JP2013006724A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer for laminated glass capable of giving a laminated glass having excellent heat-shielding property and suppressing generation of bubbles and growth of bubbles.SOLUTION: When the interlayer 21A for laminated glass has a single-layer structure, the interlayer is provided with a first layer 21 containing a thermoplastic resin, a plasticizer and an infrared absorber. When the interlayer 1 has a laminated structure having two or more layers, the interlayer is provided with first and second layers 2, 3 containing a thermoplastic resin and a plasticizer, and the first layer 2 or the second layer 3 contains the infrared absorber. The ratio of a high-molecular weight component having an absolute molecular weight of ≥1,000,000 in the thermoplastic resin of the first layer 2, 21 is ≥7.4% or the ratio of the high-molecular weight component having a polystyrene-reduced molecular weight of ≥1,000,000 in the thermoplastic resin of the first layer 2, 21 is ≥9%.

Description

  The present invention relates to an interlayer film for laminated glass used for laminated glass for automobiles and buildings, and more specifically, an interlayer film for laminated glass containing a thermoplastic resin, a plasticizer, and an infrared absorber, and the laminated glass. The present invention relates to a laminated glass using an interlayer film.

  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.

JP 2001-097745 A JP 2007-070200 A

  When the laminated glass is formed using the interlayer film described in Patent Document 1, the sound insulation in the frequency region near 2000 Hz of the laminated glass is not sufficient, and therefore the sound insulation performance is inevitably lowered due to the coincidence effect. There is. 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.

  Furthermore, when a laminated glass is formed using a conventional interlayer film for laminated glass, there is a problem that the heat shielding property of the laminated glass is low.

  An object of the present invention is to provide an interlayer film for laminated glass that is excellent in heat-shielding properties and that can obtain a laminated glass capable of suppressing the occurrence of foaming and the growth of foam, and a laminated glass using the interlayer film for laminated glass. Is to provide.

  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 A thermoplastic resin comprising a first layer containing a resin and a plasticizer, wherein the first layer contains an infrared absorber and is an interlayer film for laminated glass having a laminated structure of two or more layers; And a first layer containing a plasticizer, and a second layer laminated on one surface of the first layer and containing a thermoplastic resin and a plasticizer. The layer contains an infrared absorber, or the second layer contains an infrared absorber, and 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 more. Or 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 occupies the thermoplastic resin in the first layer. An interlayer film for laminated glass having a ratio of 9% or more is provided.

  It is preferable that the infrared absorber contains heat shielding particles. The infrared absorber preferably contains metal oxide particles.

  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. The second layer preferably contains the infrared absorber.

  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. The third layer preferably contains an infrared absorber.

  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, and in the case of a one-layer structure, the first layer contains an infrared absorber. In the case of a laminated structure of more than one layer, the first layer or the second layer contains an infrared absorber, so that the heat shielding property of the laminated glass using the intermediate film can be improved.

  Furthermore, the interlayer film for laminated glass according to the present invention includes the first layer or the first and second layers, and the thermoplastic resin in the first layer is absolutely The ratio of the high molecular weight component that includes a high molecular weight component having a molecular weight of 1 million or more and occupies the thermoplastic resin in the first layer is 7.4% or more, or in the first layer The thermoplastic resin contains a high molecular weight component having a polystyrene equivalent 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 9% or more. Generation of foaming and growth of foaming in the laminated glass used can be suppressed.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the second embodiment of the present invention. FIG. 3 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, a plasticizer, and an infrared absorber. 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. When the interlayer film for laminated glass according to the present invention has a laminated structure of two or more layers, the first layer contains an infrared absorber or the second layer contains an infrared absorber. When the interlayer film for laminated glass according to the present invention has a laminated structure of two or more layers, both the first layer and the second layer may contain an infrared absorber.

  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.

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

  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.

  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.

  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 intermediate film 1, the 1st layer 2 contains an infrared absorber, or the 2nd layer 3 contains an infrared absorber. Only the first layer 2 may contain an infrared absorber, only the second layer 3 may contain an infrared absorber, both the first layer 2 and the second layer 3. May contain an infrared absorber. The third layer 4 may or may not contain an infrared absorber. The first layer 2 that is an intermediate layer is relatively thin, and thickness variations are likely to occur. The second and third layers 3 and 4 which are surface layers are relatively thicker than the first layer 2 and thickness variations are less likely to occur. For this reason, by using an infrared absorber for the second and third layers 3 and 4, the heat shielding property can be made uniform and good. In addition, when the first layer 2 is thinner than the second layer 3 or the first layer 2 is thinner than the third layer 4, the second and third layers 3 and 4 are irradiated with infrared rays. By using the absorbent, the heat shielding uniformity is increased.

