10 ppm or more, and still more preferably 20 ppm or more. , Preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less. When the total content of Mg and K is equal to or greater than the lower limit and equal to or less than the upper limit, the adhesiveness between the interlayer and the laminated glass member or the adhesiveness between the layers in the interlayer can be more favorably controlled.

(UV shielding agent)
The intermediate film preferably contains an ultraviolet shielding agent. The first layer preferably contains an ultraviolet shielding agent. The second layer preferably contains an ultraviolet shielding agent. The third layer preferably contains an ultraviolet shielding agent. By using the ultraviolet ray shielding agent, even if the interlayer film and the laminated glass are used for a long period of time, the visible light transmittance becomes more difficult to decrease. Only one kind of the ultraviolet shielding agent may be used, or two or more kinds may be used in combination.

  The ultraviolet ray shielding agent includes an ultraviolet ray absorbent. It is preferable that the ultraviolet shielding agent is an ultraviolet absorbing agent.

  Examples of the ultraviolet shielding agent include an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure (benzotriazole compound), and an ultraviolet shielding agent having a benzophenone structure (benzophenone compound). ), An ultraviolet shielding agent having a triazine structure (triazine compound), an ultraviolet shielding agent having a malonic ester structure (malonic ester compound), an ultraviolet shielding agent having an oxalic acid anilide structure (anilide oxalate compound), and having a benzoate structure UV shielding agents (benzoate compounds) and the like.

  Examples of the ultraviolet ray shielding agent containing a metal atom include platinum particles, particles whose surfaces are coated with silica, palladium particles, and particles whose surfaces are coated with silica. It is preferable that the ultraviolet shielding agent is not a heat shielding particle.

  The ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure, an ultraviolet shielding agent having a benzophenone structure, an ultraviolet shielding agent having a triazine structure, or an ultraviolet shielding agent having a benzoate structure. The ultraviolet shielding agent is more preferably an ultraviolet shielding agent having a benzotriazole structure or an ultraviolet shielding agent having a benzophenone structure, and further preferably an ultraviolet shielding agent having a benzotriazole structure.

  Examples of the ultraviolet shielding agent containing the metal oxide include zinc oxide, titanium oxide, cerium oxide, and the like. Further, the surface of the ultraviolet shielding agent containing the metal oxide may be coated. Examples of the coating material on the surface of the ultraviolet shielding agent containing the metal oxide include an insulating metal oxide, a hydrolyzable organosilicon compound, and a silicone compound.

  Examples of the ultraviolet shielding agent having the benzotriazole structure include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“Tinuvin P” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (“Tinuvin 320” manufactured by BASF), 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (BASF) "Tinuvin 326"), 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole ("Tinuvin 328", manufactured by BASF) and the like. The ultraviolet ray shielding agent is preferably an ultraviolet ray shielding agent having a benzotriazole structure containing a halogen atom, and is preferably an ultraviolet ray shielding agent having a benzotriazole structure containing a chlorine atom, since it has excellent performance of absorbing ultraviolet rays. More preferred.

  Examples of the ultraviolet shielding agent having the benzophenone structure include octabenzone (“Chimassorb 81” manufactured by BASF).

  Examples of the ultraviolet shielding agent having the triazine structure include "LA-F70" manufactured by ADEKA and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl). Oxy] -phenol (“Tinuvin 1577FF” manufactured by BASF) and the like.

  Examples of the ultraviolet shielding agent having the malonic ester structure include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene). -Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) malonate and the like.

  Commercial products of the ultraviolet shielding agent having the malonic ester structure include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).

  Examples of the ultraviolet shielding agent having the oxalic acid anilide structure include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide and N- (2-ethylphenyl)- Oxalic acid diamide having an aryl group substituted on a nitrogen atom such as N '-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("SanduvorVSU" manufactured by Clariant) And the like.

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

  In 100% by weight of the layer containing the ultraviolet ray shielding agent (first layer, second layer or third layer), the content of the ultraviolet ray shielding agent is preferably 0.1% by weight or more, more preferably 0% by weight or more. It is at least 0.2% by weight, more preferably at least 0.3% by weight, particularly preferably at least 0.5% by weight. In 100% by weight of the layer containing the ultraviolet ray shielding agent (first layer, second layer or third layer), the content of the ultraviolet ray shielding agent is preferably 2.5% by weight or less, more preferably 2% by weight or less. % By weight, more preferably 1% by weight or less, particularly preferably 0.8% by weight or less. When the content of the ultraviolet ray shielding agent is equal to or more than the lower limit and equal to or less than the upper limit, a decrease in visible light transmittance after a lapse of time can be 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 layer containing the ultraviolet shielding agent, the visible light transmittance of the interlayer film and the laminated glass after the lapse of the period is reduced. It can be suppressed significantly.

