JP2013006725A - 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: The interlayer 1 for laminated glass is provided with first and second layers 2, 3 containing a polyvinyl acetal resin and a plasticizer. The first layer 2 or the second layer 3 of the interlayer 1 contains an infrared absorber. when viscoelasticity of a resin film is measured using the resin film (glass transition temperature Tg(°C)) consisting of the first layer 2 or on a resin film (glass transition temperature Tg(°C)) containing 100 pts.wt. of the polyvinyl acetal resin in the first layer 2 and 60 pts.wt. of triethylene glycol di-2-ethyl hexanoate (3GO) as the plasticizer, the ratio of elastic modulus G'(Tg+80) measured at (Tg+80)°C to the elastic modulus G'(Tg+30) measured at (Tg+30)°C is ≥0.65.

Description

  The present invention relates to an interlayer film for laminated glass having a multilayer structure of at least two layers, and more specifically, an interlayer film for laminated glass in which each layer contains a polyvinyl acetal resin and a plasticizer, respectively, and the interlayer film for laminated glass It is related with the laminated glass using.

  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, the following Patent Document 1 discloses that 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one of an alkali metal salt and an alkaline earth metal salt. A sound insulation layer containing 0.001 to 1.0 parts by weight of a metal salt of 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.

  Furthermore, the following Patent Document 1 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 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.

  In addition, when a laminated glass is formed using a multilayer interlayer film in which the sound insulating layer described in Patent Document 1 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, a first layer containing a polyvinyl acetal resin and a plasticizer is laminated on one surface of the first layer, and contains a polyvinyl acetal resin and a plasticizer. The first layer contains an infrared absorber, or the second layer contains an infrared absorber, and the first layer is used as a resin film, When the viscoelasticity of the resin film is measured and the glass transition temperature of the resin film is Tg (° C.), the elastic modulus at (Tg + 80) ° C. of the elastic modulus G ′ (Tg + 80) at (Tg + 30) ° C. An interlayer film for laminated glass having a ratio to G ′ (Tg + 30) (G ′ (Tg + 80) / G ′ (Tg + 30)) of 0.65 or more is provided.

  According to a wide aspect of the present invention, a first layer containing a polyvinyl acetal resin and a plasticizer is laminated on one surface of the first layer, and the polyvinyl acetal resin and the plasticizer are And the first layer contains an infrared absorber, or the second layer contains an infrared absorber, and the polyvinyl acetal is contained in the first layer. When the viscoelasticity of the resin film was measured using a resin film containing 100 parts by weight of resin and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, the resin film The ratio of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. to the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. (G ′ (Tg + 80) / G ′ (Tg + 30) But not less than 0.65, the interlayer film for a laminated glass is provided.

  According to another broad aspect of the present invention, the first layer containing a polyvinyl acetal resin and a plasticizer is laminated on one surface of the first layer, and the polyvinyl acetal resin and the plasticizer are laminated. A second layer containing an agent, wherein the first layer contains an infrared absorber, or the second layer contains an infrared absorber, and the polyvinyl in the first layer The acetal resin provides an interlayer film for laminated glass obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000. In this case, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) may not be 0.65 or more, but is preferably 0.65 or more. Furthermore, in this interlayer film for laminated glass, the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in the first layer. The amount is preferably 40 parts by weight or more, and the hydroxyl group content of the polyvinyl acetal resin in the first layer is preferably 30 mol% or less.

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

  On the specific situation with the intermediate film for laminated glasses which concerns on this invention, the acetylation degree of the said polyvinyl acetal resin in the said 1st layer is 8 mol% or more, or the said polyvinyl in the said 1st layer It is preferable that the degree of acetylation of the acetal resin is less than 8 mol% and the degree of acetalization is 68 mol% or more. The degree of acetylation of the polyvinyl acetal resin in the first layer is preferably 8 mol% or more. Furthermore, it is also preferable that the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol% and the degree of acetalization is 68 mol% or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the elastic modulus G ′ (Tg + 30) is 200,000 Pa or more.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 6.5. It is as follows.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 2. 5 to 3.2.

  In 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 polyvinyl acetal resin in the first layer is 50 parts by weight or more.

  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 polyvinyl acetal resin in the first layer is 55 parts by weight or more.

  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 30 mol% or less.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, a third layer that is laminated on the other surface of the first layer and contains a polyvinyl acetal resin and a plasticizer is further provided. It has been. 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 polyvinyl acetal resin in the first layer is in the second and third layers. The content of the plasticizer is more than 100 parts by weight of the polyvinyl acetal resin.

  Each of the polyvinyl acetal resins contained in the first to third layers preferably contains a polyvinyl butyral resin. The plasticizers contained in the first to third layers are triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate, respectively. It is preferable to include at least one selected from the group consisting of

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film for laminated glass includes a carboxylic acid-modified polyvinyl acetal resin as the polyvinyl acetal resin included in the first layer.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the first layer includes a compound having a boron atom.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the compound having a boron atom is at least one selected from the group consisting of sodium tetraborate, potassium tetraborate, and boric acid. including.

  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 includes a first layer containing a polyvinyl acetal resin and a plasticizer, laminated on one surface of the first layer, and a polyvinyl acetal resin and a plasticizer. Since the said 1st layer or the said 2nd layer contains an infrared absorber, the heat-shielding property of the laminated glass using an intermediate film can be improved.

  Further, the interlayer film for laminated glass according to the present invention includes the first and second layers, and the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more. The occurrence of foaming and the growth of foaming in laminated glass using an intermediate film can be suppressed.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG. FIG. 3 shows a loss tangent tan δ when the viscoelasticity of the resin film is measured using a resin film containing polyvinyl acetal resin contained in the first layer and triethylene glycol di-2-ethylhexanoate. It is a figure for demonstrating the relationship between temperature, and the relationship between elastic modulus G 'and temperature.

  Hereinafter, the present invention will be clarified by giving specific embodiments and examples of the present invention with reference to the drawings.

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

  The intermediate film 1 shown in FIG. 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 of the first layer 2. And a third layer 4 laminated on the surface 2b (second surface). The intermediate film 1 is used to obtain a laminated glass. The intermediate film 1 is an intermediate film for laminated glass. The intermediate film 1 is a multilayer intermediate film.

  The first layer 2 is disposed between the second layer 3 and the third layer 4, and is sandwiched between the second layer 3 and the third layer 4. In the present embodiment, the first layer 2 is an intermediate layer, and the second and third layers 3 and 4 are surface layers. However, the second and third layers 3 and 4 are intermediate layers, and other interlayer films for laminated glass are further laminated on the outer surfaces 3a and 4a of the second and third layers 3 and 4. May be.

