JP2013001594A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer for laminated glass with which laminated glass capable of suppressing the generation of bubbles and the growth of bubbles can be obtained.SOLUTION: In the case of a one-layer structure, the interlayer for laminated glass comprises a first layer 2 containing a thermoplastic resin and a plasticizer. In the case of a laminated structure of two or more layers, the interlayer 1 for laminated glass comprises first and second layers 2, 3 containing a thermoplastic resin and a plasticizer. The proportion of a high molecular weight component having an absolute molecular weight of ≥1 million in the thermoplastic resin in the first layer 2 is ≥7.4%, or the proportion of a high molecular weight component having a molecular weight (expressed in terms of polystyrene) of ≥1 million in the thermoplastic resin in the first layer 2 is ≥9%. The thickness of one end 1a of the interlayer 1 for laminated glass is smaller than the thickness of the other end 1b.

Description

  The present invention relates to an interlayer film for laminated glass suitably used for, for example, a head-up display. More specifically, the present invention relates to an interlayer film for laminated glass containing a thermoplastic resin and a plasticizer, and the interlayer film for laminated glass. It relates to laminated glass.

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

  As an example of the interlayer film for laminated glass, Patent Document 1 listed below includes 100 parts by weight of polyvinyl acetal resin, triethylene glycol mono-2-ethylhexanoate, and triethylene glycol di-2-ethylhexanoate. An intermediate film containing 20 to 60 parts by weight of a mixture is disclosed.

  Further, in Patent Document 2 below, 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 0.001 to 1 of an alkali metal salt and an alkaline earth metal salt A sound insulation layer containing 0.0 part by weight and 30 parts by weight or more of a plasticizer is disclosed. This sound insulation layer may be a single layer and used as an intermediate film.

  Further, Patent Document 2 below also describes a multilayer intermediate film in which the sound insulation layer and other layers are laminated. The other layer laminated on the sound insulation layer is composed of 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 0.001 to 0.001. 1.0 part by weight and a plasticizer of 30 parts by weight or less are included.

  In addition, a head-up display (HUD) is known as the laminated glass used in automobiles. In HUD, measurement information such as speed, which is driving data of a car, can be displayed on the windshield of the car.

  In the HUD, there is a problem that the measurement information displayed on the windshield looks double.

  In order to suppress double images, the following Patent Document 3 discloses a laminated glass in which a wedge-shaped interlayer film having a predetermined wedge angle is sandwiched between a pair of glass plates. In such a laminated glass, by adjusting the wedge angle of the interlayer film, the display of measurement information reflected by one glass plate and the display of measurement information reflected by another glass plate can be performed in the driver's field of view. Can be tied to one point. For this reason, it is hard to see the display of measurement information double, and does not disturb a driver's field of view.

JP 2001-097745 A JP 2007-070200 A Japanese National Publication No. 4-502525

  When the laminated glass is configured using the interlayer film described in Patent Documents 1 to 3 above, the sound insulation in the frequency region near 2000 Hz of the laminated glass is not sufficient, and therefore a decrease in the sound insulation due to the coincidence effect can be avoided. There may not be. In particular, the sound insulation properties at around 20 ° C. of this laminated glass may not be sufficient.

  Here, the coincidence effect means that when a sound wave is incident on the glass plate, the transverse wave propagates on the glass surface due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs.

  Even when the laminated glass is constituted by using the sound insulating layer described in Patent Document 2 as a single layer as an intermediate film, the sound insulating property in the vicinity of 20 ° C. of the laminated glass may not be sufficient.

  In addition, when a laminated glass is formed using a multilayered interlayer film in which the sound insulating layer described in Patent Document 2 and other layers are laminated, the sound insulating property in the vicinity of 20 ° C. of the laminated glass can be increased to some extent. it can. However, since the multilayer interlayer film has the sound insulating layer, foaming may occur in the laminated glass using the multilayer interlayer film.

  Furthermore, in recent years, in order to improve the sound insulation of the laminated glass, it has been studied to increase the content of the plasticizer in the interlayer film. When the content of the plasticizer in the interlayer film is increased, the sound insulation of the laminated glass can be improved. However, when the plasticizer content is increased, foaming may occur in the laminated glass.

  The objective of this invention is providing the laminated glass which can obtain the laminated glass which can suppress generation | occurrence | production of foaming, and the growth of foam, and the laminated glass using this intermediate film for laminated glass.

  A limited object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass excellent in sound insulation, and a laminated glass using the interlayer film for laminated glass.

  According to a wide aspect of the present invention, in the case of an interlayer film for laminated glass having a one-layer structure or a laminated structure of two or more layers, and being an interlayer film for laminated glass having a one-layer structure, thermoplasticity In the case of the interlayer film for laminated glass having a first layer containing a resin and a plasticizer and having a laminated structure of two or more layers, a first layer containing a thermoplastic resin and a plasticizer; And a second layer containing a thermoplastic resin and a plasticizer, the thermoplastic resin in the first layer having an absolute molecular weight of 1,000,000. The ratio of the high molecular weight component containing the above high molecular weight component and occupying the thermoplastic resin in the first layer is 7.4% or more, or the heat in the first layer The plastic resin contains a high molecular weight component having a polystyrene equivalent molecular weight of 1 million or more, and For laminated glass, the proportion of the high molecular weight component in the thermoplastic resin in the first layer is 9% or more, and the thickness of one end is thinner than the thickness of the other end opposite to the one end. An interlayer film is provided.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film for laminated glass has a shape in which the thickness gradually increases from one end to the other end.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the cross-sectional shape in the thickness direction is a wedge shape.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin in the first layer contains a high molecular weight component having an absolute molecular weight of 1 million or more, and the heat in the first layer. The proportion of the high molecular weight component in the plastic resin is 7.4% or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin in the first layer contains a high molecular weight component having a polystyrene equivalent molecular weight of 1 million or more, and in the first layer. The proportion of the high molecular weight component in the thermoplastic resin is 9% or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin in the first layer is a polyvinyl acetal resin.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the content of hydroxyl groups in the polyvinyl acetal resin in the first layer is 31 mol% or less.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the plasticizer content in the first layer is in the range of 40 to 80 parts by weight with respect to 100 parts by weight of the thermoplastic resin. .

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film for laminated glass has a laminated structure of two or more layers, and includes the first layer and the second layer.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the first layer is the heat in the second layer. The content of the plasticizer is more than 100 parts by weight of the plastic resin.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, in the case of the interlayer film for laminated glass having a laminated structure of three or more layers, the first layer, the second layer, A third layer that is laminated on the other surface of the first layer and contains a thermoplastic resin and a plasticizer is further provided.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film for laminated glass has a laminated structure of three or more layers, and the first layer, the second layer, and the third layer. And a layer.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the first layer is the heat in the third layer. The content of the plasticizer is more than 100 parts by weight of the plastic resin.

  Note that, for example, the plasticizer may migrate between the first layer and the second layer. In addition, the plasticizer may migrate between the first layer and the third layer.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin in the first layer is a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin is 8 mol% or less. In addition, the degree of acetalization is 70 mol% or more, or the thermoplastic resin in the first layer is a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin exceeds 8 mol%. It is preferable that the thermoplastic resin in the first layer is a polyvinyl acetal resin, the degree of acetylation of the polyvinyl acetal resin is 8 mol% or less, and the degree of acetalization is 70 mol% or more. Furthermore, it is also preferable that the thermoplastic resin in the first layer is a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin exceeds 8 mol%.

  The laminated glass according to the present invention comprises first and second laminated glass constituent members and an intermediate film sandwiched between the first and second laminated glass constituent members, and the intermediate film comprises: 1 is an interlayer film for laminated glass constructed according to the present invention.

  The interlayer film for laminated glass according to the present invention has a one-layer structure including a first layer containing a thermoplastic resin and a plasticizer, or a first layer containing a thermoplastic resin and a plasticizer. And a second layer containing a thermoplastic resin and a plasticizer, a high molecular weight component having a laminated structure of two or more layers, and wherein the thermoplastic resin in the first layer has an absolute molecular weight of 1,000,000 or more And the proportion of the high molecular weight component in the thermoplastic resin in the first layer is 7.4% or more, or the thermoplastic resin in the first layer is a polystyrene equivalent molecular weight Since the ratio of the high molecular weight component containing 9 million or more of the high molecular weight component and occupying the thermoplastic resin in the first layer is 9% or more, the thickness of one end is opposite to the one end Despite being thinner than the other end of the The occurrence and growth of the foam of the foam in the laminated glass can be suppressed. Furthermore, since the thickness of one end of the interlayer film for laminated glass according to the present invention is smaller than the thickness of the other end, for example, when a head-up display (HUD) is manufactured using the interlayer film, double images are suppressed. You can also

1A and 1B are a cross-sectional view and a plan view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention. 2A and 2B are a cross-sectional view and a plan 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 showing a first modification of the cross-sectional shape in the thickness direction of the interlayer film for laminated glass. FIG. 4 is a cross-sectional view showing a second modification of the cross-sectional shape in the thickness direction of the interlayer film for laminated glass. FIG. 5 is a cross-sectional view showing a third modification of the cross-sectional shape in the thickness direction of the interlayer film for laminated glass. FIG. 6 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG.

  Details of the present invention will be described below.

  The interlayer film for laminated glass according to the present invention has a single-layer structure or a laminated structure of two or more layers. When the interlayer film for laminated glass according to the present invention has a single-layer structure, the interlayer film includes a first layer containing a thermoplastic resin and a plasticizer. When the interlayer film for laminated glass according to the present invention has a laminated structure of two or more layers, a first layer containing a thermoplastic resin and a plasticizer and one surface of the first layer (first 1) and a second layer containing a thermoplastic resin and a plasticizer.

  In the interlayer film for laminated glass according to the present invention, the thermoplastic resin in the first layer contains a high molecular weight component having an absolute molecular weight of 1 million or more (hereinafter sometimes referred to as high molecular weight component X). The thermoplastic resin in the first layer contains or has a high molecular weight component (hereinafter referred to as a high molecular weight component Y) of 1 million or more in terms of polystyrene equivalent molecular weight (hereinafter sometimes referred to as molecular weight y). Is included). The high molecular weight components X and Y are thermoplastic resins. In the interlayer film for laminated glass according to the present invention, the proportion of the high molecular weight component X in the thermoplastic resin in the first layer is 7.4% or more, or in the first layer. The proportion of the high molecular weight component Y in the thermoplastic resin is 9% or more.

  1A and 1B schematically show a cross-sectional view and a plan view of an interlayer film for laminated glass according to a first embodiment of the present invention. Fig.1 (a) is front sectional drawing which follows the II line | wire in FIG.1 (b).

  In FIG. 1A, a cross section in the thickness direction of the intermediate film 1 is shown. In FIG. 1A and the drawings described later, for convenience of illustration, the thickness of each layer constituting the intermediate film and the intermediate film, and the wedge angle θ are shown to be different from the actual thickness and wedge angle. .

  The intermediate film 1 shown in FIG. 1 has a laminated structure of two or more layers, and more specifically has a laminated structure of three or more layers, and is a multilayered intermediate film. Specifically, the intermediate film 1 has a three-layer structure. The intermediate film 1 includes a first layer 2, a second layer 3 stacked on one surface 2 a (first surface) of the first layer 2, and the other surface 2 b ( And a third layer 4 laminated on the second surface). The intermediate film 1 is used to obtain a laminated glass. The intermediate film 1 is an intermediate film for laminated glass.