(Antioxidant)
The intermediate film preferably contains an antioxidant. The first layer preferably contains an antioxidant. Preferably, the second layer contains an antioxidant. The third layer preferably contains an antioxidant. One of the above antioxidants may be used alone, or two or more thereof may be used in combination.

  Examples of the antioxidant include a phenolic antioxidant, a sulfuric antioxidant, and a phosphorus antioxidant. 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), butylhydroxyanisole (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-hydroxide (Xy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,3′- (t-butylphenol) butyric acid glycol ester and bis (3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylenebis (oxyethylene). One or more of these antioxidants are preferably used.

  Examples of the phosphorus antioxidants include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonyl phenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, and bis (decyl) pentaerythritol diphosphite. Phyte, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, and 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.

  Commercial products of the above antioxidants include, for example, “IRGANOX 245” manufactured by BASF, “IRGAFOS 168” manufactured by BASF, “IRGAFOS 38” manufactured by BASF, “Sumilyzer BHT” manufactured by Sumitomo Chemical Co., Ltd., manufactured by Sakai Chemical Industry Co., Ltd. "H-BHT" and "IRGANOX 1010" manufactured by BASF are included.

  In order to maintain a high visible light transmittance of the interlayer film and the laminated glass for a long period of time, a layer (first layer, second layer or third layer) containing 100% by weight of the interlayer or containing an antioxidant. ) In 100% by weight, the content of the antioxidant is preferably 0.1% by weight or more. In addition, since the effect of adding the antioxidant is saturated, the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the interlayer film or 100% by weight of the layer containing the antioxidant. .

(Other ingredients)
The intermediate film, the first layer, the second layer, and the third layer each include, as necessary, a coupling agent containing silicon, aluminum, or titanium, a dispersant, a surfactant, a flame retardant, It may contain additives such as an antistatic agent, a filler, a pigment, a dye, an adhesion regulator, a moisture resistant agent, a fluorescent brightener and an infrared absorber. One of these additives may be used alone, or two or more thereof may be used in combination.

  In order to control the shear storage modulus in a suitable range, the interlayer, the first layer, the second layer, and the third layer may include a filler. Examples of the filler include calcium carbonate particles and silica particles. From the viewpoint of effectively increasing the flexural rigidity and effectively suppressing the decrease in transparency, silica particles are preferred.

  In 100% by weight of the layer containing the filler (first layer, second layer or third layer), the content of the filler is preferably 1% by weight or more, more preferably 5% by weight or more, and further preferably It is at least 10 parts by weight, preferably at most 60% by weight, more preferably at most 50% by weight.

(Other details of interlayer for laminated glass)
The thickness of the intermediate film is not particularly limited. From the viewpoint of practical use, and from the viewpoint of sufficiently enhancing the penetration resistance and bending rigidity of the laminated glass, the thickness of the interlayer is preferably 0.1 mm or more, more preferably 0.25 mm or more, and preferably 3 mm or less. Preferably it is 1.5 mm or less. When the thickness of the intermediate film is equal to or more than the above lower limit, the penetration resistance and the bending rigidity of the laminated glass are further increased. When the thickness of the interlayer is not more than the above upper limit, the transparency of the interlayer is further improved.

  The intermediate film may be an intermediate film having a uniform thickness or an intermediate film having a varying thickness. The cross-sectional shape of the intermediate film may be rectangular or wedge-shaped.

  The method for producing the interlayer according to the present invention is not particularly limited. Examples of the method for producing an interlayer according to the present invention include a method of extruding a resin composition using an extruder in the case of a single-layer interlayer. As a method of manufacturing an intermediate film according to the present invention, in the case of a multilayer intermediate film, for example, a method of forming each layer using each resin composition for forming each layer, and then laminating the obtained layers And a method of laminating each layer by co-extruding each resin composition for forming each layer using an extruder. Since it is suitable for continuous production, a production method of extrusion molding is preferred.