  Each of the first to third layers 2 to 4 preferably contains a polyvinyl acetal resin and a plasticizer. 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.

  That is, the main feature of the present invention is that the first layer 2 contains an infrared absorber or the second layer 3 contains an infrared absorber. Thereby, the heat shielding property of the laminated glass of the intermediate film can be enhanced.

  Furthermore, another main feature of the present embodiment is that 100 parts by weight of the polyvinyl acetal resin contained in the first layer 2 and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer. When the viscoelasticity of the resin film A is measured using the resin film A including the part (Test Method A), when the glass transition temperature of the resin film A is Tg (° C.), (Tg + 80) The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) of the elastic modulus G ′ (Tg + 80) at 0 ° C. to the elastic modulus G ′ (Tg + 30) at 0 ° C. is 0.65 or more. .

  In this embodiment, when the first layer 2 is used as the resin film B and the viscoelasticity of the resin film B is measured (test method B), the glass transition temperature of the resin film B is Tg (° C. ), The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. to the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. 0.65 or more.

  In the test method B, the first layer 2 is used as the resin film B, and the first layer 2 itself is the resin film B.

  The resin film B is the first layer 2 and includes the polyvinyl acetal resin and the plasticizer in a weight ratio in the first layer 2. In the test method B, it is preferable to measure the elastic modulus G ′ (Tg + 80) and the elastic modulus G ′ (Tg + 30) after transferring the plasticizer in the interlayer film 1 for laminated glass. In the test method B, after the interlayer film 1 for laminated glass is stored at 30% humidity (± 3%, temperature 23 ° C. for one month) and the plasticizer is transferred in the interlayer film 1 for laminated glass, the elastic modulus is It is more preferable to measure G ′ (Tg + 80) and elastic modulus G ′ (Tg + 30).

  In the interlayer film for laminated glass having a multilayer structure, the present inventors have found that a plasticizer migrates between the respective layers, and as a result, a layer having a high plasticizer content is formed. It was found that the plasticizer migrated from the first layer to the first layer, and as a result, the plasticizer content in the first layer increased. Furthermore, when a layer having a high plasticizer content is formed, that is, when the content of the plasticizer in the first layer is increased, foaming is likely to occur in the laminated glass using the interlayer film for laminated glass, and further foaming occurs. It has also been found that once foaming occurs, foaming grows with the resulting foaming as a nucleus.

  As a result of intensive studies to suppress the occurrence of foaming and the growth of foaming, the present inventors have found that the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to Test Method A or Test Method B is It was also found that the occurrence of foaming and the growth of foaming in the laminated glass can be sufficiently suppressed by being 0.65 or more. Even if there is much content of the plasticizer in the 1st layer 2, since generation | occurrence | production of foaming and the growth of foaming in a laminated glass can fully be suppressed, the sound-insulating property of a laminated glass can be improved. In particular, the second and third layers 3 and 4 are laminated on both surfaces of the first layer 2 configured so that the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more. Further, the use of the interlayer film 1 for laminated glass can further suppress the generation of foam and the growth of foam in the laminated glass.

  The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more, preferably 1.0 or less. When the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more, even if the laminated glass is stored under considerably severe conditions or for a long period of time, the occurrence of foaming and foaming in the laminated glass Can be sufficiently suppressed. Further, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is not less than the above lower limit and not more than the above upper limit, even if the laminated glass is stored under considerably severe conditions or for a long time, Generation of foaming and growth of foaming can be more effectively suppressed. The glass transition temperature Tg (° C.) indicates the peak temperature of the loss tangent tan δ obtained from the measurement result obtained by measuring the viscoelasticity.

  The glass transition temperature Tg (° C.) indicates the peak temperature of the loss tangent tan δ obtained from the measurement result obtained by measuring the viscoelasticity. From the viewpoint of further suppressing the generation of foaming and the growth of foaming in the laminated glass, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is more preferably 0.7 or more, and more preferably 0.95. Or less, more preferably 0.75 or more, and further preferably 0.9 or less. In particular, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is controlled by the average degree of polymerization of the polyvinyl alcohol resin, the occurrence of foaming and the growth of foam in the laminated glass are sufficiently suppressed, and Since the sound insulation can be further improved, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is preferably 0.65 or more, more preferably 0.66 or more, and further preferably 0.67 or more. Particularly preferably, it is 0.7 or more, preferably 0.82 or less, more preferably 0.8 or less. Further, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.82 or less, or 0.8 or less, the intermediate film can be easily formed.

  As a method of setting the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to the test method A or the test method B to 0.65 or more, when synthesizing the polyvinyl acetal resin in the first layer 2 Examples thereof include a method using a polyvinyl alcohol resin having a relatively high average degree of polymerization and a method for strengthening the interaction between molecules of the polyvinyl acetal resin in the first layer 2. Examples of a method for strengthening the interaction between the molecules of the polyvinyl acetal resin in the first layer 2 include a method for physically crosslinking the molecules of the polyvinyl acetal resin and a method for chemically crosslinking the molecules. Especially, since the intermediate film 1 can be easily formed by an extruder, a method of using a polyvinyl alcohol resin having a relatively high average degree of polymerization when synthesizing the polyvinyl acetal resin in the first layer 2. Alternatively, a method of physically cross-linking the molecules of the polyvinyl acetal resin in the first layer 2 is preferable.

  An example of the relationship between the loss tangent tan δ obtained by the viscoelasticity measurement and the temperature and the relationship between the elastic modulus G ′ and the temperature will be described with reference to FIG.

  The loss tangent tan δ and the temperature have a relationship as shown in FIG. The temperature at the peak P of the loss tangent tan δ is the glass transition temperature Tg.

  Further, the glass transition temperature Tg at the elastic modulus G ′ of the broken line A2 shown in FIG. 3 and the glass transition temperature Tg at the elastic modulus G ′ of the solid line A1 are the same temperature. For example, the smaller the change amount D of the elastic modulus G ′ (Tg + 80) with respect to the elastic modulus G ′ (Tg + 30), the more effectively the occurrence of foaming and the growth of foaming in the laminated glass can be suppressed. The change amount D1 in the elastic modulus G ′ of the solid line A1 is smaller than the change amount D2 in the elastic modulus G ′ of the broken line A2. Therefore, in FIG. 3, the case where the change amount D1 shows the elastic modulus G ′ of the solid line A1 where the change amount D1 shows a relatively small amount is larger than the case where the change amount D1 shows the elastic modulus G ′ of the solid line A1. Generation of foaming and growth of foaming can be effectively suppressed.