  From the viewpoint of effectively enhancing the heat shielding properties of the interlayer film and the laminated glass, the second layer 3 preferably contains the infrared absorber, and the third layer 4 preferably contains an infrared absorber. . In this case, the 1st layer 2 may contain the infrared absorber and does not need to contain it.

  In FIG. 2, the intermediate film for laminated glasses which concerns on the 2nd Embodiment of this invention is typically shown with sectional drawing.

  A synthetic intermediate film 21 </ b> A shown 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 first layer 21 contains a thermoplastic resin, a plasticizer, and an infrared absorber. 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.

  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 the high molecular weight component X having an absolute molecular weight of 1 million or more in 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.

(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 the high molecular weight component X having an absolute molecular weight of 1 million 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 A preferred lower limit is 50 mol%, a more preferred lower limit is 53 mol%, a still more preferred lower limit is 60 mol%, a particularly preferred lower limit is 63 mol%, a preferred upper limit is 85 mol%, a more preferred upper limit is 80 mol%, and a 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.

(Infrared absorber)
In the case of a single-layer structure, the first layer contains the infrared absorber, and in the case of a laminated structure of two or more layers, the first layer or the second layer contains the infrared absorber. Thereby, the heat-shielding property of the intermediate film for laminated glass and laminated glass can be improved effectively.

  Examples of the infrared absorber include heat shielding particles, and also include at least one component (hereinafter sometimes referred to as component X) among phthalocyanine compounds, naphthalocyanine compounds, and anthracocyanine compounds. The infrared absorber is preferably a heat shielding particle or the component X.

  By the way, in recent years, for example, in the United States, the California Air Resources Board (CARB) has proposed reducing the amount of carbon dioxide emitted from automobiles in order to reduce greenhouse gases. It was. In order to reduce the amount of carbon dioxide emitted from automobiles, the CARB regulates the heat energy that passes through the laminated glass and flows into the automobile, reducing the fuel consumed by the air conditioner and reducing the fuel consumption of the automobile. I was considering improving it. Specifically, the CARB had planned to introduce cool car regulations (Cool Cars Standards).

  Specifically, in the above-mentioned cool car regulation, in 2012, Tts (Total Solar Transmission) of laminated glass used for automobiles was expected to be 50% or less. In 2016, it was expected that the Tts of the laminated glass was 40% or less. The Tts is an index of heat ray shielding.

  In addition, the heat ray reflective laminated glass using the glass which vapor-deposited the metal thin film or heat ray reflective PET generally called a thermoreflex type reflects the communication wave of not only infrared rays but a communication wavelength range. When the heat ray reflective laminated glass is used for the windshield, it is necessary to cut out the heat ray reflective portion in order to cope with many sensors. As a result, the average Tts of the entire windshield using the heat ray reflective laminated glass having a Tts of 50% is about 53%. Therefore, in a type of laminated glass that transmits communication waves and absorbs infrared rays, Tts was expected to be allowed up to 53%.

  As of September 2010, the introduction of the cool car regulations has been postponed, but there is still a tendency for laminated glass having a low Tts.

  Thus, in recent years, there has been a considerable increase in demand for improving the heat shielding properties of laminated glass. Moreover, it is calculated | required that the laminated glass using the intermediate film containing the said infrared absorber to make high heat-shielding property and high visible light transmittance | permeability (Visible Transmittance) compatible. That is, in the laminated glass, it is necessary to increase the heat shielding property while keeping the visible light transmittance high.

  Of the first to third layers, the layer containing the infrared absorber preferably contains both the heat shielding particles and the component X as the infrared absorber. In this case, the heat shielding property and visible light transmittance of the laminated glass can be effectively increased.

  The present inventors have found that the use of a layer containing heat-shielding particles and a specific component X described above can increase both the heat-shielding property and the visible light transmittance of the laminated glass.

  In the layer containing the thermoplastic resin and the infrared absorber among the first to third layers, a preferable lower limit of the content of the infrared absorber is 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 01 parts by weight, more preferred lower limit is 0.1 parts by weight, even more preferred lower limit is 0.14 parts by weight, still more preferred lower limit is 0.2 parts by weight, still more preferred lower limit is 0.55 parts by weight, and particularly preferred lower limit is 0.6 parts by weight, the preferred upper limit is 3 parts by weight, the more preferred upper limit is 2 parts by weight, the still more preferred upper limit is 1.8 parts by weight, and the still more preferred upper limit is 1.65 parts by weight. If content of the said infrared absorber satisfy | fills the said preferable minimum, heat-shielding property can be made still higher. When the content of the infrared absorber satisfies the preferable upper limit, the visible light transmittance can be further increased.