  The second layer and the third layer preferably contain the same polyvinyl acetal resin because the production efficiency of the interlayer is excellent. It is more preferable that the second layer and the third layer contain the same polyvinyl acetal resin and the same plasticizer, since the production efficiency of the intermediate film is excellent. It is more preferable that the second layer and the third layer are formed of the same resin composition because the production efficiency of the intermediate film is excellent.

  It is preferable that the intermediate film has an uneven shape on at least one of the surfaces on both sides. More preferably, the intermediate film has irregularities on both surfaces. The method for forming the above-mentioned uneven shape is not particularly limited, and examples thereof include a lip embossing method, an embossing roll method, a calendar roll method, and a profile extrusion method. The embossing roll method is preferable because it is possible to quantitatively form embosses having a large number of uneven shapes having a constant uneven pattern.

(Laminated glass)
FIG. 3 is a cross-sectional view schematically showing one example of a laminated glass using the laminated glass intermediate film shown in FIG.

  The laminated glass 31 shown in FIG. 3 includes a first laminated glass member 21, a second laminated glass member 22, and the intermediate film 11. The intermediate film 11 is disposed between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched therebetween.

  On the first surface 11a of the intermediate film 11, a first laminated glass member 21 is laminated. A second laminated glass member 22 is laminated on a second surface 11b of the intermediate film 11 opposite to the first surface 11a. The first laminated glass member 21 is laminated on the outer surface 2 a of the second layer 2. The second laminated glass member 22 is laminated on the outer surface 3a of the third layer 3.

  FIG. 4 is a cross-sectional view schematically showing one example of a laminated glass using the laminated glass intermediate film shown in FIG.

  A laminated glass 31A shown in FIG. 4 includes a first laminated glass member 21, a second laminated glass member 22, and an intermediate film 11A. The intermediate film 11A is arranged between the first laminated glass member 21 and the second laminated glass member 22, and is sandwiched therebetween.

  The first laminated glass member 21 is laminated on the first surface 11a of the intermediate film 11A. A second laminated glass member 22 is laminated on a second surface 11b of the intermediate film 11A opposite to the first surface 11a.

  As described above, the laminated glass according to the present invention includes the first laminated glass member, the second laminated glass member, and the intermediate film, and the intermediate film is an intermediate film for laminated glass according to the present invention. It is. In the laminated glass according to the present invention, the intermediate film is disposed between the first laminated glass member and the second laminated glass member.

  The first laminated glass member is preferably a first glass plate. The second laminated glass member is preferably a second glass plate.

  Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. The laminated glass includes not only a laminated glass having an interlayer film sandwiched between two glass plates, but also a laminated glass having an interlayer film sandwiched between a glass plate and a PET film or the like. The laminated glass is a laminate having a glass plate, and it is preferable that at least one glass plate is used. The first laminated glass member and the second laminated glass member are each a glass plate or a PET film, and the laminated glass is one of the first laminated glass member and the second laminated glass member. It is preferable to provide a glass plate as at least one.

  Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include a float plate glass, a heat ray absorption plate glass, a heat ray reflection plate glass, a polished plate glass, a mold plate glass, and a lined plate glass. The organic glass is a synthetic resin glass replacing the inorganic glass. Examples of the organic glass include a polycarbonate plate and a poly (meth) acrylic resin plate. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

  The thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. When the laminated glass member is a glass plate, the thickness of the glass plate is preferably 0.5 mm or more, more preferably 0.7 mm or more, preferably 5 mm or less, more preferably 3 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, preferably 0.5 mm or less.

  By using the interlayer film according to the present invention, the bending rigidity of the laminated glass can be kept high even if the thickness of the laminated glass is small. The thickness of the glass plate is preferably 2 mm or less, more preferably 1.8 mm or less, still more preferably 1.6 mm or less, even more preferably 1.5 mm or less, still more preferably 1.4 mm or less, and still more preferably 1 mm or less. 0.3 mm or less, still more preferably 1.0 mm or less, particularly preferably 0.7 mm or less. In this case, the weight of the laminated glass can be reduced, the environmental load can be reduced by reducing the material of the laminated glass, and the fuel consumption of the automobile can be improved by reducing the weight of the laminated glass, thereby reducing the environmental load. . The total of the thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, more preferably 3.2 mm or less, still more preferably 3 mm or less, and particularly preferably 2.8 mm or less. It is. In this case, the weight of the laminated glass can be reduced, the environmental load can be reduced by reducing the material of the laminated glass, and the fuel consumption of the automobile can be improved by reducing the weight of the laminated glass, thereby reducing the environmental load. .