  The G ′ (Tg + 30) is preferably 200,000 Pa or more. G ′ (Tg + 30) is more preferably 220,000 Pa or more, further preferably 230,000 Pa or more, particularly preferably 240,000 Pa or more, preferably 10 million Pa or less, more preferably 5 million Pa or less, particularly preferably It is 1,000,000 Pa or less, most preferably 500,000 Pa or less, and most preferably 300,000 Pa or less. Generation | occurrence | production of foaming and growth of foaming in a laminated glass can be suppressed more effectively as said G '(Tg + 30) is more than the said minimum.

  The relationship between the elastic modulus G ′ and the temperature is greatly influenced by the kind of the polyvinyl acetal resin, particularly greatly influenced by the average degree of polymerization of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin. It is not greatly affected by the type, and the content of the general plasticizer is not greatly affected by the content of the plasticizer. The above ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) when a plasticizer such as a monobasic organic acid ester other than 3GO is used as the plasticizer, in particular triethylene glycol di- The above ratio when using 2-ethylbutyrate (3GH) and triethylene glycol di-n-heptanoate (3G7) (G ′ (Tg + 80) / G ′ (Tg + 30)) is the above ratio when using 3GO. This is not significantly different from (G ′ (Tg + 80) / G ′ (Tg + 30)). Further, when the content of the plasticizer is 50 to 80 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) does not greatly differ. The above ratio (G ′ (Tg + 80) / G ′) measured using a resin film containing 100 parts by weight of polyvinyl acetal resin and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer. (Tg + 30)) is not significantly different from the above ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) measured using the first layer 2 itself. Both of the above ratios (G ′ (Tg + 80) / G ′ (Tg + 30)) obtained by the above test method A and the above test method B are preferably 0.65 or more. The ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is more preferably 0.65 or more.

  Moreover, when the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer 2 is 50 parts by weight or more, the sound insulation of the laminated glass can be sufficiently enhanced.

  Moreover, in order to suppress generation | occurrence | production of the foaming in the intermediate film for laminated glasses, the said polyvinyl acetal resin in the 1st layer 2 is obtained by acetalizing the polyvinyl alcohol resin with an average degree of polymerization exceeding 3000. It is also preferable. In this case, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) may not be 0.65 or more, but is preferably 0.65 or more.

  That is, in this specification, in order to suppress the occurrence of foaming in the interlayer film for laminated glass, the polyvinyl acetal resin in the first layer 2 acetalizes a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000. The interlayer film for laminated glass (hereinafter, sometimes referred to as a second interlayer film for laminated glass) obtained by the above is also disclosed. In the second interlayer film for laminated glass, the polyvinyl acetal resin in the first layer 2 is obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree exceeding 3000, and the ratio (G An interlayer film for laminated glass in which '(Tg + 80) / G' (Tg + 30)) is less than 0.65 is included. In the second interlayer film for laminated glass, the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in the first layer. The content is preferably 40 parts by weight or more, and the hydroxyl group content of the polyvinyl acetal resin in the first layer is preferably 30 mol% or less.

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

(Polyvinyl acetal resin)
When the first to third layers each contain a polyvinyl acetal resin and a plasticizer, the adhesive strength of the first to third layers can be increased. For this reason, the adhesive force of the intermediate film with respect to the laminated glass constituent member can be further increased.

  The polyvinyl acetal resin in the first layer can be produced by acetalizing a polyvinyl alcohol resin with an aldehyde. The polyvinyl acetal resin in the first layer is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin.

  From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass, the polyvinyl acetal resin in the first layer is obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000. It is preferable.

  From the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass, the preferred lower limit of the average degree of polymerization of the polyvinyl alcohol resin used to obtain the polyvinyl acetal resin in the first layer is 3010, preferably The lower limit is 3050, the preferred lower limit is 3,500, the preferred lower limit is 3600, the preferred lower limit is 4000, the preferred lower limit is 4050, the preferred upper limit is 7000, the preferred upper limit is 6000, the preferred upper limit is 5000, the preferred upper limit is 4900, and the preferred upper limit is 4500. . In particular, the occurrence of foaming and the growth of foaming in the laminated glass are further suppressed, the sound insulation of the laminated glass is sufficiently enhanced, and the interlayer film can be easily molded, so that the polyvinyl acetal resin in the first layer is obtained. The average degree of polymerization of the polyvinyl alcohol resin used for the above is preferably 3010 or more, more preferably 3020 or more, preferably 4000 or less, more preferably less than 4000, or 3800 or less. More preferably, it is more preferably 3600 or less, and most preferably 3500 or less.

  Since the average degree of polymerization of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin in the first layer is equal to or higher than the lower limit, the present inventors are based on the test method A or the test method B. It has also been found that it is easy for the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) to satisfy the lower limit and the upper limit.

  In the present invention, the first layer may contain only a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree exceeding 3000 as a polyvinyl acetal resin, and the average polymerization degree is 3000. A polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin exceeding the above range and other polyvinyl acetal resins may be contained. When the other polyvinyl acetal resin is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree of 3000 or less (hereinafter also referred to as “polyvinyl acetal resin Z”), the average polymerization degree is 3000. Polyvinyl acetal obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in a total of 100% by weight of the polyvinyl acetal resin and the polyvinyl acetal resin Z obtained by acetalizing a polyvinyl alcohol resin exceeding The preferred lower limit of the resin content is 5% by weight, the more preferred lower limit is 50% by weight, the still more preferred lower limit is 70% by weight, the particularly preferred lower limit is 90% by weight, the preferred upper limit is 100% by weight, and the more preferred upper limit is 95% by weight. In . In particular, since the occurrence of foaming and the growth of foaming in laminated glass can be further suppressed, the other polyvinyl acetal resin is a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000. It is preferable.

  The average degree of polymerization of the polyvinyl alcohol resin is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.

  The polyvinyl acetal resin in the second and third layers can be produced by acetalizing a polyvinyl alcohol resin. The preferable lower limit of the average polymerization degree of the polyvinyl alcohol resin for obtaining the polyvinyl acetal resin in the second and third layers is 200, the more preferable lower limit is 500, the still more preferable lower limit is 1000, the particularly preferable lower limit is 1500, and the preferable upper limit is 4000, a more preferred upper limit is 3,500, a still more preferred upper limit is 3000, and a particularly preferred upper limit is 2500. When the average degree of polymerization satisfies the preferable lower limit, the penetration resistance of the laminated glass can be further enhanced. When the average degree of polymerization satisfies the preferable upper limit, the intermediate film can be easily formed.

  The average degree of polymerization of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin in the first layer is higher than the average degree of polymerization of the polyvinyl alcohol resin used for obtaining the polyvinyl acetal resin in the second and third layers. It is preferably high, preferably 500 or higher, preferably 800 or higher, more preferably 1000 or higher, still more preferably 1300 or higher, and particularly preferably 1800 or higher.