  Content of the said heat-shielding particle in the layer containing the said thermoplastic resin and the said infrared absorber is not specifically limited. In 100% by weight of the layer containing the thermoplastic resin and the infrared absorber, the content of the infrared absorber is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and further preferably 1% by weight. Above, particularly preferably 1.5% by weight or more, preferably 6% by weight or less, more preferably 5.5% by weight or less, further preferably 4% by weight or less, particularly preferably 3.5% by weight or less, most preferably 3.0% by weight or less. When the content of the infrared absorber in the layer containing the thermoplastic resin and the infrared absorber is within the preferable range, the heat shielding property can be sufficiently increased, and the visible light transmittance is sufficiently high. can do.

  In the layer containing the thermoplastic resin and the heat shielding particles, the content of the heat shielding particles with respect to 100 parts by weight of the thermoplastic resin is defined as content A, and the content of the component X with respect to 100 parts by weight of the thermoplastic resin When the content is B, the content A is in the range of 0.1 to 3 parts by weight, and the ratio of the content A to the content B (the content A / the content B ) Is preferably in the range of 3 to 2000. In this case, a laminated glass having a sufficiently high heat shielding property and a sufficiently high visible light transmittance can be obtained. However, even if the content A is 0.01 parts by weight or more, the heat shielding property and the visible light transmittance are increased.

Thermal barrier particles:
From the viewpoint of further improving the heat shielding property of the laminated glass, the infrared absorber preferably contains heat shielding particles, and more preferably contains metal oxide particles. The heat shielding particles are preferably particles (metal oxide particles) formed of a metal oxide. Only 1 type may be used for a heat-shielding particle and 2 or more types may be used together.

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

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

  The tungsten oxide particles are generally represented by the following formula (X1) or the following formula (X2). In the interlayer film for laminated glass according to the present invention, tungsten oxide particles represented by the following formula (X1) or the following formula (X2) are preferably used.

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

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

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

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

  The preferable lower limit of the average particle diameter of the heat shielding particles is 0.01 μm, the more preferable lower limit is 0.02 μm, the preferable upper limit is 0.1 μm, and the more preferable upper limit is 0.05 μm. When the average particle diameter satisfies the above preferable lower limit, the heat ray shielding property can be sufficiently enhanced. When the average particle diameter satisfies the preferable upper limit, the dispersibility of the heat shielding particles can be improved.

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

  In the layer including the thermoplastic resin and the heat shielding particles in the first to third layers, the content A indicating the content of the heat shielding particles is in the range of 0.1 to 3 parts by weight. It is preferable that When the content A is within the above range, the heat shielding property can be sufficiently increased, and the visible light transmittance can be sufficiently increased. Further, when the content A is 3 parts by weight or less, the haze value of the obtained laminated glass is further reduced. The preferred lower limit of the content A is 0.14 parts by weight, the more preferred lower limit is 0.2 parts by weight, the still more preferred lower limit is 0.55 parts by weight, the particularly preferred lower limit is 0.6 parts by weight, and the preferred upper limit is 2 parts by weight. A more preferred upper limit is 1.8 parts by weight, and a still more preferred upper limit is 1.65 parts by weight. When the content A satisfies the preferable lower limit, the heat shielding property can be further increased. When the content A satisfies the preferable upper limit, the visible light transmittance can be further increased.

  The content of the heat shielding particles in the layer containing the thermoplastic resin and the heat shielding particles is not particularly limited. In 100% by weight of the layer containing the thermoplastic resin and the heat shielding particles, the content of the heat shielding particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and further preferably 1% by weight. % Or more, particularly preferably 1.5% by weight or more, preferably 6% by weight or less, more preferably 5.5% by weight or less, still more preferably 4% by weight or less, particularly preferably 3.5% by weight or less, most preferably Is 3.0% by weight or less. When the content of the heat shielding particles in the layer containing the thermoplastic resin and the heat shielding particles is within the preferred range, the heat shielding property can be sufficiently enhanced, and the visible light transmittance is sufficiently high. can do.

The interlayer film for laminated glass of the present invention preferably contains the heat shielding particles at a rate of 0.1 to 12 g / m ² . When the ratio of the heat shielding particles is within the above range, the heat shielding property can be sufficiently increased, and the visible light transmittance can be sufficiently increased. A preferred lower limit of the ratio of the heat shielding particles, 0.5g / ^{m 2,} and more preferable lower limit is 0.8 g / ^{m 2,} still more preferred lower limit 1.5 g / ^{m 2,} especially preferred lower limit is at 3 g / ^{m 2} The preferred upper limit is 11 g / m ² , the more preferred upper limit is 10 g / m ² , the still more preferred upper limit is 9 g / m ² , and the particularly preferred upper limit is 7 g / m ² . When the said ratio satisfy | fills the said preferable minimum, heat-shielding property can be made still higher, and when the said ratio satisfy | fills the said preferable upper limit, the said visible light transmittance | permeability can be made still higher.