  The method for producing the laminated glass is not particularly limited. First, a laminate is obtained between the first laminated glass member and the second laminated glass member with an interlayer film interposed therebetween. Next, for example, by passing the obtained laminate through a pressing roll or putting it in a rubber bag and sucking it under reduced pressure, the first laminated glass member, the second laminated glass member, and the intermediate film are separated from each other. Degas any remaining air. Thereafter, the laminate is pre-bonded at about 70 to 110 ° C. to obtain a pre-pressed laminate. Next, the preliminarily pressed laminate is put into an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. Thus, a laminated glass can be obtained. When manufacturing the laminated glass, the first layer, the second layer, and the third layer may be laminated.

  The interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The interlayer film and the laminated glass can be used for other purposes. The intermediate film and the laminated glass are preferably an intermediate film and a laminated glass for a vehicle or a building, and more preferably an intermediate film and a laminated glass for a vehicle. The interlayer film and the laminated glass can be used for a windshield, a side glass, a rear glass, a roof glass, and the like of an automobile. The interlayer film and the laminated glass are suitably used for automobiles. The interlayer is used to obtain laminated glass for automobiles.

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

  The following materials were prepared.

(Polyvinyl acetal resin)
The polyvinyl acetal resins shown in Tables 1 to 3 below were appropriately used.

  Regarding the polyvinyl acetal resin, the degree of acetalization, the degree of acetylation, and the content of hydroxyl groups were measured by a method based on JIS K6728 “Testing method for polyvinyl butyral”. In addition, when it measured by ASTM D1396-92, the same numerical value as the method based on JISK6728 "test method for polyvinyl butyral" was shown. When the type of acetal is acetoacetal, benzyl acetal or cumin acetal, the degree of acetalization is similarly measured by measuring the degree of acetylation and the content of hydroxyl groups, and determining the mole fraction from the measurement results obtained. It is calculated by subtracting the degree of acetylation and the content of hydroxyl groups from 100 mol%, and then calculating.

  In Tables 1 to 3, when the value of the degree of butyralization (degree of acetalization) is described, the polyvinyl butyral resin is used, and the value of the degree of acetoacetalization (degree of acetalization) is described. Polyvinyl acetoacetal resin is used. In Tables 1 to 3, when the value of the degree of benzyl acetalization (degree of acetalization) is described, a polyvinyl benzyl acetal resin is used, and the value of the degree of cumin acetalization (degree of acetalization) is described. In this case, a polyvinyl cumin acetal resin is used.

(Second resin)
The acrylic polymers shown in Tables 1 to 3 below were used as appropriate.

  The acrylic polymers shown in the following Tables 1 to 3 are acrylic polymers obtained by polymerizing polymerizable components containing the following compounds in the contents shown in the following Tables 1 to 3.

Ethyl acrylate butyl acrylate benzyl acrylate 2-hydroxyethyl acrylate glycidyl methacrylate (crosslinking agent)
Tripropylene glycol diacrylate (crosslinking agent)

(Plasticizer)
Triethylene glycol di-2-ethylhexanoate (3GO)

(UV shielding agent)
Tinuvin 326 (2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, "Tinuvin 326" manufactured by BASF)

(Antioxidant)
BHT (2,6-di-t-butyl-p-cresol)

(Example 1)
Preparation of the composition for forming the first layer:
100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, 150 parts by weight of an acrylic polymer of the type shown in Table 1 below, 10 parts by weight of a plasticizer (3GO), and an ultraviolet shielding agent (Tinuvin 326). 2 parts by weight and 0.2 parts by weight of an antioxidant (BHT) were mixed to obtain a composition for forming a first layer.

Preparation of the composition for forming the second layer and the third layer:
100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, 10 parts by weight of a plasticizer (3GO), 0.2 parts by weight of an ultraviolet shielding agent (Tinuvin 326), and 0.2 parts by weight of an antioxidant (BHT) Were mixed to obtain a composition for forming the second layer and the third layer.

Preparation of interlayer:
The composition for forming the first layer and the composition for forming the second layer and the third layer are co-extruded using a co-extruder to form a second layer / second layer. An intermediate film having a laminated structure of one layer / third layer was produced. The thickness of each layer is described in Table 1 below.