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

  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.

  The polyvinyl acetal resin is preferably a polyvinyl butyral resin. Each of the polyvinyl acetal resins contained in the first to third layers preferably contains a polyvinyl butyral resin. Synthesis of polyvinyl butyral resin is easy. Furthermore, the use of the polyvinyl butyral resin allows the intermediate film to have a more appropriate adhesive force with respect to the laminated glass component. Furthermore, light resistance, weather resistance, etc. can be further improved.

  The preferred lower limit of the hydroxyl group content (hydroxyl content) of the polyvinyl acetal resin contained in the first layer as the intermediate layer is 16 mol%, more preferred lower limit is 18 mol%, and still more preferred lower limit is 20 mol%. A particularly preferred lower limit is 22 mol%, a preferred upper limit is 30 mol%, a more preferred upper limit is 29 mol%, a still more preferred upper limit is 27 mol%, and a particularly preferred upper limit is 25 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.

  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. When the hydroxyl group content of the polyvinyl acetal resin in the first layer is lower than the hydroxyl group content of the polyvinyl acetal resin in the second and third layers, the plasticity of the first layer is The content of the agent can be increased. Since the sound insulation of the laminated glass can be further enhanced, the hydroxyl group content of the polyvinyl acetal resin in the first layer is determined by the hydroxyl groups of the polyvinyl acetal resin in the second and third layers. The content is preferably 2 mol% or less, more preferably 4 mol% or less, still more preferably 6 mol% or less, and particularly preferably 8 mol% or less.

  The preferred lower limit of the hydroxyl group content of the polyvinyl acetal resin contained in the second and third layers as the surface layer is 26 mol%, more preferred lower limit is 27 mol%, and still more preferred lower limit is 28 mol%, A particularly preferred lower limit is 29 mol%, a most preferred lower limit is 30 mol%, a preferred upper limit is 35 mol%, a more preferred upper limit is 34 mol%, a still more preferred upper limit is 33 mol%, a particularly preferred upper limit is 32 mol%, and a most preferred upper limit. Is 31.5 mol%. When the hydroxyl group content satisfies the preferable lower limit, the adhesive strength of the intermediate film 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.

  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 K6728 “Testing method for polyvinyl butyral”. it can.

  The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin contained in the first layer is preferably 30 mol% or less. When the degree of acetylation exceeds 30 mol%, the reaction efficiency in producing a polyvinyl acetal resin may be reduced.

  The preferable lower limit of the degree of acetylation of the polyvinyl acetal resin contained in the first layer is 0.1 mol%, the more preferable lower limit is 0.5 mol%, the still more preferable lower limit is 0.8 mol%, and the preferable upper limit. Is 24 mol%, a more preferred upper limit is 20 mol%, a still more preferred upper limit is 19.5 mol%, and a particularly preferred upper limit is 15 mol%. The preferable lower limit of the degree of acetylation of the polyvinyl acetal resin contained in the second and third layers is 0.1 mol%, the more preferable lower limit is 0.5 mol%, and the still more preferable lower limit is 0.8 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. When the acetylation degree satisfies the preferable upper limit, the moisture resistance of the intermediate film can be further enhanced. Since the sound insulation of the laminated glass can be further enhanced, the degree of acetalization of the polyvinyl acetal resin in the first layer is different from the degree of acetalization of the polyvinyl acetal resin in the second and third layers. The acetylation degree of the polyvinyl acetal resin in the first layer is 3 mol% or more higher than the acetylation degree of the polyvinyl acetal resin in the second and third layers. Preferably, it is more preferably at least 5 mol%, more preferably at least 7 mol%, particularly preferably at least 10 mol%.

  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”.

  The preferred lower limit of the degree of acetalization of the polyvinyl acetal resin contained in the first layer is 50 mol%, more preferred lower limit is 54 mol%, still more preferred lower limit is 58 mol%, and particularly preferred lower limit is 60 mol%, preferably The upper limit is 85 mol%, the more preferable upper limit is 80 mol%, and the more preferable upper limit is 79 mol%. The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin contained in the second and third layers is 60 mol%, the more preferable lower limit is 65 mol%, the still more preferable lower limit is 66 mol%, and the particularly preferable lower limit is 67 mol%. %, A preferred upper limit is 75 mol%, a more preferred upper limit is 72 mol%, a still more preferred upper limit is 71 mol%, and a particularly preferred upper limit is 70 mol%. When the degree of acetalization satisfies the preferable lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further enhanced. 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. Since the sound insulation of the laminated glass can be further enhanced, the degree of acetylation of the polyvinyl acetal resin in the first layer and the degree of acetylation of the polyvinyl acetal resin in the second and third layers. When the absolute value of the difference between the first and second layers is 3 or less, the degree of acetalization of the polyvinyl acetal resin in the first layer is greater than the degree of acetalization of the polyvinyl acetal resin in the second and third layers. Is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, and particularly preferably 10 mol% or more.

  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%.

  Furthermore, since the occurrence of foaming and the growth of foaming in the laminated glass can be further suppressed, and the sound insulation of the laminated glass can be further enhanced, the polyvinyl acetal resin contained in the first layer is Polyvinyl acetal resin (hereinafter also referred to as “polyvinyl acetal resin A”) having an acetylation degree of less than 8 mol%, or a polyvinyl acetal resin (hereinafter referred to as “polyvinyl acetal resin B”) having an acetylation degree of 8 mol% or more. It is also preferred that

  The degree of acetylation a of the polyvinyl acetal resin A is less than 8 mol%, preferably 7.5 mol% or less, preferably 7 mol% or less, and preferably 6 mol% or less, 5 mol% or less is preferable, 0.1 mol% or more is preferable, 0.5 mol% or more is preferable, 0.8 mol% or more is preferable, and 1 mol% or more is preferable. Preferably, it is 2 mol% or more, preferably 3 mol% or more, and preferably 4 mol% or more. When the acetylation degree a is not more than the above upper limit and not less than the above lower limit, the compatibility between the polyvinyl acetal resin A and the plasticizer is further enhanced, and the sound insulation of the laminated glass can be further enhanced.