  The first layer 2 is disposed between the second layer 3 and the third layer 4, and is sandwiched between the second layer 3 and the third layer 4. In the first embodiment, the first layer 2 is an intermediate layer, and the second and third layers 3 and 4 are surface layers. Thus, it is preferable to use both the second and third layers 3 and 4. However, it is possible to use only the second layer 3 without using the third layer 4. Another interlayer film for laminated glass may be further laminated on the outer surfaces 3 a and 4 a of the second and third layers 3 and 4.

  The intermediate film 1 has one end 1a and the other end 1b opposite to the one end 1a. The one end 1a and the other end 1b are opposite ends on opposite sides. The cross-sectional shape in the thickness direction of the second and third layers 3 and 4 is a wedge shape. The cross-sectional shape in the thickness direction of the first layer 2 is a wedge shape. The thickness of the second and third layers 3 and 4 is thinner on the one end 1a side than on the other end 1b side. The thickness of the first layer 2 is thinner on the one end 1a side than on the other end 1b side. Therefore, the thickness of one end 1a of the intermediate film 1 is thinner than the thickness of the other end 1b. Therefore, the intermediate film 1 has a thin region and a thick region. The thickness of the thin region is thinner than that of the thick region.

  One of the main features of this embodiment is that the thickness of one end 1a of the intermediate film 1 is thinner than the thickness of the other end 1b. Since the thickness of one end 1a of the intermediate film 1 is smaller than the thickness of the other end 1b, for example, when laminated glass using the intermediate film 1 is used for a head-up display (HUD), the speed that is the driving data of the automobile, etc. Even if the measurement information is displayed, it is possible to suppress the measurement information from appearing double.

  Each of the first to third layers 2 to 4 contains a thermoplastic resin and a plasticizer. The thermoplastic resin in the first layer 2 contains a high molecular weight component X having an absolute molecular weight of 1,000,000 or more, and the proportion of the high molecular weight component X in the thermoplastic resin in the first layer 2 is 7 .4% or more. The thermoplastic resin in the first layer 2 includes a high molecular weight component Y having a molecular weight y of 1,000,000 or more, and the proportion of the high molecular weight component Y in the thermoplastic resin in the first layer 2 May be 9% or more.

  The proportion of the high molecular weight component X in the thermoplastic resin in the first layer 2 is the high molecular weight component X in the peak area of the thermoplastic resin component obtained when measuring the absolute molecular weight. Is defined as a value expressed as a percentage (%). The proportion of the high molecular weight component Y in the thermoplastic resin in the first layer 2 is the high molecular weight component in the peak area of the thermoplastic resin component obtained when measuring the polystyrene equivalent molecular weight. The area ratio of the area corresponding to Y is defined as a value expressed as a percentage (%).

  The compositions of the second and third layers 3 and 4 are preferably different from the composition of the first layer 2. The thermoplastic resin in the second and third layers 3 and 4 contains a high molecular weight component X having an absolute molecular weight of 1 million or more, and occupies the thermoplastic resin in the second and third layers 3 and 4. The ratio of the high molecular weight component X may be 7.4% or more, includes the high molecular weight component Y having a molecular weight y of 1,000,000 or more, and the thermoplasticity in the second and third layers 3 and 4 The proportion of the high molecular weight component Y in the resin may be 9% or more.

  Moreover, in the laminated glass using the intermediate film in which the thickness of one end is thinner than the thickness of the other end, foaming tends to occur easily in a thin region. On the other hand, even if the thickness of one end of the intermediate film is thinner than the thickness of the other end, the proportion of the high molecular weight component X in the thermoplastic resin in the first layer 2 is 7.4% or more. Or the ratio of the high molecular weight component Y to the thermoplastic resin in the first layer 2 is 9% or more, so that the occurrence of foaming of the laminated glass in the entire region including the thin region and Foam growth can be effectively suppressed.

  2A and 2B schematically show a cross-sectional view and a plan view of an interlayer film for laminated glass according to a second embodiment of the present invention. Fig.2 (a) is front sectional drawing which follows the II line | wire in FIG.2 (b). FIG. 2A shows a cross section in the thickness direction of the intermediate film 21A.

  An intermediate film 21 </ b> A illustrated in FIG. 2 includes a first layer 21. The intermediate film 21A has a single-layer structure including only the first layer 21, and is a single-layer intermediate film. The intermediate film 21 </ b> A is the first layer 21. The intermediate film 21A is used to obtain a laminated glass. The intermediate film 21A is an intermediate film for laminated glass.

  The intermediate film 21A has one end 21a and the other end 21b opposite to the one end 21a. The one end 21a and the other end 21b are opposite ends on opposite sides. The thickness of one end 21a of the intermediate film 21A is thinner than the thickness of the other end 21b. Therefore, the intermediate film 21A and the first layer 21 have a thin region and a thick region.

  The thermoplastic resin in the first layer 21 contains a high molecular weight component X having an absolute molecular weight of 1 million or more, and the proportion of the high molecular weight component X in the thermoplastic resin in the first layer 21 is 7 .4% or more. The thermoplastic resin in the first layer 21 includes a high molecular weight component Y having a molecular weight y of 1,000,000 or more, and the proportion of the high molecular weight component Y in the thermoplastic resin in the first layer 21 May be 9% or more. Thereby, generation | occurrence | production and foaming growth of a laminated glass can be effectively suppressed in the whole area | region including a thin area | region.

  The multilayer intermediate film 1 is preferable to the single-layer intermediate film 21A. In the case where the second and third layers 3 and 4 are laminated on both surfaces of the first layer 2, the second and third layers 3 and 4 can be used even if the adhesive strength of the first layer 2 is low. By increasing the adhesive strength, the adhesive strength between the multilayer intermediate film 1 and the laminated glass constituent member can be increased. For this reason, the penetration resistance of a laminated glass can be improved further.

  Furthermore, in the case of the multilayer intermediate film 1, the laminated glass tends to be foamed more easily than in the case of the single-layer intermediate film 21 </ b> A. In particular, the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the first layer 2 is such that the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the second and third layers 3 and 4. When the amount is larger than the amount, foaming tends to occur more easily. Furthermore, once foaming occurs, the generated foam becomes a nucleus and the foam tends to grow. However, in the first embodiment, since the thermoplastic resin in the first layer 2 contains a high molecular weight component having an absolute molecular weight of 1,000,000 or more at the specific ratio, it is possible to suppress foaming from occurring in the laminated glass. Even if the thermoplastic resin in the first layer 2 contains a high molecular weight component Y having a molecular weight y of 1,000,000 or more in the above specific ratio, foaming of the laminated glass can be suppressed.

  From the viewpoint of further improving the sound insulating properties of the laminated glass and further suppressing the occurrence of foaming and the growth of foaming, a high absolute molecular weight of 1 million or more in the thermoplastic resin in the first layers 2 and 21. The preferable lower limit of the ratio of the molecular weight component X is 8%, the more preferable lower limit is 8.5%, the still more preferable lower limit is 9%, the particularly preferable lower limit is 9.5%, and the most preferable lower limit is 10%. The ratio of the high molecular weight component X is preferably 11% or more, more preferably 12% or more, and still more preferably 14 because the sound insulation of the laminated glass can be further enhanced and the generation of foaming and the growth of foaming can be further suppressed. % Or more, particularly preferably 16% or more. Although the upper limit of the ratio of the high molecular weight component X is not particularly limited, the preferable upper limit is 40%, the more preferable upper limit is 30%, and the further preferable upper limit is 25%.

  When the thermoplastic resin in the first layer 2, 21 contains a high molecular weight component Y having a molecular weight y of 1,000,000 or more, the heat in the first layer 2, 21 containing the high molecular weight component Y The preferred lower limit of the proportion of the high molecular weight component Y having a molecular weight y of 1,000,000 or more in the plastic resin is 10%, more preferred lower limit is 11%, still more preferred lower limit is 11.5%, and particularly preferred lower limit is 12%. . The ratio of the high molecular weight component Y is preferably 12.5% or more, more preferably 13.5% or more, since the sound insulation of the laminated glass can be further enhanced and the occurrence of foaming and the growth of foaming can be further suppressed. More preferably, it is 14% or more, particularly preferably 15% or more, and most preferably 18% or more. The upper limit of the proportion of the high molecular weight component Y is not particularly limited, but the preferable upper limit is 40%, the more preferable upper limit is 30%, and the further preferable upper limit is 25%. When the proportion of the high molecular weight component Y is not less than the above lower limit, the sound insulating properties of the laminated glass can be further enhanced, and the generation of foam and the growth of foam can be further suppressed.

  From the viewpoint of further improving the penetration resistance of the laminated glass, the preferable lower limit of the thickness of the multilayer intermediate film 1 and the single-layer intermediate film 21A is 0.05 mm, the more preferable lower limit is 0.25 mm, and the preferable upper limit is 3 mm. A preferable upper limit is 1.5 mm. When the thickness of the multilayer intermediate film 1 and the single-layer intermediate film 21A satisfies the preferable lower limit and the preferable upper limit, respectively, the penetration resistance and transparency of the laminated glass can be further improved.

  The intermediate film 1 shown in FIG. 1 has a structure in which a wedge-shaped first layer 2 is sandwiched between wedge-shaped second and third layers 3 and 4. 3 to 5 show first to third modifications in which the shape of each layer of the intermediate film is changed.

  The intermediate film 51 according to the first modified example shown in FIG. 3 is between the second and third layers 53 and 54 whose cross-sectional shape in the thickness direction is wedge-shaped, and the second and third layers 53 and 54. And a first layer 52 having a rectangular cross-sectional shape in the thickness direction. The thickness of one end 51a of the intermediate film 51 is thinner than the thickness of the other end 51b on the opposite side to the one end 51a. Regarding the thickness of the second and third layers 53 and 54, the one end 51a side is thinner than the other end 51b side.

  The intermediate film 61 according to the second modification shown in FIG. 4 includes a second layer 63 having a wedge-shaped cross-sectional shape in the thickness direction, a third layer 64 having a rectangular cross-sectional shape in the thickness direction, The first layer 62 is sandwiched between the third layers 63 and 64 and has a rectangular cross-sectional shape in the thickness direction. The thickness of one end 61a of the intermediate film 61 is smaller than the thickness of the other end 61b on the opposite side to the one end 61a. The thickness of the second layer 63 is thinner on the one end 61a side than on the other end 61b side.

  An intermediate film 71 according to the third modification shown in FIG. 5 is provided between the second and third layers 73 and 74 whose cross-sectional shape in the thickness direction is rectangular and the second and third layers 73 and 74. And a first layer 72 sandwiched and having a wedge-shaped cross-sectional shape in the thickness direction. The thickness of one end 71a of the intermediate film 71 is thinner than the thickness of the other end 71b on the opposite side to the one end 71a. The thickness of the first layer 72 is thinner on the one end 71a side than on the other end 71b side.

  The intermediate films 1, 51, 61, 71 have one end 1a, 51a, 61a, 71a having a minimum thickness and the other end 1b, 51b, 61b, 71b having a maximum thickness.