Preparation of laminated glass (for measuring bending rigidity):
The obtained intermediate film was cut into a size of 20 cm long × 2.5 cm wide. As a first laminated glass member and a second laminated glass member, two glass plates (clear float glass, length 20 cm × width 2.5 cm) having the thickness shown in Table 1 below were prepared. The obtained intermediate film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was put in a rubber bag and degassed at a vacuum of 2660 Pa (20 torr) for 20 minutes. Thereafter, the laminate was vacuum-pressed while being kept degassed at 90 ° C. for 30 minutes in an autoclave. The laminate preliminarily pressed in this manner was pressed in an autoclave at 135 ° C. under a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

Preparation of laminated glass (for sound insulation measurement):
The obtained intermediate film was cut into a size of 30 cm long × 2.5 cm wide. As a first laminated glass member and a second laminated glass member, two glass plates (clear float glass, length 30 cm × width 2.5 cm) having the thickness shown in Table 1 below were prepared. An interlayer was sandwiched between two glass plates to obtain a laminate. This laminate is placed in a rubber bag and degassed at a degree of vacuum of 2.6 kPa for 20 minutes, then transferred to an oven while deaerated, further held at 90 ° C. for 30 minutes and vacuum pressed to prepare a laminate. Crimped. The pre-pressed laminate was pressed in an autoclave at 135 ° C. and a pressure of 1.2 MPa for 20 minutes to obtain a laminated glass.

(Example 2 and Comparative Example 1)
The composition of the composition for forming the first layer and the composition of the composition for forming the second layer and the third layer are set as shown in Table 1 below, and the first layer In the same manner as in Example 1 except that the thicknesses of the second layer, the third layer, the first laminated glass member, and the second laminated glass member were set as shown in Table 1 below, an intermediate film was formed. And a laminated glass. In Example 2 and Comparative Example 1, the same kind of ultraviolet ray shielding agent and antioxidant as in Example 1 were used in the same amount as in Example 1 (0.2 parts by weight with respect to 100 parts by weight of polyvinyl acetal resin). ).

(Example 3)
Preparation of composition for forming intermediate film (first layer):
100 parts by weight of a polyvinyl acetal resin of the type shown in Table 2 below, 120 parts by weight of an acrylic polymer of the type shown in Table 2 below, 0.2 part by weight of an ultraviolet shielding agent (Tinuvin 326), and an antioxidant (BHT) ) Was mixed with 0.2 parts by weight to obtain a composition for forming an interlayer film.

Preparation of interlayer:
The composition for forming the intermediate film was extruded using an extruder to produce an intermediate film having a thickness shown in Table 2 below.

Preparation of laminated glass (for measuring bending rigidity):
Using the obtained intermediate film, a laminated glass was produced in the same manner as in Example 1.

Preparation of laminated glass (for sound insulation measurement):
Using the obtained intermediate film, a laminated glass was produced in the same manner as in Example 1.

(Examples 4 to 11 and Comparative Examples 2 to 4)
The composition of the composition for forming the intermediate film was set as shown in Tables 2 and 3 below, and the thicknesses of the intermediate film, the first laminated glass member and the second laminated glass member were set forth in Table 2 below. In the same manner as in Example 3 except that the settings were made as shown in FIGS. In Examples 4 to 11 and Comparative Examples 2 to 4, the same kind of ultraviolet ray shielding agent and antioxidant as in Example 3 were added in the same amount (0 to 100 parts by weight of polyvinyl acetal resin) as in Example 3. .2 parts by weight).

(Evaluation)
(1) Viscoelasticity Shear storage modulus:
At a frequency of 1 Hz, the shear storage modulus G ′ (70 ° C.) at 70 ° C. (in the case of a multilayer interlayer, the shear storage equivalent modulus) was measured. Specifically, immediately after storing the obtained interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd. Was used to measure the viscoelasticity. The intermediate film was cut out at a length of 8 mm and a width of 5 mm, and measured in a shearing mode at a rate of 3 ° C./min to increase the temperature from −50 ° C. to 150 ° C., and at a frequency of 1 Hz and a strain of 0.08%. Was done. When there was no measurement failure due to slippage between the layers in the multilayer interlayer, the measurement was performed by the above method. When there was a defect, the viscoelasticity of each layer in the multilayer interlayer was measured by the above method, and the shear storage modulus was calculated by calculation.