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

  The combined use of the heat shielding particles and the component X can sufficiently block infrared rays (heat rays). By using the metal oxide particles and the component X in combination, infrared rays can be blocked more effectively. In combination with the ITO particles or the tungsten oxide particles and the component X, infrared rays can be blocked more effectively.

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

  From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass and sufficiently increasing the visible light transmittance, the component X is a group consisting of phthalocyanine, a derivative of phthalocyanine, naphthalocyanine, and a derivative of naphthalocyanine. It is preferable that it is at least one selected from.

  From the viewpoint of effectively increasing the heat shielding property and maintaining the visible light transmittance at a higher level over a long period of time, the component X preferably contains a vanadium atom or a copper atom, and contains a vanadium atom. Is more preferable. The component X is preferably at least one of a phthalocyanine derivative containing a vanadium atom or a copper atom and a naphthalocyanine derivative containing a vanadium atom or a copper atom. From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X preferably has a structure containing vanadium atoms.

  In the layer containing the thermoplastic resin and the heat shielding particles in the first to third layers, the content (content B) of the component X with respect to 100 parts by weight of the thermoplastic resin is not particularly limited. The preferable lower limit of the content B of the component X is 0.0005 parts by weight, the preferable lower limit is 0.001 parts by weight, the more preferable lower limit is 0.0014 parts by weight, the still more preferable lower limit is 0.002 parts by weight, and the particularly preferable lower limit. Is 0.0025 parts by weight, the preferred upper limit is 0.05 parts by weight, the more preferred upper limit is 0.025 parts by weight, the still more preferred upper limit is 0.02 parts by weight, and the particularly preferred upper limit is 0.01 parts by weight. When the said content B satisfy | fills the said preferable minimum, heat-shielding property can be made still higher. When the content B satisfies the preferable upper limit, the visible light transmittance can be further increased. Moreover, when the said content B satisfy | fills the said preferable upper limit, the saturation of a laminated glass can be made low. The saturation can be measured according to JIS Z8729. The preferable upper limit of the saturation of the laminated glass is 65, the more preferable upper limit is 50, the still more preferable upper limit is 40, and the particularly preferable upper limit is 35. When the saturation satisfies the preferable upper limit, coloring of the laminated glass can be suppressed.

  Further, in 100% by weight of the layer containing the thermoplastic resin and the heat shielding particles, the content of the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.00. 05% by weight or more, particularly preferably 0.1% by weight or more, preferably 0.2% by weight or less, more preferably 0.18% by weight or less, still more preferably 0.16% by weight or less, particularly preferably 0.15% or less. % By weight or less. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the heat shielding property can be sufficiently increased, and the visible light transmittance can be sufficiently increased.

(Yellow dye)
Each of the first to third layers may contain a yellow dye as necessary. Moreover, the layer containing the yellow dye among the first to third layers may contain the yellow dye in the entire layer containing the yellow dye, or may partially contain the yellow dye. .

  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. In this case, it is preferable that the colored region R1 contains a yellow dye. When the colored region R1 contains a yellow dye, the heat shielding property of the colored region can be increased. As a result, the heat shielding property of the laminated glass can be enhanced due to the colored region having a high heat shielding property. It is preferable that the colored region R1 is provided at the edge on the upper end side of the intermediate film. The colored region R1 may be provided in a region other than the edge portion on the upper end side of the intermediate film, and may be provided in an edge portion on the lower end side of the intermediate film, for example. Further, the colored region R1 may be provided on both the upper edge portion and the lower edge portion of the intermediate film.

  The visible light transmittance of the second region R2 is preferably higher than the visible light transmittance of the colored region R1. In this case, the visual field can be improved in the second region R2. The colored region R1 is preferably darker than the second region R2.

  The colored region R1 is preferably present in a strip shape at least at the edge on one end side. Laminated glass for vehicles such as automobiles, especially windshields, may be provided with a band-like colored region for the purpose of preventing the driving driver from feeling dazzled by sunlight or outdoor lighting. is there.

  The layer containing the infrared absorbing agent among the first to third layers includes a heat shielding particle, at least one component X of a phthalocyanine compound, a naphthalocyanine compound, and an anthocyanin compound, and a yellow dye. It is preferable. In this case, it is possible to obtain a laminated glass having higher heat shielding properties and higher visible light transmittance.