  In the direction connecting the one end and the other end having different thicknesses, the cross-sectional shape in the thickness direction of the intermediate film is preferably a wedge shape. The intermediate film preferably has a shape in which the thickness gradually increases from one end to the other end, and preferably has a shape in which the thickness continuously increases from one end to the other end. “Thickness gradually increases” includes not only the case where the thickness increases continuously but also the case where the thickness increases stepwise. Examples of the cross-sectional shape in the thickness direction of the intermediate film include a trapezoid or a triangle.

  In order to suppress the double image, the wedge angle θ of the interlayer film can be appropriately set according to the attachment angle of the laminated glass. From the viewpoint of further suppressing double images, the wedge angle θ of the interlayer film is preferably 0.01 mrad (0.0006 degrees) or more, more preferably 0.2 mrad (0.0115 degrees) or more, preferably 2 mrad ( 0.1146 degrees) or less, more preferably 0.7 mrad (0.0401 degrees) or less.

  Hereinafter, the detail of each component contained in the said 1st-3rd layer of an intermediate film is demonstrated.

(Thermoplastic resin)
The kind of the thermoplastic resin contained in the first to third layers is not particularly limited. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin.

  The preferable lower limit of the weight average molecular weight of the thermoplastic resin is 100,000, the more preferable lower limit is 300,000, the preferable upper limit is 10,000,000, and the more preferable upper limit is 5,000,000. When the weight average molecular weight of the thermoplastic resin is not more than the preferable lower limit, the strength of the interlayer film may be lowered. When the weight average molecular weight of the thermoplastic resin exceeds the preferable upper limit, the strength of the obtained interlayer film may become too strong. In addition, the said weight average molecular weight shows the weight average molecular weight in polystyrene conversion by gel permeation chromatography (GPC) measurement.

  The thermoplastic resin is preferably a polyvinyl acetal resin. By the combined use of the polyvinyl acetal resin and the plasticizer, the adhesive force of the interlayer film to the laminated glass constituent member can be further increased. When the thermoplastic resin is a polyvinyl acetal resin, the high molecular weight components X and Y are polyvinyl acetal resins.

  Furthermore, when the thermoplastic resin is a polyvinyl acetal resin, foaming tends to occur particularly easily in the laminated glass using the intermediate film. However, since the polyvinyl acetal resin contains the high molecular weight component X having an absolute molecular weight of 1,000,000 or more or the high molecular weight component Y having a molecular weight y of 1,000,000 or more in the above specific ratio, in the laminated glass using the interlayer film for laminated glass Generation of foaming and growth of foaming can be sufficiently suppressed.

  When the first layer that is an intermediate layer and the first layer that is a single-layer intermediate film contain a polyvinyl acetal resin, the hydroxyl group content of the polyvinyl acetal resin contained in the first layer The (hydroxyl group amount) is preferably 31 mol% or less. In this case, the sound insulation of the laminated glass can be further enhanced. In addition, when the content rate of the hydroxyl group of polyvinyl acetal resin is low, the hydrophilic property of polyvinyl acetal resin will become low. For this reason, content of a plasticizer can be increased and as a result, the sound insulation of a laminated glass can be made still higher.

  The preferable lower limit of the hydroxyl group content of the polyvinyl acetal resin contained in the first layer is 13 mol%, the more preferable lower limit is 18 mol%, the still more preferable lower limit is 20 mol%, and the particularly preferable lower limit is 21.5. More preferably, the upper limit is 30 mol%, the upper limit is more preferably 28 mol%, and the upper limit is particularly preferably 26 mol%. When the hydroxyl group content satisfies the preferable lower limit, the adhesive strength of the first layer can be further increased. When the hydroxyl group content satisfies the preferable upper limit, the sound insulating properties of the laminated glass can be further enhanced. Furthermore, the flexibility of the intermediate film is increased, and the handleability of the intermediate film can be further enhanced.

  When the second and third layers contain a polyvinyl acetal resin, the preferred lower limit of the hydroxyl group content of the polyvinyl acetal resin contained in the second and third layers is 26 mol%, more preferred lower limit. Is 27 mol%, a more preferred lower limit is 28 mol%, a preferred upper limit is 35 mol%, a more preferred upper limit is 33 mol%, a still more preferred upper limit is 32 mol%, and a particularly preferred upper limit is 31.5 mol%. When the hydroxyl group content satisfies the preferable lower limit, the adhesive strength of the second and third layers can be further increased. When the hydroxyl group content satisfies the preferable upper limit, the flexibility of the intermediate film is increased, and the handleability of the intermediate film can be further enhanced.

  From the viewpoint of further improving the sound insulation of the laminated glass, the hydroxyl group content of the polyvinyl acetal resin contained in the first layer is the same as that of the polyvinyl acetal resin contained in the second and third layers. It is preferable that the content of each hydroxyl group is lower. From the viewpoint of further improving the sound insulation of the laminated glass, the hydroxyl group content of the polyvinyl acetal resin contained in the first layer is the same as that of the polyvinyl acetal resin contained in the second and third layers. It is preferably 1 mol% or less, more preferably 3 mol% or less, still more preferably 5 mol% or less, and particularly preferably 7 mol% or less than the respective hydroxyl group contents.

  The content of hydroxyl groups in the polyvinyl acetal resin is a value obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, as a percentage (mol%). . The amount of ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of the polyvinyl acetal resin is bonded by a method based on JIS K6726 “Testing method for polyvinyl alcohol”. it can.

  When the first layer contains a polyvinyl acetal resin, the preferred lower limit of the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin contained in the first layer is more preferably 0.1 mol%. The lower limit is 0.4 mol%, the more preferable lower limit is 0.8 mol%, the preferable upper limit is 30 mol%, the more preferable upper limit is 25 mol%, the still more preferable upper limit is 20 mol%, and the particularly preferable upper limit is 15 mol%. . When the second and third layers contain a polyvinyl acetal resin, the preferred lower limit of the degree of acetylation of the polyvinyl acetal resin contained in the second and third layers is more preferably 0.1 mol%. The lower limit is 0.4 mol%, the preferred upper limit is 20 mol%, the more preferred upper limit is 5 mol%, the still more preferred upper limit is 2 mol%, and the particularly preferred upper limit is 1.5 mol%. When the acetylation degree satisfies the preferable lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further enhanced, and the glass transition temperature of the interlayer film can be sufficiently lowered. When the acetylation degree satisfies the preferable upper limit, the moisture resistance of the intermediate film can be further enhanced.

  From the viewpoint of further improving the sound insulation of the laminated glass, the degree of acetylation of the polyvinyl acetal resin contained in the first layer is the same as that of the polyvinyl acetal resin contained in the second and third layers. It is preferable that the degree of conversion is higher. From the viewpoint of further improving the sound insulation of the laminated glass, the degree of acetylation of the polyvinyl acetal resin contained in the first layer is the same as that of the polyvinyl acetal resin contained in the second and third layers. It is preferably at least 0.1 mol% higher than the degree of conversion, more preferably at least 1 mol%, more preferably at least 5 mol%, particularly preferably at least 10 mol%.

  From the viewpoint of further improving the sound insulation of the laminated glass, the degree of acetalization of the polyvinyl acetal resin contained in the first layer is the same as that of the polyvinyl acetal resin contained in the second and third layers. It is preferable that the degree of conversion is higher.

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

  When the first layer containing a high molecular weight component having an absolute molecular weight of 1,000,000 or more in the specific ratio contains a polyvinyl acetal resin, the degree of acetalization of the polyvinyl acetal resin contained in the first layer is preferable. The lower limit is 50 mol%, the more preferred lower limit is 53 mol%, the still more preferred lower limit is 60 mol%, the particularly preferred lower limit is 63 mol%, the preferred upper limit is 85 mol%, the more preferred upper limit is 80 mol%, and the more preferred upper limit is 78. Mol%. When the second and third layers contain a polyvinyl acetal resin, the preferred lower limit of the degree of acetalization of the polyvinyl acetal resin contained in the second and third layers is 55 mol%, and the more preferred lower limit is 60 mol%, a more preferred lower limit is 65 mol%, a particularly preferred lower limit is 67 mol%, a preferred upper limit is 75 mol%, a more preferred upper limit is 72 mol%, and a still more preferred upper limit is 71 mol%. When the said acetalization degree satisfy | fills the said preferable minimum, the compatibility of polyvinyl acetal resin and a plasticizer becomes still higher, and the glass transition temperature of an intermediate film can fully be reduced. When the said acetalization degree satisfy | fills the said preferable upper limit, reaction time required in order to manufacture polyvinyl acetal resin can be shortened.

  The degree of acetalization is a value obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, and expressed as a percentage (mol%).

  The degree of acetalization was determined by measuring the amount of acetyl groups and the amount of vinyl alcohol (hydroxyl content) by a method based on JIS K6728 “Testing methods for polyvinyl butyral”, and calculating the mole fraction from the obtained measurement results. Then, it can be calculated by subtracting the amount of acetyl groups and the amount of vinyl alcohol from 100 mol%.

  When the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the amount of acetyl group can be calculated from the results measured by a method according to JIS K6728 “Testing methods for polyvinyl butyral”. .

  When the first layer contains a polyvinyl acetal resin, the sound insulation of the intermediate film is further enhanced. Therefore, the polyvinyl acetal resin has an acetylation degree a of 8 mol% or less and an acetalization degree a of It is preferable that the polyvinyl acetal resin A is 70 mol% or more, or the polyvinyl acetal resin B has a degree of acetylation b exceeding 8 mol%. The polyvinyl acetal resin may be a polyvinyl acetal resin A having an acetylation degree a of 8 mol% or less and an acetalization degree a of 70 mol% or more, and the acetylation degree b exceeds 8 mol%. Polyvinyl acetal resin B may be used.

  The upper limit of the degree of acetylation a of the polyvinyl acetal resin A is 8 mol%, the preferable upper limit is 7.5 mol%, the more preferable upper limit is 7 mol%, the still more preferable upper limit is 6.5 mol%, and the particularly preferable upper limit is 5 mol%. %, A preferred lower limit is 0.1 mole%, a more preferred lower limit is 0.5 mole%, a still more preferred lower limit is 0.8 mole%, and a particularly preferred lower limit is 1 mole%. When the acetylation degree a is not more than the above upper limit and not less than the above lower limit, the migration of the plasticizer can be easily controlled, and the sound insulation of the laminated glass can be further enhanced.

  The lower limit of the degree of acetalization a of the polyvinyl acetal resin A is 70 mol%, the preferred lower limit is 70.5 mol%, the more preferred lower limit is 71 mol%, the still more preferred lower limit is 71.5 mol%, and the particularly preferred lower limit is 72 mol%. %, A preferred upper limit is 85 mol%, a more preferred upper limit is 83 mol%, a still more preferred upper limit is 81 mol%, and a particularly preferred upper limit is 79 mol%. When the acetalization degree a is not less than the above lower limit, the sound insulation of the laminated glass can be further enhanced. When the acetalization degree a is not more than the above upper limit, the reaction time necessary for producing the polyvinyl acetal resin A can be shortened.