Glass-transition temperature:
Immediately after storing the obtained intermediate film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd. was used. There is a method of measuring elasticity. The intermediate film was cut out at a length of 8 mm and a width of 5 mm, and measured in a shearing mode at a rate of 3 ° C./min to increase the temperature from −50 ° C. to 150 ° C., and at a frequency of 1 Hz and a strain of 0.08%. did. The glass transition temperature of the polyvinyl acetal resin (the glass transition temperature of the component derived from the polyvinyl acetal resin) and the glass transition temperature of the second resin (the glass transition temperature of the component derived from the second resin) were evaluated.

Ratio B / A:
Immediately after storing the obtained intermediate film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd. was used. There is a method of measuring elasticity. The intermediate film was cut out at a length of 8 mm and a width of 5 mm, and measured in a shearing mode at a rate of 3 ° C./min to increase the temperature from −50 ° C. to 150 ° C., and at a frequency of 1 Hz and a strain of 0.08%. Was done.
FIG. 6 shows the relationship between G ′ and temperature in Example 11 and Comparative Example 4.

(2) Gel fraction 0.2 g of the intermediate film was immersed in 40 g of tetrahydrofuran and immersed in a shaker at 23 ° C. for 24 hours. Thereafter, the mixture was centrifuged at 10 ° C. and 10,000 rpm by a centrifuge (manufactured by KUBOTA, high-speed large-capacity cooling centrifuge 7780), and the supernatant was removed. The residue in the container was dried by heating at 110 ° C. for 1 hour. Thereafter, the weight of the residue was measured. The gel fraction was calculated by the above formula (X). The gel fraction was determined based on the following criteria.

[Judgment criteria for gel fraction]
A: Gel fraction is 10% by weight or more B: Gel fraction is less than 10% by weight

(3) Flexural rigidity The flexural rigidity was evaluated by a test method schematically shown in FIG. As a measuring apparatus, UTA-500 manufactured by Orientec Co., Ltd. equipped with a three-point bending test jig was used. As measurement conditions, the measurement temperature is 20 ° C. (20 ° C. ± 3 ° C.), 40 ° C. (40 ° C. ± 3 ° C.), 60 ° C. (60 ° C. ± 3 ° C.) or 70 ° C. (70 ° C. ± 3 ° C.), and the distance D1 is The laminated glass was deformed in the direction of F at a displacement speed of 1 mm / min at a displacement speed of 1 mm / min, and the stress when a displacement of 1.5 mm was applied was measured to calculate the bending stiffness. The bending stiffness was determined based on the following criteria. The higher the value of the bending stiffness, the better the bending stiffness.

[Criteria for flexural rigidity at 20 ° C and flexural rigidity at 40 ° C]
：: Flexural rigidity of 55 N / mm or more Δ: Flexural rigidity of 45 N / mm or more and less than 55 N / mm ×: Flexural rigidity of less than 45 N / mm

[Criteria for flexural rigidity at 60 ° C and flexural rigidity at 70 ° C]
○: Flexural rigidity of 55 N / mm or more ○: Flexural rigidity of 45 N / mm or more and less than 55 N / mm △: Flexural rigidity of 35 N / mm or more and less than 45 N / mm ×: Flexural rigidity of less than 35 N / mm

(4) Sound insulation The obtained laminated glass was vibrated by a vibration generator for vibration damping test ("Vibrator G21-005D" manufactured by Shinken Co., Ltd.). The vibration characteristics obtained therefrom were amplified by a mechanical impedance measuring device (“XG-81” manufactured by Rion), and the vibration spectrum was analyzed by an FFT spectrum analyzer (“FFT Analyzer HP3582A” manufactured by Yokogawa Hewlett Packard).

  From the ratio between the loss coefficient 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) was created. , The minimum sound transmission loss (TL value) was determined. The higher the TL value, the higher the sound insulation. Sound insulation was determined based on the following criteria.

[Sound insulation criterion]
：: TL value is 35 dB or more Δ: TL value is 30 dB or more and less than 35 dB ×: TL value is less than 30 dB

(5) Laminating properties Two glass plates obtained by washing and drying the obtained intermediate film (first laminated glass member and second laminated glass member, clear float glass, 100 cm long × 100 cm wide × 2.0 mm thick) To obtain a laminate. The obtained laminate was held at Tg + 10 ° C. and a set pressure of 100 kPa for 5 minutes with a vacuum laminator (“LAMINATOR1222S” manufactured by Nisshinbo Industries, Ltd.), and the bonding property when vacuum pressed was evaluated. In the multilayer intermediate film, evaluation was performed at Tg + 10 ° C., which is higher in glass transition temperature among polyvinyl acetal resins included in the intermediate film.