  The yellow dye is not particularly limited. As for the said yellow dye, only 1 type may be used and 2 or more types may be used together. The yellow dye preferably absorbs transmitted light of 380 to 500 nm, more preferably absorbs transmitted light of 390 to 480 nm, and effectively absorbs transmitted light of 395 to 460 nm. More preferably, it is particularly preferable to effectively absorb transmitted light of 400 to 450 nm. As a result, in addition to the heat shielding particles and the component X, the heat shielding properties can be further enhanced by using a yellow dye. Since the shielding property of heat rays can be sufficiently increased, the preferable lower limit of the maximum absorption wavelength of the yellow dye is 380 nm, the more preferable lower limit is 390 nm, the still more preferable lower limit is 395 nm, the particularly preferable lower limit is 400 nm, and the preferable upper limit is 500 nm, more preferable. The upper limit is 480 nm, the more preferable upper limit is 460 nm, and the particularly preferable upper limit is 450 nm. For example, the maximum absorption wavelength of the yellow dye is a solution in which 0.01 part by weight of the yellow dye is dissolved in 100 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) (cell length: 1 mm, It can be measured with a spectrophotometer (Hitachi High-Tech "U-4100") using a quartz cell.

  Specific examples of the yellow dye include anthraquinone dye, quinoline dye, isoquinoline dye, monoazo dye, disazo dye, quinophthalone dye, perylene dye, triphenylmethane dye, and methine dye. Among these, anthraquinone dyes are preferable from the viewpoint of further improving the heat shielding property of the interlayer film for laminated glass.

  As commercially available yellow dyes, “ORACEET Yellow GHS” manufactured by Ciba Japan (anthraquinone dye, maximum absorption wavelength 450 nm), “KP Last Yellow G” (methine dye, maximum absorption wavelength 400 nm) manufactured by Kiwa Chemical Industry Co., Ltd. ), “KP Plast Yellow 2G” (quinophthalone dye, maximum absorption wavelength 420 nm), “KP Plast Yellow 3G” (monoazo dye, maximum absorption wavelength 395 nm), “KP Plast Yellow F” (isoquinoline dye, maximum absorption wavelength 415 nm), “KP Past Yellow 7G” (perylene dye, maximum absorption wavelength 460 nm) and the like.

  In the layer containing the thermoplastic resin and the yellow dye in the first and third layers, the content of the yellow dye with respect to 100 parts by weight of the thermoplastic resin is 0.005 to 0.24 parts by weight. It is preferable to be within the range. The more preferable lower limit of the content of the yellow dye with respect to 100 parts by weight of the thermoplastic resin in the layer containing the thermoplastic resin and the yellow dye is 0.01 parts by weight, and the more preferable lower limit is 0.04 parts by weight. A preferred lower limit is 0.06 parts by weight, a more preferred upper limit is 0.2 parts by weight, a still more preferred upper limit is 0.15 parts by weight, and a particularly preferred upper limit is 0.1 parts by weight. When the yellow dye is partially contained, the lower limit and the upper limit of the preferred content of the yellow dye in the portion containing the yellow dye (for example, the colored region) are the same as those described above. When the content of the yellow dye is within the above range, the heat shielding property can be further increased and the visible light transmittance can be further increased.

The interlayer film for laminated glass according to the present invention preferably contains the yellow dye at a rate of 0.025 to 1.45 g / m ² . A more preferred lower limit of the content of the yellow dye of the combined glass interlayer film for 0.05 g / ^{m 2,} still more preferred lower limit 0.2 g / ^{m 2,} especially preferred lower limit is 0.3 g / ^{m 2,} more a preferred upper limit is 1.2 g / ^{m 2,} still more preferred upper limit 1 g / ^{m 2,} particularly preferred upper limit is 0.8 g / ^{m 2.} When the content ratio of the yellow dye is within the above range, the heat shielding property can be further increased, and the visible light transmittance can be further increased.

  In the layer containing the thermoplastic resin, the component X and the yellow dye in the first and third layers, the total content of the component X and the yellow dye with respect to 100 parts by weight of the thermoplastic resin A preferred lower limit is 0.005 parts by weight, a more preferred lower limit is 0.03 parts by weight, a still more preferred lower limit is 0.04 parts by weight, a particularly preferred lower limit is 0.07 parts by weight, and a more preferred upper limit is 0.24 parts by weight. A more preferred upper limit is 0.2 parts by weight, a particularly preferred upper limit is 0.18 parts by weight, and a most preferred upper limit is 0.15 parts by weight. When the yellow dye is partially contained, the lower limit and the upper limit of the preferable content of the total content of the component X and the yellow dye in the portion containing the yellow dye are the same as the above-described values. When the total content of the yellow dye and the component X is within the above range, the heat shielding property can be further increased, and the visible light transmittance can be further increased.

The sum of component A preferred lower limit of the content of the X and yellow dye 0.005 g / ^{m 2} in the interlayer film for a laminated glass, and more preferable lower limit is 0.03 g / ^{m 2,} still more preferred lower limit 0.2 g / ^{m 2} , especially preferred lower limit is 0.25 g / ^{m 2,} a preferred upper limit is 1.5 g / ^{m 2,} and more preferable upper limit is 1.2 g / ^{m 2,} still more preferred upper limit 1 g / ^{m 2,} particularly preferred upper limit 0. 7 g / m ² . When the total content of the component X and the yellow dye satisfies the preferable lower limit, the heat shielding property of the laminated glass can be further enhanced. When the total content of the component X and the yellow dye satisfies the preferable upper limit, the visible light transmittance can be further increased.