  The preferable lower limit of the hydroxyl group content a of the polyvinyl acetal resin A is 18 mol%, the more preferable lower limit is 19 mol%, the still more preferable lower limit is 20 mol%, the particularly preferable lower limit is 21 mol%, and the preferable upper limit is 31 mol%, A more preferred upper limit is 30 mol%, a still more preferred upper limit is 29 mol%, and a particularly preferred upper limit is 28 mol%. When the hydroxyl group content a satisfies the preferable lower limit, the adhesive strength of the interlayer film can be further increased. When the hydroxyl group content a satisfies the above preferable upper limit, the sound insulation of the laminated glass can be further enhanced.

  The polyvinyl acetal resin A is preferably a polyvinyl butyral resin.

  The degree of acetylation b of the polyvinyl acetal resin B exceeds 8 mol%, the preferred lower limit is 9 mol%, the more preferred lower limit is 9.5 mol%, the still more preferred lower limit is 10 mol%, and the particularly preferred lower limit is 10.5. The upper limit is 30 mol%, the more preferable upper limit is 28 mol%, the still more preferable upper limit is 26 mol%, and the particularly preferable upper limit is 24 mol%. When the acetylation degree b is not less than the above lower limit, the sound insulation of the laminated glass can be further enhanced. When the acetylation degree b is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin B can be shortened.

  The preferable lower limit of the degree of acetalization b of the polyvinyl acetal resin B is 50 mol%, the more preferable lower limit is 53 mol%, the still more preferable lower limit is 55 mol%, the particularly preferable lower limit is 60 mol%, and the preferable upper limit is 80 mol%. A preferable upper limit is 78 mol%, a more preferable upper limit is 76 mol%, and a particularly preferable upper limit is 74 mol%. When the acetalization degree b is equal to or higher than the lower limit, the sound insulation of the laminated glass can be further enhanced. When the acetalization degree b is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin B can be shortened.

  The preferable lower limit of the hydroxyl group content b of the polyvinyl acetal resin B is 18 mol%, the more preferable lower limit is 19 mol%, the still more preferable lower limit is 20 mol%, the particularly preferable lower limit is 21 mol%, and the preferable upper limit is 31 mol%, A more preferred upper limit is 30 mol%, a still more preferred upper limit is 29 mol%, and a particularly preferred upper limit is 28 mol%. When the hydroxyl group content b satisfies the preferable lower limit, the adhesive strength of the intermediate film can be further increased. When the hydroxyl group content b satisfies the preferable upper limit, the sound insulation of the laminated glass can be further enhanced.

  The polyvinyl acetal resin B is preferably a polyvinyl butyral resin.

  The polyvinyl acetal resin A and the polyvinyl acetal resin B are obtained by acetalizing polyvinyl alcohol with an aldehyde. The aldehyde is preferably an aldehyde having 1 to 10 carbon atoms, and more preferably an aldehyde having 4 or 5 carbon atoms.

  The polyvinyl acetal resin A and the polyvinyl acetal resin B are preferably polyvinyl acetal resins obtained by acetalizing polyvinyl alcohol X having a polymerization degree of 1600 to 3000 with an aldehyde. Since the occurrence of foaming and the growth of foaming in the laminated glass using the interlayer film for laminated glass can be sufficiently suppressed, the degree of polymerization of the polyvinyl alcohol X is preferably 1700 or more, preferably more than 1700, preferably 1800. Preferably, it is 2000 or more, preferably 2100 or more, preferably 2200 or more, preferably 2900 or less, and preferably 2800 or less. The degree of polymerization indicates an average degree of polymerization. The average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.

(Method for producing a polyvinyl acetal resin containing a high molecular weight component X having an absolute molecular weight of 1 million or more or a high molecular weight component Y having a molecular weight y of 1 million or more)
As an example of the thermoplastic resin containing the high molecular weight component X having an absolute molecular weight of 1,000,000 or more or the high molecular weight component Y having a molecular weight y of 1,000,000 or more at a ratio of the above lower limit or more, the high molecular weight component X having an absolute molecular weight of 1,000,000 or more The specific manufacturing method of the polyvinyl acetal resin containing the high molecular weight component Y whose molecular weight y is 1 million or more is demonstrated below.

  First, polyvinyl alcohol is prepared. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is generally in the range of 70 to 99.9 mol%, preferably in the range of 75 to 99.8 mol%, and preferably in the range of 80 to 99.8 mol%. It is more preferable.

  The preferred lower limit of the degree of polymerization of the polyvinyl alcohol is 200, the more preferred lower limit is 500, the still more preferred lower limit is 1,000, the particularly preferred lower limit is 1,500, the preferred upper limit is 3,000, the more preferred upper limit is 2,900, and further A preferred upper limit is 2,800, and a particularly preferred upper limit is 2,700. When the said polymerization degree is too low, there exists a tendency for the penetration resistance of a laminated glass to fall. If the polymerization degree is too high, it may be difficult to mold the intermediate film.

  Next, the polyvinyl alcohol and aldehyde are reacted using a catalyst to acetalize the polyvinyl alcohol. At this time, a solution containing the polyvinyl alcohol may be used. Water etc. are mentioned as a solvent used for the solution containing this polyvinyl alcohol.

  The method for producing the polyvinyl acetal resin contained in the first layer is a method for producing a polyvinyl acetal resin by reacting polyvinyl alcohol with an aldehyde using a catalyst to acetalize the polyvinyl alcohol. Is preferred.

  The manufacturing method of the said 1st layer is the process of obtaining polyvinyl acetal resin by making polyvinyl alcohol and an aldehyde react using a catalyst, and acetalizing polyvinyl alcohol, and the obtained polyvinyl acetal resin and a plasticizer, It is preferable to provide the process of obtaining the said 1st layer using the mixture which mixed. In the step of obtaining the first layer, or after obtaining the first layer, a second layer is laminated on the first layer, and a third layer is further laminated as necessary. Thus, a multilayer intermediate film can be obtained. Further, a multilayer intermediate film may be produced by coextrusion of the first layer and the second layer, and the multilayer may be produced by coextrusion of the first layer, the second layer, and the third layer. An intermediate film may be manufactured.

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

  From the viewpoint of easily obtaining a polyvinyl acetal resin containing high molecular weight components X and Y having an absolute molecular weight of 1 million or more or a molecular weight y of 1 million or more in the above specific ratio, for example, before or during the acetalization reaction with an aldehyde, In order to crosslink the main chain of the adjacent polyvinyl alcohol, a method of adding a crosslinking agent such as dialdehyde, a method of promoting an acetalization reaction between molecules by adding an excess of aldehyde, and a high degree of polymerization Examples include a method of adding polyvinyl alcohol. Moreover, these methods may be used independently and 2 or more types may be used together.

  The catalyst is preferably an acid catalyst. Examples of the acid catalyst include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and paratoluenesulfonic acid.

  The molecular weight in terms of polystyrene indicates the molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC). The ratio (%) of the high molecular weight component Y having a molecular weight y of 1 million or more in the thermoplastic resin is a peak area detected by an RI detector when measuring the molecular weight in terms of polystyrene by GPC of the thermoplastic resin. Of these, the molecular weight y is calculated from the ratio of the area corresponding to the region of 1 million or more. The peak area means the area between the peak of the component to be measured and the baseline.

  The molecular weight in terms of polystyrene is measured, for example, as follows.

  In order to measure the molecular weight in terms of polystyrene, GPC measurement of a polystyrene standard sample with a known molecular weight is performed. As polystyrene standard samples (“Shodex Standard SM-105”, “Shodex Standard SH-75” manufactured by Showa Denko KK), weight average molecular weights 580, 1,260, 2,960, 5,000, 10,100, 21, 14 samples of 000, 28,500, 76,600, 196,000, 630,000, 11,130,000, 2,190,000, 3,150,000, 3,900,000 are used. An approximate straight line obtained by plotting the weight average molecular weight against the elution time indicated by the peak top of each standard sample peak is used as a calibration curve. For example, the proportion (%) of the high molecular weight component Y having a molecular weight y of 1 million or more in the thermoplastic resin in the intermediate layer in the multilayer intermediate film in which the surface layer, the intermediate layer, and the surface layer are laminated in this order. Is measured, the surface layer and the intermediate layer are peeled from the multi-layered intermediate film left for one month in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.). The peeled intermediate layer is dissolved in tetrahydrofuran (THF) to prepare a 0.1% by weight solution. The obtained solution is analyzed by a GPC apparatus, and the peak area of the thermoplastic resin in the intermediate layer is measured. Next, an area corresponding to a region where the polystyrene-converted molecular weight of the thermoplastic resin in the intermediate layer is 1 million or more is calculated from the elution time of the thermoplastic resin in the intermediate layer and a calibration curve. By expressing the area corresponding to the area of polystyrene equivalent molecular weight of 1 million or more of the thermoplastic resin in the intermediate layer by the peak area of the thermoplastic resin in the intermediate layer as a percentage (%), the above thermoplasticity The ratio (%) of the high molecular weight component Y in which the molecular weight y is 1 million or more can be calculated. For example, a Gel Permeation Chromatography (GPC) apparatus (manufactured by Hitachi High-Tech, "RI: L2490, autosampler: L-2200, pump: L-2130, column oven: L-2350, column: GL-A120-S and GL-A100MX -S series ") can be used to measure polystyrene equivalent molecular weight.

(Plasticizer)
The said plasticizer contained in the said 1st-3rd layer is not specifically limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

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

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

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

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

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

  The plasticizer is preferably a diester plasticizer represented by the following formula (1). By using this diester plasticizer, the sound insulation of the laminated glass can be further enhanced.

  In said formula (1), R1 and R2 respectively represent a C5-C10 organic group, R3 represents an ethylene group, an isopropylene group, or n-propylene group, p represents the integer of 3-10. . R1 and R2 in the above formula (1) are each preferably an organic group having 6 to 10 carbon atoms.

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

  The content of the plasticizer in the interlayer film for laminated glass is not particularly limited.

  In the case of the first layer in which the thermoplastic resin contains the high molecular weight component X having an absolute molecular weight of 1 million or more in the specific ratio, the amount of the plasticizer relative to 100 parts by weight of the thermoplastic resin in the first layer. The preferred lower limit of the content is 40 parts by weight, the more preferred lower limit is 50 parts by weight, the still more preferred lower limit is 55 parts by weight, the particularly preferred lower limit is 60 parts by weight, the preferred upper limit is 80 parts by weight, and the more preferred upper limit is 78 parts by weight. A preferred upper limit is 75 parts by weight, and a particularly preferred upper limit is 72 parts by weight. In the case of the first layer containing the high molecular weight component Y having a molecular weight y of 1,000,000 or more in the specific ratio, the thermoplastic resin in the first layer with respect to 100 parts by weight of the thermoplastic resin is also included. The preferred lower limit of the plasticizer content is 40 parts by weight, the more preferred lower limit is 50 parts by weight, the still more preferred lower limit is 55 parts by weight, the particularly preferred lower limit is 60 parts by weight, the preferred upper limit is 80 parts by weight, and the more preferred upper limit is 78 parts by weight. Parts, and a more preferred upper limit is 75 parts by weight, and a particularly preferred upper limit is 72 parts by weight. When content of the said plasticizer satisfy | fills the said preferable minimum, the penetration resistance of a laminated glass can be improved further. When content of the said plasticizer satisfy | fills the said preferable upper limit, transparency of an intermediate film can be improved further.