  A preferable lower limit of the degree of acetalization a of the polyvinyl acetal resin A is 68 mol%, a more preferable lower limit is 70 mol%, a further preferable lower limit is 71 mol%, a particularly preferable lower limit is 72 mol%, and a preferable upper limit is 85 mol%. A preferred upper limit is 83 mol%, a 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 hydroxyl group content a of the polyvinyl acetal resin A is preferably 30 mol% or less, preferably 27.5 mol% or less, preferably 27 mol% or less, and 26 mol% or less. It is preferably 25 mol% or less, preferably 24 mol% or less, preferably 23 mol% or less, preferably 16 mol% or more, and 18 mol% or more. It is preferable that it is 19 mol% or more, and it is preferable that it is 20 mol% or more. When the hydroxyl group content a is not more than the above upper limit, the sound insulation of the laminated glass can be further enhanced. When the hydroxyl group content a is equal to or higher than the lower limit, the adhesive strength of the intermediate film can be further increased.

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

  The degree of acetylation b of the polyvinyl acetal resin B is 8 mol% or more, preferably 9 mol% or more, preferably 10 mol% or more, preferably 11 mol% or more, 12 It is preferably at least mol%, preferably at most 30 mol%, preferably at most 28 mol%, preferably at most 26 mol%, preferably at most 24 mol%, It is preferably at most 1 mol%, more preferably at most 19.5 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. Especially, since reaction time required in order to manufacture polyvinyl acetal resin B can be shortened further, it is preferable that the acetylation degree b of the said polyvinyl acetal resin B is less than 20 mol%.

  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 52.5 mol%, the still more preferable lower limit is 54 mol%, the particularly preferable lower limit is 60 mol%, and the preferable upper limit is 80 mol%. A more preferred upper limit is 77 mol%, a still more preferred upper limit is 74 mol%, and a particularly preferred upper limit is 71 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 hydroxyl content b of the polyvinyl acetal resin B is preferably 30 mol% or less, preferably 27.5 mol% or less, preferably 27 mol% or less, and 26 mol% or less. It is preferably 25 mol% or less, preferably 18 mol% or more, preferably 20 mol% or more, preferably 22 mol% or more, and 23 mol% or more. It is preferable. When the hydroxyl group content b is not more than the above upper limit, the sound insulation of the laminated glass can be further enhanced. When the hydroxyl group content b is not less than the above lower limit, the adhesive strength of the intermediate film can be further increased.

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

  The polyvinyl acetal resin A and the polyvinyl acetal resin B are preferably obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree exceeding 3000 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 preferred lower limit of the average degree of polymerization of the polyvinyl alcohol resin is 3010, the preferred lower limit is 3050, the preferred lower limit is 3500, the preferred lower limit is 3600, the preferred lower limit is 4000, the preferred lower limit is 4050, the preferred upper limit is 7000, and the preferred upper limit is 6000, preferred. The upper limit is 5000, the preferred upper limit is 4900, and the preferred upper limit is 4500. The polyvinyl acetal resin in the first layer is particularly preferably obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization of more than 3000 and less than 4000. In particular, the occurrence of foaming and the growth of foaming in the laminated glass are further suppressed, the sound insulation of the laminated glass is sufficiently enhanced, and the interlayer film can be easily molded, so that the polyvinyl acetal resin in the first layer is obtained. The average degree of polymerization of the polyvinyl alcohol resin used for the above is preferably 3010 or more, more preferably 3020 or more, preferably 4000 or less, more preferably less than 4000, or 3800 or less. More preferably, it is more preferably 3600 or less, and most preferably 3500 or less.

  The molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is generally 1.1 or more, preferably 1.2 or more, more preferably 2 As mentioned above, Preferably it is 6.7 or less, More preferably, it is 6.5 or less, More preferably, it is 3.4 or less.

  The preferred lower limit of the molecular weight distribution ratio of the polyvinyl acetal resin contained in the first layer is 1.2, the more preferred lower limit is 1.5, the still more preferred lower limit is 2.0, and the particularly preferred lower limit is 2.5. The preferred upper limit is 5.5, the more preferred upper limit is 5, the still more preferred upper limit is 4.6, and the particularly preferred upper limit is 3.2. The molecular weight distribution ratio of the polyvinyl acetal resin contained in the first layer is particularly preferably 2.5 to 3.2. The molecular weight distribution ratio indicates the ratio of the weight average molecular weight Mw of the polyvinyl acetal resin contained in the first layer to the number average molecular weight Mn of the polyvinyl acetal resin contained in the first layer. When the molecular weight distribution ratio of the polyvinyl acetal resin contained in the first layer is equal to or higher than the lower limit and equal to or lower than the upper limit, or 2.5 to 3.2. It is easy to make the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to the test method A or the test method B satisfy the lower limit and the upper limit, and generation of foaming in the laminated glass. It was also found that the growth of foaming can be more effectively suppressed. Among them, the occurrence of foaming and the growth of foaming in the laminated glass can be further effectively suppressed, and the sound insulation of the laminated glass can be further enhanced, so that the polyvinyl acetal resin contained in the first layer is used. Preferably, the plasticizer content is 50 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin contained in the first layer. In particular, when the polyvinyl acetal resin contained in the first layer contains the polyvinyl acetal resin B, the molecular weight distribution ratio of the polyvinyl acetal resin B is 6.5 or less, and the first layer It is preferable that content of the said plasticizer with respect to 100 weight part of said polyvinyl acetal resins contained in is 55 weight part or more.

  In addition, the said weight average molecular weight and the said number average molecular weight show the weight average molecular weight and number average molecular weight in polystyrene conversion by a gel permeation chromatography (GPC) measurement. For example, in order to measure a weight average molecular weight and a number average molecular weight in terms of polystyrene, GPC measurement of a polystyrene standard sample having 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, 21,000 , 28,500, 76,600, 196,000, 630,000, 11,130,000, 2,190,000, 3,150,000, 3,900,000. An approximate straight line obtained by plotting the molecular weight against the elution time indicated by the peak top of each standard sample peak is used as a calibration curve. From the multilayer intermediate film left in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for one month, the surface layer (the second and third layers) and the intermediate layer (the first layer) And the peeled first layer (intermediate layer) is dissolved in tetrahydrofuran (THF) to prepare a 0.1 wt% solution. The obtained solution can be analyzed by a GPC apparatus, and a weight average molecular weight and a number average molecular weight can be measured. As a GPC apparatus, a GPC apparatus (Hitachi High-Tech "RI: L2490, Autosampler: L-2200, Pump: L-2130, GPC apparatus to which a GPC light scattering detector (" Model 270 (RALS + VISCO) "manufactured by VISCOTEK)) is connected. Column oven: L-2350, column: series of GL-A120-S and GL-A100MX-S ”), the weight average molecular weight and the number average molecular weight can be analyzed.