(Metal salt)
Each of the first to third layers preferably contains at least one metal salt (hereinafter sometimes referred to as metal salt M) of an alkali metal salt and an alkaline earth metal salt. The first layer preferably contains a metal salt M. In particular, the second and third layers preferably each contain the metal salt M. By using the metal salt M, it becomes easy to control the adhesion between the laminated glass constituent member and the interlayer film or the adhesion between the layers in the interlayer film. Furthermore, since the first layer contains the upper metal salt M, the dispersibility of the infrared absorber such as the heat-shielding particles is further improved, and as a result, the weather resistance of the intermediate film is further increased and is high. Visible light transmittance can be maintained for a longer period of time. As for the said metal salt M, only 1 type may be used and 2 or more types may be used together.

  The metal salt M preferably contains at least one metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba. The metal salt M is preferably contained in the layer of the intermediate film in the state of metal ion, hydrated metal ion, complexed metal ion, metal inorganic salt, or metal organic acid ester. When present in the form of metal ions, hydrated metal ions, or complex metal ions, it is easy to control the adhesion between the laminated glass component and the interlayer film, or the adhesion between each layer in the interlayer film. is there. The metal salt M contained in the interlayer film layer preferably contains at least one metal selected from K and Mg.

  The metal salt M is more preferably an alkali metal salt of an organic acid having 2 to 16 carbon atoms or an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, and a carboxylic acid having 2 to 16 carbon atoms. More preferably, it is a magnesium salt or a carboxylic acid potassium salt having 2 to 16 carbon atoms.

  Although it does not specifically limit as said C2-C16 carboxylic acid magnesium salt and said C2-C16 carboxylic acid potassium salt, For example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, 2-ethylbutanoic acid Examples include magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.

  In the layer containing the metal salt M among the first to third layers, the content of the metal salt M is the content of metal ions (for example, magnesium concentration in the case of magnesium ions, potassium concentration in the case of potassium ions). ) Is preferably 5 ppm or more, more preferably 10 ppm or more, still more preferably 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less. When the content of the metal salt M is not less than the above lower limit and not more than the above upper limit, the adhesiveness between the laminated glass constituent member and the intermediate film or the adhesiveness between each layer in the intermediate film can be controlled even better. Furthermore, when the content of the metal salt M is equal to or higher than the lower limit, the weather resistance of the intermediate film is further increased, and high visible light transmittance can be maintained for a further long period.

(UV shielding agent)
In the interlayer film for laminated glass according to the present invention, it is more preferable that the first layer contains an ultraviolet shielding agent or the second layer contains an ultraviolet shielding agent. Specifically, when the interlayer film for laminated glass according to the present invention has a single-layer structure, the first layer preferably contains an ultraviolet shielding agent. When the interlayer film for laminated glass according to the present invention has a laminated structure of two or more layers, the first layer contains an ultraviolet shielding agent, or the second layer contains an ultraviolet shielding agent. It is preferable that the second layer contains an ultraviolet shielding agent. When the interlayer film for laminated glass according to the present invention has a laminated structure of two or more layers, both the first layer and the second layer may contain an ultraviolet shielding agent. The third layer preferably contains an ultraviolet shielding agent. By using the ultraviolet shielding agent, even if the interlayer film and the laminated glass are used for a long time, the visible light transmittance is hardly lowered. As for this ultraviolet shielding agent, only 1 type may be used and 2 or more types may be used together. The ultraviolet shielding agents used for the first, second and third layers may be the same or different.

  As a result of the study by the present inventors, only by producing a laminated glass using an interlayer film containing the heat shielding particles and the specific component X, when the obtained laminated glass is used for a long period of time, the heat shielding properties are obtained. It was found that there was a tendency to decrease. Therefore, as a result of further studies by the present inventors, the present inventors have also found a configuration of an interlayer film for laminated glass that can maintain high heat shielding properties for a long period of time.

  That is, the present inventors dared to make the interlayer film for laminated glass into a multilayer of two or more layers, and by adopting a configuration comprising the layer containing the infrared absorber and the layer containing the ultraviolet shielding agent, It has been found that even when laminated glass is used for a long period of time, the visible light transmittance is hardly lowered. In particular, the use of an ultraviolet shielding agent can suppress the chemical change of the component X and the deterioration of the resin accompanying the chemical change of the component X. For this reason, the outstanding heat insulation can be maintained over a long period of time.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the ultraviolet shielding agent is not particularly limited. From the viewpoint of further suppressing the decrease in visible light transmittance after time, the content of the ultraviolet shielding agent is preferably in 100% by weight of the first to third layers containing the ultraviolet shielding agent. Is 0.1% by weight or more, more preferably 0.2% by weight or more, further preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably 2.5% by weight or less, more preferably It is 2% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less. In particular, the content of the ultraviolet screening agent in 100% by weight of the first layer is 0.2% by weight or more, or the content of the ultraviolet screening agent in 100% by weight of the second and third layers. When the amount is 0.2% by weight or more, a decrease in visible light transmittance after aging of the interlayer film and the laminated glass can be remarkably suppressed.