  In the case of the second and third layers, the preferred lower limit of the plasticizer content relative to 100 parts by weight of the thermoplastic resin is 25 parts by weight, the more preferred lower limit is 30 parts by weight, and the still more preferred lower limit is 35 parts by weight. The preferred upper limit is 50 parts by weight, the more preferred upper limit is 45 parts by weight, the still more preferred upper limit is 43 parts by weight, and the particularly preferred upper limit is 38 parts by weight. When content of the said plasticizer satisfy | fills the said preferable minimum, the adhesive force of an intermediate film will become high and the penetration resistance of a laminated glass can be improved further. When content of the said plasticizer satisfy | fills the said preferable upper limit, transparency of an intermediate film can be improved further.

  From the viewpoint of further improving the sound insulation of the laminated glass, the content of the plasticizer relative to 100 parts by weight of the thermoplastic resin in the first layer is 100 parts by weight of the thermoplastic resin in the second and third layers. It is preferable that there is more content of the plasticizer with respect to. From the viewpoint of further improving the sound insulation of the laminated glass, the content of the plasticizer relative to 100 parts by weight of the thermoplastic resin in the first layer is 100 parts by weight of the thermoplastic resin in the second and third layers. It is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more.

(Other ingredients)
Each of the first to third layers is, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, and a fluorescent whitening. An additive such as an agent and an infrared absorber may be contained.

(Method for producing interlayer film for laminated glass and laminated glass)
The manufacturing method of the interlayer film for laminated glass according to the present invention is not particularly limited. In the case of the single-layer interlayer film, the method for producing the interlayer film for laminated glass according to the present invention includes using a resin composition containing the polyvinyl acetal resin and the plasticizer, and extruding the resin composition. Examples thereof include a method of obtaining a single-layer intermediate film as the first layer by extruding using a machine. In the case of the multilayer interlayer film, the method for producing the interlayer film for laminated glass according to the present invention uses the resin composition containing the polyvinyl acetal resin and the plasticizer, and the first to third layers. For example, a method of laminating the second layer, the first layer, and the third layer in this order, and coextruding the resin composition using an extruder. And a method of laminating the second layer, the first layer, and the third layer in this order. Since the production efficiency of the intermediate film is excellent, the second and third layers preferably contain the same plasticizer, and preferably contain the same polyvinyl acetal resin. More preferably, the third layer contains the same polyvinyl acetal resin and the same plasticizer, and the second and third layers are more preferably formed of the same resin composition. .

  The interlayer film for laminated glass according to the present invention is used for obtaining laminated glass.

  FIG. 6 is a cross-sectional view schematically showing an example of a laminated glass using the multilayer intermediate film 1 shown in FIG.

  A laminated glass 11 shown in FIG. 6 includes a first laminated glass constituting member 12, a second laminated glass constituting member 13, and a multilayer interlayer film 1. The multilayer intermediate film 1 is sandwiched between the first and second laminated glass constituent members 12 and 13.

  The first laminated glass constituting member 12 is laminated on the outer surface 3 a of the second layer 3. The second laminated glass component 13 is laminated on the outer surface 4 a of the third layer 4. Accordingly, the laminated glass 11 is composed of the first laminated glass constituting member 12, the second layer 3, the first layer 2, the third layer 4, and the second laminated glass constituting member 13 in this order. It is laminated and configured.

  Examples of the first and second laminated glass constituent members include glass plates and PET (polyethylene terephthalate) films. Laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like. Laminated glass is a laminated body provided with a glass plate, and preferably at least one glass plate is used.

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

  The thickness of the single-layer interlayer film and the multilayer interlayer film is not particularly limited. In the case of a multilayer intermediate film, the thickness of the intermediate film indicates the total thickness of each layer constituting the intermediate film. Therefore, in the case of a multilayer intermediate film including the first, second, and third layers, the thickness of the intermediate film indicates the total thickness of the first, second, and third layers. From the viewpoint of further improving the penetration resistance of the laminated glass, the preferable lower limit of the thickness of the interlayer film is 0.05 mm, the more preferable lower limit is 0.25 mm, the preferable upper limit is 3 mm, and the more preferable upper limit is 1.5 mm. When the thickness of the interlayer film satisfies the preferable lower limit and the preferable upper limit, the penetration resistance and transparency of the laminated glass can be further enhanced. From the viewpoint of practical use and the viewpoint of sufficiently improving penetration resistance, the maximum thickness of the intermediate film is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1.5 mm or less. The minimum thickness of the interlayer film is preferably 0.1 mm or more, more preferably 0.25 mm or more, still more preferably 0.5 mm or more, and particularly preferably 0.8 mm or more. It is preferable that one end of the intermediate film has a maximum thickness and the other end of the intermediate film has a minimum thickness.

  In the case of the multilayer interlayer film, the preferred lower limit of the thickness of the first layer is 0.01 mm, the more preferred lower limit is 0.04 mm, the still more preferred lower limit is 0.07 mm, the preferred upper limit is 0.3 mm, and the more preferred upper limit. Is 0.2 mm, and a more preferable upper limit is 0.18 mm, and a particularly preferable upper limit is 0.16 mm. When the thickness of the first layer satisfies the above lower limit, the sound insulating property of the laminated glass can be further increased, and when the upper limit is satisfied, the transparency of the laminated glass can be further increased. From the viewpoint of practical use and the viewpoint of sufficiently increasing penetration resistance, the maximum thickness of the first layer is preferably 0.8 mm or less, more preferably 0.6 mm or less. The minimum thickness of the first layer is preferably 0.001 mm or more, more preferably 0.05 mm or more.

  In the case of the multilayer interlayer film, the preferred lower limit of the thickness of the second and third layers is 0.1 mm, the more preferred lower limit is 0.2 mm, the still more preferred lower limit is 0.25 mm, and the particularly preferred lower limit is 0.3 mm. The preferred upper limit is 0.6 mm, the more preferred upper limit is 0.5 mm, the still more preferred upper limit is 0.45 mm, and the particularly preferred upper limit is 0.4 mm. When the thicknesses of the second and third layers satisfy the above lower limit, the penetration resistance of the laminated glass can be further increased, and when the upper limit is satisfied, the transparency of the laminated glass can be further increased. From the viewpoint of practical use and the viewpoint of sufficiently increasing the adhesive strength and penetration resistance, the maximum thicknesses of the second and third layers are each preferably 1 mm or less, more preferably 0.8 mm or less. The minimum thickness of each of the second and third layers is preferably 0.001 mm or more, more preferably 0.2 mm or more.

  In the case of the multilayer interlayer film, the ratio of the minimum thickness of the first layer to the thickness of the interlayer film ((minimum thickness of the first layer) / (thickness of the interlayer film)) is small. As the content of the plasticizer contained in the first layer is larger, foaming in the laminated glass occurs and the foam tends to grow. In particular, when the ratio in the intermediate film is 0.05 to 0.35 and the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 55 parts by weight or more, Generation | occurrence | production of foaming and the growth of foaming in the laminated glass using the intermediate film for laminated glass which concerns on invention can fully be suppressed, and the sound-insulating property of laminated glass can be improved further. The preferable lower limit of the ratio ((minimum thickness of the first layer) / (intermediate film thickness)) is 0.06, the more preferable lower limit is 0.07, the still more preferable lower limit is 0.08, and the particularly preferable lower limit is 0. 0.1, a preferred upper limit is 0.3, a more preferred upper limit is 0.25, a still more preferred upper limit is 0.2, and a particularly preferred upper limit is 0.15. In the ratio of the minimum thickness of the first layer to the thickness of the intermediate film, the thickness of the intermediate film means the thickness of the intermediate film at the minimum thickness portion of the first layer.

  The interlayer film for laminated glass according to the present invention may have a transparent or opaque colored region and a second region different from the colored region. The intermediate film may have a transparent or opaque colored region R1 (first region) and a second region R2 different from the colored region R1. The intermediate film may have a colored band in a partial region. When the multilayer intermediate film has a colored band, it is preferable that either one of the second and third surface layers has a colored band. However, the first layer may have a colored band. The colored band can be formed, for example, by blending a colorant into a predetermined region when extrusion molding the interlayer film for laminated glass or each layer of the interlayer film.

  The thickness of the first and second laminated glass constituting members is preferably 0.5 mm or more, more preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. Moreover, when the said laminated glass structural member is a glass plate, it is preferable that the thickness of this glass plate exists in the range of 1-3 mm. When the laminated glass component is a PET film, the thickness of the PET film is preferably in the range of 0.03 to 0.5 mm.

  The manufacturing method of a laminated glass is not specifically limited. For example, the intermediate film is sandwiched between the first and second laminated glass constituent members, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, and the first and second laminated glass The air remaining between the glass component and the intermediate film is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained.

  The laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used in addition to these. The laminated glass is preferably laminated glass for buildings or vehicles, and more preferably laminated glass for vehicles. Laminated glass can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile.

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

  First, the following polyvinyl acetal resins A to Q and U to Z were synthesized.

(Synthesis Example 1)
Synthesis of polyvinyl acetal resin A:
A reactor equipped with a stirrer was charged with 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average polymerization degree of 2300 and a saponification degree of 87.5 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution so that the hydrochloric acid concentration became 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 14.2 g of n-butyraldehyde was added with stirring. did. Thereafter, when 170 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 35 wt% hydrochloric acid was added so that the hydrochloric acid concentration was 3.9 wt%, heated to 45 ° C., and aged at 45 ° C. for 3 hours. Then, after cooling and neutralizing the solution, the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin A.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin A was 11.5%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin A was 13.8%. The resulting polyvinyl butyral resin A has a number average molecular weight of 102,000, a weight average molecular weight of 750,000, a hydroxyl group content of 22.3 mol%, an acetylation degree of 12.5 mol%, and a butyralization degree of 65. It was 2 mol%.

(Synthesis Example 2)
Synthesis of polyvinyl acetal resin B:
A reactor equipped with a stirrer was charged with 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average polymerization degree of 2300 and a saponification degree of 87.5 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution so that the hydrochloric acid concentration became 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 14.2 g of n-butyraldehyde was added with stirring. did. Then, when 175 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 35 wt% hydrochloric acid was added so that the hydrochloric acid concentration was 3.9 wt%, heated to 45 ° C., and aged at 45 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin B.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin B was 15.4%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin B was 17.3%. The resulting polyvinyl butyral resin B has a number average molecular weight of 105,000, a weight average molecular weight of 1,175,000, a hydroxyl group content of 22.0 mol%, an acetylation degree of 12.5 mol%, and a butyralization degree. Was 65.5 mol%.

(Synthesis Example 3)
Synthesis of polyvinyl acetal resin C:
A reactor equipped with a stirrer was charged with 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average polymerization degree of 2300 and a saponification degree of 87.5 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution so that the hydrochloric acid concentration became 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 14.2 g of n-butyraldehyde was added with stirring. did. Then, when 186 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 35 wt% hydrochloric acid was added so that the hydrochloric acid concentration was 3.9 wt%, heated to 45 ° C., and aged at 45 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin C.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin C was 20.9%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin C was 24.5%. The resulting polyvinyl butyral resin C has a number average molecular weight of 120,000, a weight average molecular weight of 2,565,000, a hydroxyl group content of 23.0 mol%, an acetylation degree of 12.5 mol%, and a butyralization degree. Was 64.5 mol%.