  Moreover, from the viewpoint of further suppressing the occurrence of foaming and the growth of foaming in the laminated glass and obtaining a laminated glass excellent in sound insulation, the polyvinyl acetal resin contained in the first layer is modified with carboxylic acid. A polyvinyl acetal resin is preferable, and a carboxylic acid-modified polyvinyl butyral resin is more preferable. By using a carboxylic acid-modified polyvinyl acetal resin, it is easy to make the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to Test Method A or Test Method B satisfy the lower limit and the upper limit. is there. The carboxylic acid-modified polyvinyl acetal resin has an ethylene group having an acetal group, an ethylene group having an acetyl group, an ethylene group having a hydroxyl group, and an ethylene group modified with a carboxylic acid. Examples of the carboxylic acid include unsaturated dicarboxylic acids and unsaturated tricarboxylic acids. The carboxylic acid is preferably an unsaturated dicarboxylic acid such as maleic acid or itaconic acid. When the total of the ethylene group having the acetal group, the ethylene group having the acetyl group, the ethylene group having the hydroxyl group, and the ethylene group modified with the carboxylic acid is 100 mol%, the carboxylic acid The ratio of the modified ethylene group is preferably more than 0 mol% and 10 mol% or less. The preferable upper limit of the proportion of the ethylene group modified with the carboxylic acid is 9 mol%, the preferable upper limit is 8 mol%, the preferable upper limit is 7 mol%, the preferable upper limit is 6 mol%, the preferable upper limit is 5 mol%, and the preferable upper limit is 4 mol%, a preferable upper limit is 3 mol%, and a preferable upper limit is 2 mol%.

(Plasticizer)
The plasticizer contained in each of the first to third layers is not particularly limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

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

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

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

  The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di 2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl hexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, adipine Examples include a mixture of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, alkyd oil-modified sebacic acid, and a mixture of phosphate ester and adipate. Organic ester plasticizers other than these may be used. 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 is selected from the group consisting of triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-n-heptanoate (3G7). It is preferable to include at least one selected from the group consisting of triethylene glycol di-2-ethylhexanoate. The plasticizers contained in the first to third layers are triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate, respectively. It is preferable to include at least one selected from the group consisting of By using these preferable plasticizers, the sound insulation of the laminated glass can be further enhanced.

  The content of the plasticizer in each layer of the interlayer film is not particularly limited.

  From the viewpoint of sufficiently increasing the sound insulation of the laminated glass, the plasticizer content in 100 parts by weight of the polyvinyl acetal resin in the first layer is preferably 40 parts by weight or more. By configuring the first layer so that the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more even if the plasticizer content of the first layer is large. The occurrence of foaming and the growth of foaming in laminated glass can be suppressed.

  In addition, regarding the second interlayer film for laminated glass obtained by acetalizing the polyvinyl alcohol resin in which the average degree of polymerization exceeds 3000, the polyvinyl acetal resin in the first layer is the first It is preferable that the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average polymerization degree exceeding 3000 in the layer is 40 parts by weight or more. Thus, by using the polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in the first layer, the plasticizer content is 40 parts by weight or more. Even so, the occurrence of foaming and the growth of foaming in the laminated glass can be suppressed.

  The more preferred lower limit of the plasticizer content relative to 100 parts by weight of the polyvinyl acetal resin in the first layer is 45 parts by weight, the still more preferred lower limit is 50 parts by weight, the particularly preferred lower limit is 55 parts by weight, and the most preferred lower limit is 60 parts by weight. Parts, a preferred upper limit is 80 parts by weight, a more preferred upper limit is 78 parts by weight, a still more preferred upper limit is 75 parts by weight, and a particularly preferred upper limit is 70 parts by weight. Moreover, the more preferable lower limit of the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin obtained by acetalizing the polyvinyl alcohol resin having an average degree of polymerization exceeding 3000 in the first layer is 45 parts by weight, A more preferred lower limit is 50 parts by weight, a particularly preferred lower limit is 55 parts by weight, a most preferred lower limit is 60 parts by weight, a preferred upper limit is 80 parts by weight, a more preferred upper limit is 78 parts by weight, and a still more preferred upper limit is 75 parts by weight. Is 70 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. As the content of the plasticizer in the first layer is larger, the sound insulation of the laminated glass can be further enhanced. When content of the said plasticizer satisfy | fills the said preferable upper limit, transparency of an intermediate film can be improved further.

  The preferred lower limit of the plasticizer content relative to 100 parts by weight of the polyvinyl acetal resin in the second and third layers is 25 parts by weight, the more preferred lower limit is 30 parts by weight, the still more preferred lower limit is 35 parts by weight, and the preferred upper limit is 50 parts. More preferred upper limit is 45 parts by weight, still more preferred upper limit is 40 parts by weight, and particularly preferred upper limit is 39 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 plasticizer content in 100 parts by weight of the polyvinyl acetal resin in the first layer is 100 parts by weight of the polyvinyl acetal resin in the second and third layers. It is preferable that there are more than each 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 polyvinyl acetal resin in the first layer is 100 parts by weight of the polyvinyl acetal 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 12 parts by weight or more, and particularly preferably 15 parts by weight or more.

(Infrared absorber)
When the said 1st layer or the said 2nd layer contains the said infrared absorber, the thermal insulation of the intermediate film for laminated glasses and a 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.

  Of the first to third layers, the layer containing the polyvinyl acetal resin and the infrared absorber, and the preferred lower limit of the content of the infrared absorber is 100 parts by weight with respect to 100 parts by weight of the polyvinyl acetal 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.

  The content of the heat shielding particles in the layer containing the polyvinyl acetal resin and the infrared absorber is not particularly limited. In 100% by weight of the layer containing the polyvinyl acetal 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 polyvinyl acetal 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 polyvinyl acetal resin and the heat shielding particles, the content of the heat shielding particles with respect to 100 parts by weight of the polyvinyl acetal resin is defined as content A, and the content of the component X with respect to 100 parts by weight of the polyvinyl acetal 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 containing the polyvinyl acetal 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 polyvinyl acetal resin and the heat shielding particles is not particularly limited. In 100% by weight of the layer containing the polyvinyl acetal 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 polyvinyl acetal resin and the heat-shielding particles is within the preferable range, the heat-shielding property can be sufficiently increased, 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 including the polyvinyl acetal 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 polyvinyl acetal 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 polyvinyl acetal 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 polyvinyl acetal 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 polyvinyl acetal 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 polyvinyl acetal resin in the layer containing the polyvinyl acetal 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 polyvinyl acetal 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 p-polyvinyl acetal resin. The preferred lower limit is 0.005 parts by weight, the more preferred lower limit is 0.03 parts by weight, the still more preferred lower limit is 0.04 parts by weight, the particularly preferred lower limit is 0.07 parts by weight, and the more preferred upper limit is 0.24 parts by weight. Parts, and 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 contained in the interlayer film layer preferably contains at least one of 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 preferable that the first layer contains an ultraviolet shielding agent, or the second layer contains an ultraviolet shielding agent, and the second layer is an ultraviolet shielding agent. It is more preferable to contain an agent. 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)
From the viewpoint of further suppressing generation of foaming and growth of foaming in the laminated glass and obtaining a laminated glass excellent in sound insulation, the first layer preferably contains a compound having a boron atom. Although it does not specifically limit as said compound which has a boron atom, Tetraborate, a boric acid, etc. are mentioned. Examples of the tetraborate include sodium tetraborate and potassium tetraborate. By using a compound having a boron atom, it is easy to make the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to Test Method A or Test Method B satisfy the lower limit and the upper limit. .