  The interlayer film for laminated glass according to the present invention has a weight (weight%) ratio (heat shielding particles: all ultraviolet shielding agents) of the heat shielding particles and all the ultraviolet shielding agents to the entire intermediate film, and 4: It is preferable to include by 1: 1: 200, and it is more preferable to include by 2: 1-1: 100. When the weight (% by weight) ratio of the heat shielding particles to all the ultraviolet shielding agents is within the above range, the heat shielding property and visible light transmittance of the interlayer film and the laminated glass, and after the aging of the interlayer film and the laminated glass The visible light transmittance of can be further increased. The weight ratio means the content of the heat shielding particles in 100% by weight of the intermediate film (% by weight) and the content of all the ultraviolet shielding agents in the 100% by weight of the intermediate film (% by weight). Indicates the ratio.

(Antioxidant)
The interlayer film for laminated glass according to the present invention preferably contains an antioxidant. The first layer preferably contains an antioxidant, and the second and third layers preferably contain an antioxidant. As for this antioxidant, only 1 type may be used and 2 or more types may be used together.

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

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

  From the viewpoint of more effectively maintaining the high visible light transmittance of the interlayer film and the laminated glass over a long period of time, the antioxidant is preferably a phenol-based antioxidant or a phosphorus-based antioxidant.

  Commercially available products of the above-mentioned antioxidants include, for example, trade name “IRGANOX 245” manufactured by BASF, trade name “IRGAFOS 168” manufactured by BASF, trade name “IRGAFOS 38” manufactured by BASF, and Sumitomo Chemical Co., Ltd. A trade name “Sumilyzer BHT” and a trade name “Irganox 1010” manufactured by Ciba Geigy are listed.

  In order to maintain the high visible light transmittance of the interlayer film and the laminated glass for a long period of time, in 100% by weight of the layer containing the antioxidant or in 100% by weight of the interlayer film among the first to third layers. The content of the antioxidant is preferably 0.75% by weight or more. Moreover, since the effect of adding the antioxidant is saturated, the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the layer containing the antioxidant or 100% by weight of the intermediate film. In addition, in order to maintain the visible light transmittance of the intermediate film and the laminated glass after the lapse of time, the higher the content of the antioxidant, the better.

  From the viewpoint of further increasing the heat shielding properties and visible light transmittance of the interlayer film and the laminated glass, and the visible light transmittance after the lapse of time of the interlayer film and the laminated glass, the antioxidant of the first to third layers. The content of the antioxidant is preferably 0.75% by weight or more, more preferably 0.8% by weight or more in 100% by weight of the layer containing or 100% by weight of the interlayer film. In order to suppress the color change of the peripheral part due to the influence of the antioxidant, the content of the antioxidant is preferably 2% by weight in 100% by weight of the layer containing the antioxidant or 100% by weight of the intermediate film. Below, more preferably 1.8% by weight or less.

  The interlayer film for laminated glass according to the present invention includes the thermal barrier particles and the antioxidant in a weight ratio (thermal barrier particles: antioxidant) of 10: 1 to 1: 100 in the entire intermediate film. It is more preferable to include 5: 1 to 1:50. When the weight ratio between the heat shielding particles and the antioxidant is within the above range, the heat shielding property and visible light transmittance of the interlayer film and the laminated glass, and the visible light transmittance after aging of the interlayer film and the laminated glass are further increased. It can be further enhanced. The weight ratio is the ratio between the content of the heat shielding particles in 100% by weight of the intermediate film (% by weight) and the content of the antioxidant in the film of 100% by weight (% by weight). Show.

(Other ingredients)
Each of the first to third layers contains additives such as a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion modifier, a moisture-resistant agent, and a fluorescent brightening agent, as necessary. It may be.