(Synthesis Example 4)
Synthesis of polyvinyl acetal resin D:
In a reactor equipped with a stirrer, 2400 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 99.2 mol% were added and dissolved by heating to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.45% by weight, the temperature was adjusted to 15 ° C., and 27 g of n-butyraldehyde was added with stirring. Thereafter, when 181 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.1 wt%, heated to 48 ° C., and aged at 48 ° C. for 2 hours. Next, after cooling and neutralizing the solution, the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin D.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin D was 8%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin D was 9.1%. The resulting polyvinyl butyral resin D has a number average molecular weight of 100,000, a weight average molecular weight of 520,000, a hydroxyl group content of 21.7 mol%, an acetylation degree of 0.8 mol%, and a butyralization degree of 77. It was 5 mol%.

(Synthesis Example 5)
Synthesis of polyvinyl acetal resin E:
In a reactor equipped with a stirrer, 3000 g of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2300 and a degree of saponification of 87.5 mol% were added and dissolved by heating to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6% by weight, and the temperature was adjusted to 15 ° C., and then 14 g of n-butyraldehyde was added with stirring. Then, when 165 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60% by weight nitric acid was added so that the nitric acid concentration was 1.3% by weight, heated to 42 ° C., and aged at 42 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin E.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin E was 16.4%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin E was 18.7%. The resulting polyvinyl butyral resin E has a number average molecular weight of 125,000, a weight average molecular weight of 1,062,000, a hydroxyl group content of 27.0 mol%, an acetylation degree of 12.5 mol%, and a butyralization degree. Was 60.5 mol%.

(Synthesis Example 6)
Synthesis of polyvinyl acetal resin F:
A reactor equipped with a stirrer was charged with 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 99.2 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution so that the hydrochloric acid concentration was 0.2 wt%, the temperature was adjusted to 15 ° C., and 23 g of n-butyraldehyde was added with stirring. Thereafter, when 143 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 35 wt% hydrochloric acid was added so that the hydrochloric acid concentration was 1.8 wt%, heated to 60 ° C., and aged at 60 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin F.

  The resulting polyvinyl butyral resin F has a number average molecular weight of 125,000, a weight average molecular weight of 1,062,000, a hydroxyl group content of 30.4 mol%, an acetylation degree of 0.8 mol%, and a butyralization degree. Was 68.8 mol%.

(Synthesis Example 7)
Synthesis of polyvinyl acetal resin G:
In a reactor equipped with a stirrer, 3000 g of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2300 and a degree of saponification of 87.5 mol% were added and dissolved by heating to obtain a solution. Next, 60% by weight nitric acid was added to this solution as a catalyst so that the nitric acid concentration was 0.6% by weight, the temperature was adjusted to 15 ° C., and then 14.2 g of n-butyraldehyde was added with stirring. did. Then, when 165 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.3 wt%, heated to 55 ° C., and aged at 55 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin G.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin G was 7.3%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin G was 8.8%. The resulting polyvinyl butyral resin G has a number average molecular weight of 85,000, a weight average molecular weight of 509,000, a hydroxyl group content of 23.0 mol%, an acetylation degree of 12.5 mol%, and a butyralization degree of 64. It was 5 mol%.

(Synthesis Example 8)
Synthesis of polyvinyl acetal resin H:
In a reactor equipped with a stirrer, 2400 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 99.2 mol% were added and dissolved by heating to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.45% by weight, the temperature was adjusted to 15 ° C., and 27 g of n-butyraldehyde was added with stirring. Thereafter, when 181 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.1 wt%, heated to 55 ° C., and aged at 55 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin H.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin H was 6.5%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin H was 7.6%. The resulting polyvinyl butyral resin H has a number average molecular weight of 112,000, a weight average molecular weight of 500,000, a hydroxyl group content of 21.2 mol%, an acetylation degree of 0.8 mol%, and a butyralization degree of 78. 0.0 mol%.

(Synthesis Example 9)
Synthesis of polyvinyl acetal resin I:
A reactor equipped with a stirrer was charged with 3000 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2300 and a degree of saponification of 86.9 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 13 g of n-butyraldehyde was added with stirring. Then, when 180 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.7 wt%, heated to 52 ° C., and aged at 52 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin I.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin I was 9%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin I was 11.6%. The resulting polyvinyl butyral resin I has a number average molecular weight of 165,000, a weight average molecular weight of 550,000, a hydroxyl group content of 22.9 mol%, an acetylation degree of 13.1 mol%, and a butyralization degree of 64. 0.0 mol%.

(Synthesis Example 10)
Synthesis of polyvinyl acetal resin J:
In a reactor equipped with a stirrer, 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2500 and a degree of saponification of 99.2 mol% were added and dissolved by heating to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 13 g of n-butyraldehyde was added with stirring. Then, when 200 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.0 wt%, heated to 52 ° C., and aged at 52 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin J.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin J was 9.5%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin J was 11.8%. The resulting polyvinyl butyral resin J has a number average molecular weight of 167,000, a weight average molecular weight of 448,000, a hydroxyl group content of 21.2 mol%, an acetylation degree of 0.8 mol%, and a butyralization degree of 78. 0.0 mol%.

(Synthesis Example 11)
Synthesis of polyvinyl acetal resin K:
In a reactor equipped with a stirrer, 3000 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2320 and a degree of saponification of 94.4 mol% was added and dissolved by heating to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 13 g of n-butyraldehyde was added with stirring. Thereafter, when 205 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.3 wt%, heated to 51 ° C., and aged at 51 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin K.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin K was 9.8%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin K was 12.0%. The resulting polyvinyl butyral resin K has a number average molecular weight of 155,000, a weight average molecular weight of 530,000, a hydroxyl group content of 21.9 mol%, an acetylation degree of 5.6 mol%, and a butyralization degree of 72. It was 5 mol%.

(Synthesis Example 12)
Synthesis of polyvinyl acetal resin L:
In a reactor equipped with a stirrer, 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 87.5 mol% were added and dissolved by heating to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6 wt%, and the temperature was adjusted to 15 ° C., and then 13 g of n-butyraldehyde was added with stirring. Then, when 175 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.9 wt%, heated to 53 ° C., and aged at 53 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin L.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin L was 7.5%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin L was 9.0%. The resulting polyvinyl butyral resin L has a number average molecular weight of 158,000, a weight average molecular weight of 546,000, a hydroxyl group content of 23.5 mol%, an acetylation degree of 12.5 mol%, and a butyralization degree of 64. 0.0 mol%.

(Synthesis Example 13)
Synthesis of polyvinyl acetal resin M:
A reactor equipped with a stirrer was charged with 3200 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average polymerization degree of 2300 and a saponification degree of 99.2 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.4 wt%, and the temperature was adjusted to 15 ° C., and then 17 g of n-butyraldehyde was added with stirring. Thereafter, when 170 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.1 wt%, heated to 55 ° C., and aged at 55 ° C. for 2.5 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin M.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin M was 6.9%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin M was 8.4%. The resulting polyvinyl butyral resin M has a number average molecular weight of 148,000, a weight average molecular weight of 410,000, a hydroxyl group content of 20.4 mol%, an acetylation degree of 0.8 mol%, and a butyralization degree of 78. It was 8 mol%.

(Synthesis Example 14)
Synthesis of polyvinyl acetal resin N:
A reactor equipped with a stirrer was charged with 3200 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2300 and a degree of saponification of 87.8 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.5% by weight, and the temperature was adjusted to 15 ° C., and then 11 g of n-butyraldehyde was added with stirring. Thereafter, when 160 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.7 wt%, heated to 57 ° C., and aged at 57 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin N.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin N was 7.2%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin N was 8.9%. The resulting polyvinyl butyral resin N has a number average molecular weight of 152,000, a weight average molecular weight of 430,000, a hydroxyl group content of 23.4 mol%, an acetylation degree of 12.2 mol%, and a butyralization degree of 64. It was 4 mol%.

(Synthesis Example 15)
Polyvinyl acetal resin O synthesis:
In a reactor equipped with a stirrer, 300 g of polyvinyl alcohol having 3000 ml of ion-exchanged water, an average degree of polymerization of 2000, and a degree of saponification of 93.5 mol% was charged and dissolved with heating to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6% by weight, and the temperature was adjusted to 15 ° C., and then 11 g of n-butyraldehyde was added with stirring. Thereafter, when 170 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.8 wt%, heated to 58 ° C., and aged at 58 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin O.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin O was 6.6%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin O was 7.6%. The resulting polyvinyl butyral resin O has a number average molecular weight of 138,000, a weight average molecular weight of 402,000, a hydroxyl group content of 20.4 mol%, an acetylation degree of 6.5 mol%, and a butyralization degree of 73. It was 1 mol%.

(Synthesis Example 16)
Synthesis of polyvinyl acetal resin P:
A reactor equipped with a stirrer was charged with 2700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 98.9 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.7% by weight, and the temperature was adjusted to 15 ° C., and then 15 g of n-butyraldehyde was added with stirring. Then, when 175 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.6 wt%, heated to 52 ° C., and aged at 52 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin P.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin P was 5.3%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin P was 6.8%. The resulting polyvinyl butyral resin P has a number average molecular weight of 140,000, a weight average molecular weight of 390,000, a hydroxyl group content of 21.0 mol%, an acetylation degree of 1.1 mol%, and a butyralization degree of 77. It was 9 mol%.

(Synthesis Example 17)
Synthesis of polyvinyl acetal resin Q:
A reactor equipped with a stirrer was charged with 3350 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 87.8 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.5% by weight, the temperature was adjusted to 15 ° C., and then 15 g of n-butyraldehyde was added with stirring. Thereafter, when 150 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.7 wt%, heated to 57 ° C., and aged at 57 ° C. for 2.5 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin Q.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin Q was 5.1%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin Q was 6.4%. The resulting polyvinyl butyral resin Q has a number average molecular weight of 143,000, a weight average molecular weight of 395,000, a hydroxyl group content of 22.8 mol%, an acetylation degree of 12.2 mol%, and a butyralization degree of 65. 0.0 mol%.

(Synthesis Example 18)
Synthesis of polyvinyl acetal resin U:
A reactor equipped with a stirrer was charged with 3200 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average polymerization degree of 2380 and a saponification degree of 90.5 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.55 wt%, the temperature was adjusted to 15 ° C., and 13 g of n-butyraldehyde was added with stirring. Then, when 180 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60% by weight nitric acid was added so that the nitric acid concentration was 1.8% by weight, heated to 55 ° C., and aged at 55 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin U.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin U was 9.4%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin U was 11.5%. The resulting polyvinyl butyral resin U has a number average molecular weight of 170,000, a weight average molecular weight of 530,000, a hydroxyl group content of 23 mol%, an acetylation degree of 9.5 mol%, and a butyralization degree of 67.5. Mol%.