[Judgment criteria for bonding property]
：: The area of the unbonded portion is less than 5% of the entire area. Δ: The area of the unbonded portion is 5% or more and less than 10%.

  Details and results are shown in Tables 1 to 3 below. In Tables 1 to 3 below, descriptions of the ultraviolet shielding agent and the antioxidant are omitted.

DESCRIPTION OF SYMBOLS 1 ... 1st layer 1a ... 1st surface 1b ... 2nd surface 2 ... 2nd layer 2a ... Outer surface 3 ... 3rd layer 3a ... Outer surface 11 ... Interlayer 11A ... Interlayer ( 1 layer)
11a: first surface 11b: second surface 21: first laminated glass member 22: second laminated glass member 31: laminated glass 31A: laminated glass

Claims (15)

An interlayer for laminated glass having a structure of one or more layers,
The intermediate film includes a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin,
The glass transition temperature Tg of the component derived from the polyvinyl acetal resin contained in the intermediate film is 80 ° C. or higher,
The shear storage modulus G ′ at 70 ° C. is 5 MPa or more and 500 MPa or less,
Formula: (log (G ′ (Tg−20 ° C.)) − Log (G ((Tg−5 ° C.))) − Log (G ′ (Tg−20 ° C.)) G ′ (Tg−10 ° C.))) An interlayer film for laminated glass, wherein the ratio B / A to the value A obtained from / 10 is 3 or more.   The interlayer film for laminated glass according to claim 1, further comprising a first layer containing both the polyvinyl acetal resin and the second resin.   3. The interlayer film for laminated glass according to claim 1, wherein a glass transition temperature of a component derived from the second resin is −20 ° C. or more and 0 ° C. or less. 4.   The laminated glass according to any one of claims 1 to 3, wherein the content of the second resin is 20% by weight or more in a total of 100% by weight of the polyvinyl acetal resin and the second resin. Interlayer. The interlayer film for laminated glass according to any one of claims 1 to 4, wherein the gel fraction determined by the following formula (X) is 10% by weight or more.
Gel fraction (% by weight) = W2 / W1 × 100 Formula (X)
W1: Weight of the intermediate film before immersing the intermediate film in tetrahydrofuran at 23 ° C. W2: Weight of the intermediate film after immersion in the tetrahydrofuran at 23 ° C. and taken out and dried   The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the shear storage modulus G 'at 70C is 10 MPa or more and 500 MPa or less.   The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the polyvinyl acetal resin contained in the interlayer film is a polyvinyl acetoacetal resin, a polyvinyl butyral resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal resin. .   The interlayer film for laminated glass according to any one of claims 1 to 7, wherein the component derived from the polyvinyl acetal resin contained in the interlayer film has a glass transition temperature Tg of 80C or more and 120C or less.   The interlayer film for laminated glass according to any one of claims 1 to 8, further comprising a plasticizer.   The interlayer film for laminated glass according to any one of claims 1 to 9, which has a thickness of 3 mm or less.   The 1st glass plate whose thickness is 1.6 mm or less, it is arrange | positioned between the said 1st glass plate and a 2nd glass plate, and is used for obtaining laminated glass. The interlayer film for laminated glass according to any one of items 10 to 10. Disposed between a first glass plate and a second glass plate and used to obtain a laminated glass;
The interlayer film for laminated glass according to any one of claims 1 to 11, wherein a total of a thickness of the first glass plate and a thickness of the second glass plate is 3.5 mm or less. A first laminated glass member;
A second laminated glass member;
An intermediate film for laminated glass according to any one of claims 1 to 12,
A laminated glass, wherein the interlayer film for a laminated glass is disposed between the first laminated glass member and the second laminated glass member. The first laminated glass member is a first glass plate,
The laminated glass according to claim 13, wherein the thickness of the first glass plate is 1.6 mm or less. The first laminated glass member is a first glass plate,
The second laminated glass member is a second glass plate,
14. The laminated glass according to claim 12, wherein a total of a thickness of the first glass plate and a thickness of the second glass plate is 3.5 mm or less.

Images