  A preferable lower limit of the content of the compound having a boron atom with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 0.01 part by weight, a more preferable lower limit is 0.05 part by weight, and a still more preferable lower limit is 0.00. 1 part by weight, the preferred upper limit is 5 parts by weight, the more preferred upper limit is 1 part by weight, and the still more preferred upper limit is 0.5 parts by weight. When the content of the compound having a boron atom satisfies the preferable lower limit, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to the test method A or the test method B satisfies the lower limit and the upper limit. It is easy to do so. When the content of the boron atom-containing compound satisfies the preferable upper limit, the transparency of the laminated glass can be further increased.

  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.

(Method for producing interlayer film for laminated glass and 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 interlayer film is excellent, it is preferable that the second and third layers contain the same polyvinyl acetal resin, and the second and third layers contain the same polyvinyl acetal resin and More preferably, the same plasticizer is contained, and the second and third layers are more preferably formed of the same resin composition.

  Each of the interlayer films for laminated glass according to the present invention is used to obtain a laminated glass.

  FIG. 2 is a cross-sectional view schematically showing an example of a laminated glass using the intermediate film 1 shown in FIG.

  A laminated glass 11 shown in FIG. 2 includes a first laminated glass constituting member 12, a second laminated glass constituting member 13, and the intermediate film 1. The 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.

  From the viewpoint of further improving the penetration resistance of the laminated glass, the preferable lower limit of the thickness of the interlayer film is 0.05 mm, the more preferable lower limit is 0.25 mm, the preferable upper limit is 3 mm, and the more preferable upper limit is 1.5 mm. When the thickness of the interlayer film satisfies the preferable lower limit and the preferable upper limit, the penetration resistance and transparency of the laminated glass can be further enhanced. 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 the said 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, the 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 for other purposes. 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.

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 interlayer film Polyvinyl butyral resin A obtained by butyralizing a polyvinyl alcohol resin having an average polymerization degree of 3050 with n-butyraldehyde (hydroxyl group content 23.5 mol%, acetylation degree) (12.5 mol%, butyralization degree 64 mol%) 100 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer was added and kneaded thoroughly with a mixing roll. A resin composition for an intermediate layer was obtained.

  Furthermore, polyvinyl butyral resin B obtained by butyralizing a polyvinyl alcohol resin having an average polymerization degree of 1700 with n-butyraldehyde (hydroxyl group content 30.4 mol%, acetylation degree 0.8 mol%, The total amount of the dispersion was added to 100 parts by weight of (butyralization degree 68.8 mol%), and the mixture was sufficiently kneaded with a mixing roll to obtain a resin composition for the surface layer.

  By using the obtained resin composition for intermediate layer and resin composition for surface layer and coextruding with an extruder, a surface layer (thickness 350 μm), an intermediate layer (thickness 100 μm), and a surface layer (thickness 350 μm) Were produced in order.

(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 test (Laminated glass used for foaming test of Test Method A)
The obtained multilayer intermediate film was cut into a size of 30 cm (length) × 15 cm (width), and stored in an environment at a temperature of 23 ° C. for 10 hours. 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 having a diameter of 6 mm was formed at a location to obtain a multilayer intermediate film having a through-hole.

  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 the foaming test.

(Laminated glass used for foaming test of test method B)
A laminated glass used for the foaming test of Test Method B was obtained in the same manner as the laminated glass used for the foaming test of Test Method A, except that through holes were not formed in the multilayer interlayer film.

(Examples 2-46 and Comparative Examples 1-5)
Tables 1 to 3 below show the composition of the first to third layers, the composition of the dispersion (number of blended parts of the plasticizer), and the average degree of polymerization of the polyvinyl alcohol resin used to obtain the polyvinyl acetal resin used for the first layer. An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the changes were made as shown in FIG.

  In Examples 34 to 36, sodium tetraborate was added to the content shown in Table 4 below with respect to 100 parts by weight of the polyvinyl acetal resin when the resin composition for the intermediate layer was prepared. Further, in Example 37, in place of the polyvinyl butyral resin in the intermediate layer resin composition, a carboxylic acid-modified polyvinyl butyral resin (average polymerization degree 1800, hydroxyl group content 21.3 mol%, acetylation degree 12.6 mol) %, Butyralization degree 64.9 mol%, carboxylic acid modification ratio 1.2 mol%), and the composition of the first to third layers was changed as shown in Table 4 below. In the same manner as in Example 1, an interlayer film and a laminated glass were produced. Moreover, the polyvinyl butyral resin contained in the resin composition for surface layers of Examples 2-46 and Comparative Examples 1-5 was obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization of 1700.

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

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

(2) Foamed state (Test Method A and Test Method B)
Five laminated glasses used for the foaming test were prepared for each multilayer interlayer film and left in an oven at 50 ° C. for 100 hours. In the laminated glass after standing, the presence or absence of foaming and the size of foaming were visually observed in a plan view (Test Method A). Furthermore, five laminated glasses used for the foaming test produced by the above test method B were produced for each multilayer intermediate film, and left in an oven at 50 ° C. for 30 days. In the laminated glass after being left, the presence or absence of foaming and the size of foaming were visually observed in plan view (Test Method B). From the observation results, the state of foaming was determined according to the following criteria.

[Criteria for foaming state]
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) Penetration resistance Laminated glass (length 30 cm x width 30 cm) used for 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. .

(4) Measurement of Elastic Modulus G ′ by Test Method A 100 parts by weight of each polyvinyl acetal resin (polyvinyl acetal resin used for the first layer) contained in the first layer of the interlayer film for laminated glass of Examples and Comparative Examples And 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer were sufficiently kneaded to obtain a kneaded product. The obtained kneaded material was press-molded with a press molding machine to obtain a resin film A having an average thickness of 0.35 mm. The obtained resin film A was allowed to stand for 2 hours at 25 ° C. and a relative humidity of 30%. After standing for 2 hours, viscoelasticity was measured using ARES-G2 manufactured by TAINSTRUMENTS. As a jig, a parallel plate having a diameter of 8 mm was used. The measurement was performed under the condition of decreasing the temperature from 100 ° C. to −10 ° C. at a temperature decrease rate of 3 ° C./min, and under the conditions of frequency 1 Hz and strain 1%. In the obtained measurement results, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). Further, from the obtained measurement result and the glass transition temperature Tg, the value of the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. and the value of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. are read. It was. Further, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) was determined.