(Synthesis Example 19)
Synthesis of polyvinyl acetal resin V:
Synthesis of polyvinyl acetal resin V:
A reactor equipped with a stirrer was charged with 3400 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2450 and a saponification degree of 82.5 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60 wt% nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.65 wt%, the temperature was adjusted to 15 ° C., and 13 g of n-butyraldehyde was added with stirring. Then, when 175 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 1.9 wt%, heated to 55 ° C., and aged at 55 ° C. for 2.5 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin V.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin V was 8.5%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin V was 10.9%. The resulting polyvinyl butyral resin V has a number average molecular weight of 150,000, a weight average molecular weight of 500,000, a hydroxyl group content of 23.2 mol%, an acetylation degree of 17.5 mol%, and a butyralization degree of 59. It was 3 mol%.

(Synthesis Example 20)
Synthesis of polyvinyl acetal resin W:
A reactor equipped with a stirrer was charged with 3500 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2500 and a degree of saponification of 77.7 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.5% by weight, the temperature was adjusted to 15 ° C., and then 15 g of n-butyraldehyde was added with stirring. Thereafter, when 185 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.0 wt%, heated to 51 ° C., and aged at 51 ° C. for 2 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin W.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin W was 12.5%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin W was 15%. The resulting polyvinyl butyral resin W has a number average molecular weight of 170,000, a weight average molecular weight of 650,000, a hydroxyl group content of 24 mol%, an acetylation degree of 22.3 mol%, and a butyralization degree of 53.7. Mol%.

(Synthesis Example 21)
Synthesis of polyvinyl acetal resin X:
A reactor equipped with a stirrer was charged with 2900 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 92.6 mol%, and dissolved with heating to obtain a solution. Next, 60% by weight nitric acid as a catalyst was added to this solution so that the nitric acid concentration was 0.5% by weight, the temperature was adjusted to 15 ° C., and then 14 g of n-butyraldehyde was added with stirring. Then, when 200 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.1 wt%, heated to 50 ° C., and aged at 50 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin X.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin X was 17.3%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin X was 19.8%. The resulting polyvinyl butyral resin X has a number average molecular weight of 160,000, a weight average molecular weight of 670,000, a hydroxyl group content of 22 mol%, an acetylation degree of 7.4 mol%, and a butyralization degree of 70.6. Mol%.

(Synthesis Example 22)
Synthesis of polyvinyl acetal resin Y:
A reactor equipped with a stirrer was charged with 3300 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2350 and a degree of saponification of 95.8 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6% by weight, and the temperature was adjusted to 15 ° C., and then 14 g of n-butyraldehyde was added with stirring. Then, when 200 g of n-butyraldehyde was added, a white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.3 wt%, heated to 52 ° C, and aged at 52 ° C for 2.5 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin Y.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin Y was 14.2%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin Y was 17.6%. The resulting polyvinyl butyral resin Y has a number average molecular weight of 160,000, a weight average molecular weight of 620,000, a hydroxyl group content of 21.9 mol%, an acetylation degree of 4.2 mol%, and a butyralization degree of 73. It was 9 mol%.

(Synthesis Example 23)
Synthesis of polyvinyl acetal resin Z:
A reactor equipped with a stirrer was charged with 3700 ml of ion-exchanged water, 300 g of polyvinyl alcohol having an average degree of polymerization of 2400 and a degree of saponification of 98.7 mol%, and was heated and dissolved while stirring to obtain a solution. Next, 60% by weight nitric acid was added to the solution as a catalyst so that the nitric acid concentration was 0.6% by weight, and the temperature was adjusted to 15 ° C., and then 17 g of n-butyraldehyde was added with stirring. Thereafter, when 205 g of n-butyraldehyde was added, white particulate polyvinyl butyral resin was precipitated. 15 minutes after the precipitation, 60 wt% nitric acid was added so that the nitric acid concentration was 2.3 wt%, heated to 53 ° C., and aged at 53 ° C. for 3 hours. Next, the solution was cooled and neutralized, and then the polyvinyl butyral resin was washed with water and dried to obtain a polyvinyl butyral resin Z.

  The proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin Z was 11.3%. The proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin Z was 15.3%. The resulting polyvinyl butyral resin Z has a number average molecular weight of 165,000, a weight average molecular weight of 600,000, a hydroxyl group content of 20.5 mol%, an acetylation degree of 1.3 mol%, and a butyralization degree of 78. It was 2 mol%.

  Moreover, the following polyvinyl butyral resins R to T were prepared.

Polyvinyl butyral resin R: hydroxyl group content: 30.4 mol%, acetylation degree: 0.8 mol%, butyralization degree: 68.8 mol%
Polyvinyl butyral resin S: hydroxyl group content: 30.5 mol%, acetylation degree: 0.8 mol%, butyralization degree: 68.7 mol%
Polyvinyl butyral resin T: hydroxyl group content: 30.7 mol%, acetylation degree: 0.8 mol%, butyralization degree: 68.5 mol%

  Using the obtained polyvinyl acetal resins AZ (polyvinyl butyral resins AZ), multilayer interlayer films for laminated glass and laminated glass were produced as follows.

Example 1
(1) Production of multilayer intermediate film To 100 parts by weight of the obtained polyvinyl butyral resin A, 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer was added and sufficiently kneaded with a mixing roll. The intermediate layer resin composition was obtained. Further, 37.5 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer was added to 100 parts by weight of the obtained polyvinyl butyral resin F, and the mixture was sufficiently kneaded with a mixing roll, and the surface layer A resin composition was obtained.

  A multilayer intermediate film in which a surface layer, an intermediate layer, and a surface layer are sequentially laminated by co-extrusion using the obtained resin composition for an intermediate layer and the resin composition for a surface layer (length 1000 mm × width 350 mm) Was made. In this multilayer intermediate film, the thickness of one end in the vertical direction is made thinner than the thickness of the other end opposite to the one end, the thickness in the horizontal direction is made uniform, and the surface layers (second and third layers) and The maximum thickness and minimum thickness of the intermediate layer (first layer) and the wedge angle θ of the intermediate film are set as shown in Table 1 below.

(2) Preparation of laminated glass used for penetration resistance test The obtained multilayer interlayer film was cut into a size of 30 cm in length and 30 cm in width so as to take out the central portion in the vertical direction and the horizontal direction. Next, a multilayer intermediate film was sandwiched between two transparent float glasses (length 30 cm × width 30 cm × thickness 2.5 mm) to obtain a laminate. This laminated body is put in a rubber bag, deaerated at a vacuum degree of 2.6 kPa for 20 minutes, transferred to an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum-pressed. Crimped. The pre-pressed laminate was pressed for 20 minutes in an autoclave at 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass used for the penetration resistance test.

(3) Production of laminated glass used for sound insulation measurement The multilayer interlayer film is cut into a size of 30 cm in length and 2.5 cm in width so as to take out the central portion in the vertical direction and the horizontal direction. A laminated glass used for sound insulation measurement was obtained in the same manner as the laminated glass used for the penetration resistance test except that 30 cm × 2.5 cm wide × 2.5 mm thick) was used.

(4) Production of laminated glass used for foaming tests A and B The obtained multilayer interlayer film includes an end portion on one end side in the longitudinal direction so as to take out a central portion in the lateral direction and a relatively thin thickness. The sample was cut into a size of 30 cm (length) × 15 cm (width), and stored in an environment at a temperature of 23 ° C. for 10 hours. Further, the obtained multilayer intermediate film is cut into a size of 30 cm in length and 15 cm in width so as to take out the central portion in the horizontal direction and include the end portion on the other end side in the vertical direction where the thickness is relatively thick. And stored for 10 hours in an environment at a temperature of 23 ° C. In addition, embossing was formed on both surfaces of the obtained multilayer intermediate film, and the ten-point average roughness of the embossing was 30 μm. In the cut multilayer intermediate film, an intersection 4 between a position 8 cm inward in the vertical direction from the end of the multilayer intermediate film and a position 5 cm inward in the lateral direction from the end of the multilayer intermediate film. A through-hole with a diameter of 6 mm was produced at the location.

  A multilayer intermediate film having a through hole was sandwiched between two transparent float glasses (length 30 cm × width 15 cm × thickness 2.5 mm) to obtain a laminate. The outer peripheral edge of the laminate was sealed with a width of 2 cm from the end by heat sealing, thereby enclosing the air remaining in the emboss and the air remaining in the through hole. The laminated body is pressure-bonded at 135 ° C. and a pressure of 1.2 MPa for 20 minutes, so that the remaining air is dissolved in the multilayer interlayer film, and an interlayer film that is relatively thin for use in the foaming tests A and B is used. Laminated glass X and laminated glass Y using a relatively thick intermediate film were obtained.

(Examples 2 to 21 and Comparative Examples 1 to 9)
A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the compositions of the first to third interlayer films were changed as shown in Tables 1 to 4 below.

(Examples 22 to 24)
Except that the maximum thickness and minimum thickness of the surface layer (second and third layers) and intermediate layer (first layer), and the wedge angle θ of the intermediate film were set as shown in Table 5 below. In the same manner as in Example 1, a multilayer interlayer film and a laminated glass were produced.

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

  From the ratio of the loss factor thus obtained and the resonance frequency of the laminated glass, a graph showing the relationship between the sound frequency (Hz) and the sound transmission loss (dB) at 20 ° C. is created. The minimum sound transmission loss (TL value) in the vicinity of 000 Hz was determined. The higher the TL value, the higher the sound insulation. The results are shown in Tables 1 to 5 below, assuming that the case where the TL value is 35 dB or more is “◯” and the case where the TL value is less than 35 dB is “x”.

(2) Foam test A (foaming state)
Five sheets of laminated glass X and laminated glass Y used for the foaming test A were prepared for each multilayer intermediate film and left in an oven at 50 ° C. for 100 hours. In the laminated glass after being left, the presence or absence of foaming and the size of foaming were visually observed in plan view, and the state of foaming was judged according to the following criteria.

[Criteria for foaming state in foaming test A]
Foam generated in five laminated glasses was approximated by an ellipse, and the area of the ellipse was defined as the foamed area. The average value of the elliptical areas observed in the five laminated glasses was determined, and the ratio (percentage) of the average value (foamed area) of the elliptical area to the area (30 cm × 15 cm) of the laminated glass was determined.

◯: No foaming was observed in all the 5 laminated glasses. ○: The ratio of the average value of the elliptical area (foamed area) was less than 5%. △: The ratio of the average value of the elliptical area (foamed area) It was 5% or more and less than 10% x: The ratio of the average value (foaming area) of the elliptical area was 10% or more

(3) Foam test B (foaming state)
30 sheets of laminated glass X and laminated glass Y used for the foaming test B were prepared for each multilayer intermediate film and left in an oven at 50 ° C. for 24 hours. In the laminated glass after being allowed to stand, the number of laminated glasses in which foaming was visually observed was confirmed and judged according to the following criteria.

[Criteria for foaming state in foaming test B]
◯: There were 5 or less laminated glasses in which foaming was observed visually. ○: 6 or more laminated glasses in which foaming was visually observed was △: laminated in which foaming was visually observed. The glass was 11 or more and 15 or less. X: The laminated glass in which foaming was visually observed was 16 or more.