(Laminated glass)
Although the manufacturing method of the interlayer film for laminated glass according to the present invention is not particularly limited, after forming the first to third layers using a resin composition containing the polyvinyl acetal resin and the plasticizer, For example, the second layer, the first layer, and the third layer are laminated in this order, and the resin composition is coextruded using an extruder, whereby the second layer And a method of laminating 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. 3 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. 3 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 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, the more preferred upper limit is 0.2 mm, and the more preferred upper limit is 0.18 mm, and a particularly preferred 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. A preferable lower limit of the thickness of the second and third layers is 0.1 mm, a more preferable lower limit is 0.2 mm, a still more preferable lower limit is 0.25 mm, a particularly preferable lower limit is 0.3 mm, and a preferable upper limit is 0.6 mm. A preferred upper limit is 0.5 mm, a more preferred upper limit is 0.45 mm, and a 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. The ratio of the thickness of the first layer to the thickness of the intermediate film ((thickness of the first layer) / (thickness of the intermediate film)) is small, and the plasticizer contained in the first layer is contained. The larger the amount, the more foaming occurs in the laminated glass 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 ((the thickness of the first layer) / (the thickness of the intermediate film)) 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 0.00. 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.

  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 F, I to M, O, 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 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 8)
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 9)
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 10)
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 11)
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 12)
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 13)
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 14)
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 15)
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 16)
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 17)
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 18)
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 A to Z, a multilayer interlayer film for laminated glass and a laminated glass were produced as follows.

Example 1
(1) Preparation of dispersion 37.5 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), 0.98 parts by weight of ITO particles (manufactured by Mitsubishi Materials), and naphthalocyanine compound (copper naphthalocyanine) The compound, “FF IRSORB203” manufactured by Fuji Film Co., Ltd.) was mixed in 0.0182 parts by weight, and further a phosphate ester compound as a dispersant was added, followed by mixing in a horizontal microbead mill to obtain a mixed solution. . Thereafter, 0.1 part by weight of acetylacetone was added to the mixed solution with stirring to prepare a dispersion. The content of the phosphate ester compound was adjusted to be 1/10 of the content of the heat shielding particles.

(2) 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 kneaded thoroughly with a mixing roll. The intermediate layer resin composition was obtained. Furthermore, the total amount of the dispersion was added to 100 parts by weight of the obtained polyvinyl butyral resin F and sufficiently kneaded with a mixing roll to obtain a resin composition for a surface layer.

  The surface layer (thickness 350 μm), the intermediate layer (thickness 100 μm), and the surface layer (thickness 350 μm) are sequentially laminated by co-extrusion using the obtained intermediate layer resin composition and surface layer resin composition. A multilayer interlayer film was prepared.

(3) 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. 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.

(4) Production of laminated glass used for sound insulation measurement Multilayer interlayer film is cut into a size of 30 cm in length x 2.5 cm in width, and transparent float glass (length 30 cm x width 2.5 cm x thickness 2.5 mm) is obtained. 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 it was used.

(5) Preparation of laminated glass used for foaming tests A and B The obtained multilayer interlayer film was cut into a size of 30 cm in length and 15 cm in width and stored in an environment at a temperature of 23 ° C. for 10 hours. 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 was pressure-bonded at 135 ° C. and a pressure of 1.2 MPa for 20 minutes, so that the remaining air was dissolved in the multilayer interlayer film to obtain a laminated glass used for foaming tests A and B.

(Examples 2 to 21 and Comparative Examples 1 and 2)
The multilayer interlayer film was the same as in Example 1 except that the compositions of the first to third interlayer films and the composition of the dispersion (number of blended parts of the plasticizer) were changed as shown in Tables 1 to 3 below. And the laminated glass was 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 3 below, where “◯” indicates a case where the TL value is 35 dB or more and “X” indicates a case where the TL value is less than 35 dB.

(2) Foam test A (foaming state)
Five laminated glasses used for the foam 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)
Thirty laminated glasses used for the foam 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 18 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 3 below. In Tables 1 to 3 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.

DESCRIPTION OF SYMBOLS 1 ... Intermediate film 2 ... 1st layer 2a ... One side 2b ... The other side 3 ... 2nd layer 3a ... Outer surface 4 ... 3rd layer 4a ... Outer surface 11 ... Laminated glass 12 ... 1st Laminated glass constituent member 13 ... Second laminated glass constituent member 21A ... Intermediate film 21 ... First layer

Claims (19)

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, and the first layer contains an infrared absorber,
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, wherein the first layer contains an infrared absorber, or the second layer contains an infrared absorber,
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. An interlayer film for laminated glass having a component ratio of 9% or more.   The interlayer film for laminated glass according to claim 1, wherein the infrared absorbing agent includes heat shielding particles.   The interlayer film for laminated glass according to claim 1 or 2, wherein the infrared absorber contains metal oxide particles.   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 interlayer film for laminated glass according to any one of claims 1 to 9, wherein the second layer contains the infrared absorber.   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 10.   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 11, further comprising a third layer containing a plastic resin and a plasticizer.   The interlayer film for laminated glass according to claim 12, comprising a laminated structure of three or more layers, and comprising the first layer, the second layer, and the third layer.   The interlayer film for laminated glass according to claim 12 or 13, wherein the third layer contains an infrared absorber.   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 any one of 12 to 14.   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 15, 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 16, 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 18.

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