(5) Measurement of Elastic Modulus G ′ by Test Method B The interlayer films for laminated glass of Examples and Comparative Examples were stored in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for 1 month. Immediately after storage for 1 month, the intermediate layer was taken out by peeling the surface layer, intermediate layer and surface layer. 1 g of the peeled intermediate layer is placed in a formwork (length 2 cm × width 2 cm × thickness 0.76 mm) placed between two polyethylene terephthalate (PET) films, the temperature is 150 ° C., and the press pressure is 0 kg / cm. ² for 10 minutes and then press-molded at 80 kg / cm ² for 15 minutes. The press-molded intermediate layer was placed in a hand press set in advance at 20 ° C. and cooled by pressing at 10 MPa for 10 minutes. Next, after peeling off one PET film from a mold placed between two PET films and storing it in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for 24 hours Viscoelasticity was measured using ARES-G2 manufactured by TAINSTRUMENTS. As a jig, a parallel plate having a diameter of 8 mm was used. The measurement was performed under the condition of decreasing the temperature from 100 ° C. to −10 ° C. at a temperature decrease rate of 3 ° C./min, and under the conditions of frequency 1 Hz and strain 1%. In the obtained measurement results, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). Further, from the obtained measurement result and the glass transition temperature Tg, the value of the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. and the value of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. are read. It was. Further, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) was determined.

  The results are shown in Tables 1 to 5 below. In Tables 1 to 5 below, 3GO, which is a type of plasticizer, represents triethylene glycol di-2-ethylhexanoate, and 3GH represents triethylene glycol di-2-ethylbutyrate. The values of the molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin used for the first layer are also shown in Tables 1 to 5 below. In addition, the number average molecular weight Mn of the polyvinyl acetal resin used for the first layer was in the range of 50,000 to 500,000. The number average molecular weight indicates the number average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

  As shown in the said Tables 1-5, in the intermediate film for laminated glasses of an Example and a comparative example, the polyvinyl acetal resin which comprises a 1st layer, and the plasticizer which comprises a 1st layer are the said Tables 1-5. After using the resin film B (first layer) contained in the amount of the plasticizer to transfer the plasticizer between the layers of the multilayer intermediate film, the elastic modulus G ′ of the resin film B (first layer) is measured. As a result, the ratio of the resin film B (G ′ (Tg + 80) / G ′ (Tg + 30)) is 100% by weight of the polyvinyl acetal resin contained in the first layer and 60 parts by weight of 3GO. The ratio was almost the same as the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)).

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

Claims (22)

A first layer containing a polyvinyl acetal resin and a plasticizer;
A second layer that is laminated on one side of the first layer and contains a polyvinyl acetal resin and a plasticizer;
The first layer contains an infrared absorber, or the second layer contains an infrared absorber;
When the viscoelasticity of the resin film was measured using the first layer as a resin film, the elastic modulus G at (Tg + 80) ° C. when the glass transition temperature of the resin film was Tg (° C.) The interlayer film for laminated glass having a ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) of elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. to (Tg + 80) of 0.65 or more. A first layer containing a polyvinyl acetal resin and a plasticizer;
A second layer that is laminated on one side of the first layer and contains a polyvinyl acetal resin and a plasticizer;
The first layer contains an infrared absorber, or the second layer contains an infrared absorber;
Using a resin film containing 100 parts by weight of the polyvinyl acetal resin contained in the first layer and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, When measuring the viscoelasticity, when the glass transition temperature of the resin film is Tg (° C.), the elastic modulus G ′ at (Tg + 30) ° C. of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. The interlayer film for laminated glass having a ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) to Tg + 30) of 0.65 or more.   The interlayer film for laminated glass according to claim 1 or 2, wherein the second layer contains the infrared absorber.   The interlayer film for laminated glass according to any one of claims 1 to 3, wherein the infrared absorber includes heat shielding particles.   The interlayer film for laminated glass according to any one of claims 1 to 4, wherein the infrared absorber includes metal oxide particles.   The degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or more, or the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol%, and the acetal The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the degree of conversion is 68 mol% or more.   The interlayer film for laminated glass according to claim 6, wherein the degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or more.   The interlayer film for laminated glass according to claim 6, wherein the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol%, and the degree of acetalization is 68 mol% or more.   The interlayer film for laminated glass according to any one of claims 1 to 8, wherein the elastic modulus G '(Tg + 30) is 200,000 Pa or more.   The molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 6.5 or less, according to any one of claims 1 to 9. An interlayer film for laminated glass.   11. The intermediate for laminated glass according to claim 10, wherein a molecular weight distribution ratio (weight average molecular weight Mw / number average molecular weight Mn) of the polyvinyl acetal resin contained in the first layer is 2.5 to 3.2. film.   The interlayer film for laminated glass according to any one of claims 1 to 11, wherein a content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is 50 parts by weight or more.   The interlayer film for laminated glass according to claim 12, wherein a 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.   The interlayer film for laminated glass according to any one of claims 1 to 13, wherein a content of a hydroxyl group of the polyvinyl acetal resin in the first layer is 30 mol% or less.   The laminated glass according to any one of claims 1 to 14, further comprising a third layer that is laminated on the other surface of the first layer and contains a polyvinyl acetal resin and a plasticizer. Interlayer film.   The interlayer film for laminated glass according to claim 15, wherein the third layer contains an infrared absorber.   Content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is more than each content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the second and third layers. The interlayer film for laminated glass according to claim 15 or 16, wherein there are many. Each of the polyvinyl acetal resins contained in the first to third layers contains a polyvinyl butyral resin,
The plasticizers contained in the first to third layers are triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate and triethylene glycol di-n-heptanoate, respectively. The interlayer film for laminated glass according to any one of claims 15 to 17, comprising at least one selected from the group consisting of:   The interlayer film for laminated glass according to any one of claims 1 to 18, comprising a carboxylic acid-modified polyvinyl acetal resin as the polyvinyl acetal resin contained in the first layer. The interlayer film for laminated glass according to any one of claims 1 to 19, wherein the first layer contains a compound having a boron atom.   21. The interlayer film for laminated glass according to claim 20, wherein the compound having a boron atom includes at least one selected from the group consisting of sodium tetraborate, potassium tetraborate, and boric acid. 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 21.

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