(4) Penetration resistance The laminated glass (length 30 cm x width 30 cm) used in the penetration resistance test was adjusted so that the surface temperature was 23 ° C. Next, in accordance with JIS R3212, a rigid sphere having a mass of 2260 g and a diameter of 82 mm was dropped from the height of 4 m onto the center portion of the laminated glass for each of the six laminated glasses. For all six laminated glasses, the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. If the number of laminated glasses in which the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was 3 or less, it was rejected. In the case of four sheets, the penetration resistance of six new laminated glasses was evaluated. In the case of 5 sheets, one additional laminated glass was additionally tested, and the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. In the same manner, from a height of 5 m and 6 m, a rigid sphere having a mass of 2260 g and a diameter of 82 mm was dropped on the laminated glass of 6 sheets, and the penetration resistance of the laminated glass was evaluated. .

(Measurement of absolute molecular weight)
The absolute molecular weight and polystyrene equivalent molecular weight for determining the ratio of the high molecular weight components X and Y described in Synthesis Examples 1 to 5 and 7 to 23 are obtained by peeling the surface layer and the intermediate layer from the obtained multilayer intermediate film. The value obtained as follows.

  In order to measure the absolute molecular weight, first, the multilayer intermediate film was left in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for 1 month. After standing for 1 month, the surface layer and the intermediate layer were peeled from the multilayer intermediate film. The peeled intermediate layer was dissolved in tetrahydrofuran (THF) to prepare a 0.1% by weight solution. Gel Permeation Chromatography (GPC) apparatus (“HI: Hitachi, Ltd.“ RI: L2490, autosampler: L-2200, pump: L-2130, column oven: L-2350, column: GL-A120-S and GL-A100MX-S in series "). In addition, a GPC light scattering detector (“Model 270 (RALS + VISCO)” manufactured by VISCOTEK)) is connected to the GPC apparatus, and chromatogram analysis can be performed by each detector. By analyzing the peak of the polyvinyl butyral resin component in the chromatogram of the RI detector and the RALS detector using analysis software (OmniSEC), the absolute molecular weight at each elution time of the polyvinyl butyral resin was determined. The ratio of the area of the area where the absolute molecular weight of the polyvinyl butyral resin is 1 million or more to the peak area of the polyvinyl butyral resin detected by the RI detector was expressed as a percentage (%).

  The following formula is established for the peak of each component in the chromatogram.

A _RI = c × (dn / dc) × K _RI Expression (1)
A _RALS = c × M × (dn / dc) ² × K _RALS (2)

  Here, c is the polymer concentration in the solution, (dn / dc) is the refractive index increment, M is the absolute molecular weight, and K is the device constant.

  As a specific measurement procedure, first, a polystyrene standard sample (PolyCAL (registered trademark) TDS-PS-NB Mw = 98390 dn / dc = 0.185 manufactured by VISCOTEK) having known c, M, and (dn / dc). ) To prepare a 0.1 wt% THF solution. The apparatus constant K of each detector is calculated | required using Formula (1) and (2) from the GPC measurement result of the obtained polystyrene solution.

  Next, the peeled intermediate layer is dissolved in THF to prepare a THF solution. Using the formulas (1) and (2), the absolute molecular weight M of the polyvinyl butyral resin was determined from the GPC measurement results of the obtained polyvinyl butyral resin solution.

  However, in order to analyze the intermediate layer (including the polyvinyl butyral resin and the plasticizer), it is necessary to determine the concentration of the polyvinyl butyral resin in the polyvinyl butyral resin solution. The method for obtaining the concentration of the polyvinyl butyral resin was calculated from the following results (measurement of plasticizer content).

(Measurement of molecular weight y)
In the same manner as the absolute molecular weight measurement method, the polystyrene-equivalent molecular weight is measured by gel permeation chromatography (GPC), and the molecular weight of the peak area (GPC measurement result) detected by the RI detector is 1,000,000. From the proportion of the area corresponding to the above region, the proportion (%) of the high molecular weight component Y having a molecular weight y of 1,000,000 or more in the polyvinyl butyral resin was calculated.

  In order to measure the molecular weight in terms of polystyrene, GPC measurement of a polystyrene standard sample with a known molecular weight is performed. As polystyrene standard samples (“Shodex Standard SM-105”, “Shodex Standard SH-75” manufactured by Showa Denko KK), weight average molecular weights 580, 1,260, 2,960, 5,000, 10,100, 21, 14 samples of 000, 28,500, 76,600, 196,000, 630,000, 11,130,000, 2,190,000, 3,150,000, 3,900,000 were used. An approximate straight line obtained by plotting the weight average molecular weight against the elution time indicated by the peak top of each standard sample peak was used as a calibration curve. The surface layer and the intermediate layer were peeled from the multilayer intermediate film that was left in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for one month. The peeled intermediate layer was dissolved in tetrahydrofuran (THF) to prepare a 0.1% by weight solution. The obtained solution was analyzed by a GPC apparatus, and the peak area of the thermoplastic resin in the intermediate layer was measured. Subsequently, from the elution time of the thermoplastic resin in the intermediate layer and a calibration curve, an area corresponding to a region where the polystyrene-converted molecular weight of the thermoplastic resin in the intermediate layer is 1 million or more was calculated. By expressing the value corresponding to the area corresponding to the area of polystyrene equivalent molecular weight of 1 million or more of the thermoplastic resin in the intermediate layer by the peak area of the thermoplastic resin in the intermediate layer as a percentage (%), the above thermoplasticity The ratio (%) of the high molecular weight component Y in which the molecular weight y is 1 million or more in the resin was calculated.

(Measurement of plasticizer content)
Plasticize the THF so that the plasticizer content is 10%, 15%, 20%, 25%, 30%, 35%, 35%, 40%, 45% and 50% by weight. The plasticizer was dissolved to prepare a plasticizer-THF solution. The obtained plasticizer-THF solution was subjected to GPC measurement to determine the peak area of the plasticizer. The peak area of the plasticizer was plotted against the concentration of the plasticizer to obtain an approximate line. Next, the THF solution in which the intermediate layer was dissolved in THF was measured by GPC, and the content of the plasticizer was determined by using an approximate line from the peak area of the plasticizer.

  The results are shown in Tables 1 to 5 below. In Tables 1 to 5 below, “PVB” represents polyvinyl butyral, “PVA” represents polyvinyl alcohol, “3GO” represents triethylene glycol di-2-ethylhexanoate, and “3GH” represents triethylene. Glycol di-2-ethylbutyrate is shown.

  Moreover, in Comparative Examples 1-9, as for the foaming area of the foaming produced in the foaming test A, the laminated glass X using the relatively thin intermediate film used the relatively thick intermediate film. It was larger than the laminated glass Y. On the other hand, in the foaming test A of the laminated glass using the relatively thin interlayer film of all the examples, foaming was not observed or the foaming area of the generated foam was sufficiently small.

DESCRIPTION OF SYMBOLS 1 ... Intermediate film 1a ... One end 1b ... Other end 2 ... 1st layer 2a ... One side 2b ... The other side 3 ... 2nd layer 3a ... Outside surface 4 ... 3rd layer 4a ... Outside surface 11 ... Laminated glass 12 ... first laminated glass constituent member 13 ... second laminated glass constituent member 21A ... intermediate film 21 ... first layer 21a ... one end 21b ... other end 51, 61, 71 ... intermediate film 51a, 61a, 71a ... one end 51b, 61b, 71b ... the other end 52, 62, 72 ... first layer 53, 63, 73 ... second layer 54, 64, 74 ... third layer

Claims (17)

An interlayer film for laminated glass having a structure of one layer or a laminated structure of two or more layers,
In the case of an interlayer film for laminated glass having a one-layer structure, it comprises a first layer containing a thermoplastic resin and a plasticizer,
In the case of an interlayer film for laminated glass having a laminated structure of two or more layers, the first layer containing a thermoplastic resin and a plasticizer is laminated on one surface of the first layer, And a second layer containing a thermoplastic resin and a plasticizer,
The thermoplastic resin in the first layer contains a high molecular weight component having an absolute molecular weight of 1 million or more, and the proportion of the high molecular weight component in the thermoplastic resin in the first layer is 7.4%. Or the high molecular weight of the thermoplastic resin in the first layer includes a high molecular weight component having a molecular weight of 1 million or more in terms of polystyrene and occupies the thermoplastic resin in the first layer. The proportion of ingredients is 9% or more,
An interlayer film for laminated glass in which the thickness of one end is thinner than the thickness of the other end opposite to the one end.   The interlayer film for laminated glass according to claim 1, having a shape in which the thickness gradually increases from one end to the other end.   The interlayer film for laminated glass according to claim 1 or 2, wherein a cross-sectional shape in the thickness direction is a wedge shape.   The thermoplastic resin in the first layer contains a high molecular weight component having an absolute molecular weight of 1 million or more, and the proportion of the high molecular weight component in the thermoplastic resin in the first layer is 7.4%. The interlayer film for laminated glass according to any one of claims 1 to 3, which is as described above.   The thermoplastic resin in the first layer contains a high molecular weight component having a molecular weight of 1 million or more in terms of polystyrene, and the proportion of the high molecular weight component in the thermoplastic resin in the first layer is 9% or more. The interlayer film for laminated glass according to any one of claims 1 to 3, wherein   The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the thermoplastic resin in the first layer is a polyvinyl acetal resin.   The interlayer film for laminated glass according to claim 6, wherein the content of hydroxyl groups of the polyvinyl acetal resin in the first layer is 31 mol% or less.   The intermediate for laminated glass according to any one of claims 1 to 7, wherein a content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the first layer is within a range of 40 to 80 parts by weight. film.   The interlayer film for laminated glass according to any one of claims 1 to 8, wherein the interlayer film has a laminated structure of two or more layers, and includes the first layer and the second layer.   The content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the first layer is larger than the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the second layer. The interlayer film for laminated glass according to any one of 1 to 9.   In the case of an interlayer film for laminated glass having a laminated structure of three or more layers, the laminated film is laminated on the other surface of the first layer, the second layer, and the first layer, and heat The interlayer film for laminated glass according to any one of claims 1 to 10, further comprising a third layer containing a plastic resin and a plasticizer.   The interlayer film for laminated glass according to claim 11, comprising a laminated structure of three or more layers, and comprising the first layer, the second layer, and the third layer.   The content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the first layer is larger than the content of the plasticizer with respect to 100 parts by weight of the thermoplastic resin in the third layer. The interlayer film for laminated glass according to 11 or 12.   The thermoplastic resin in the first layer is a polyvinyl acetal resin, the degree of acetylation of the polyvinyl acetal resin is 8 mol% or less, and the degree of acetalization is 70 mol% or more, or The interlayer film for laminated glass according to any one of claims 1 to 13, wherein the thermoplastic resin in the first layer is a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin exceeds 8 mol%. .   The thermoplastic resin in the first layer is a polyvinyl acetal resin, the degree of acetylation of the polyvinyl acetal resin is 8 mol% or less, and the degree of acetalization is 70 mol% or more. The interlayer film for laminated glass described.   The interlayer film for laminated glass according to claim 14, wherein the thermoplastic resin in the first layer is a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin exceeds 8 mol%. First and second laminated glass components;
An intermediate film sandwiched between the first and second laminated glass constituent members,
Laminated glass, wherein the interlayer film is the interlayer film for laminated glass according to any one of claims 1 to 16.

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