JP2015147729A - Intermediate film for laminated glass, multilayer intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass which can provide laminated glass capable of suppressing occurrence of foam and growth of the foam, and to provide a multilayer intermediate film for laminated glass using the intermediate film.SOLUTION: The intermediate film for laminated glass 2 and 21 comprises a polyvinyl acetal resin and a plasticizer. The intermediate film for laminated glass 2 and 21 has a maximum tan δ value of 1.00 or less at 200°C and an angular frequency ω of 10≤ω≤10. The multilayer intermediate film for laminated glass 1 comprises a first intermediate film for laminated glass 2 and a second intermediate film for laminated glass 3 which is laminated on a first surface 2a of the first intermediate film for laminated glass 2 and comprises a polyvinyl acetal resin and a plasticizer.

Description

  The present invention relates to an interlayer film for laminated glass containing a polyvinyl acetal resin and a plasticizer, and more specifically, an interlayer film for laminated glass capable of obtaining a laminated glass that hardly causes foaming, and the interlayer film for laminated glass The present invention relates to a multilayer interlayer film for laminated glass and laminated glass.

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

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

  Further, in Patent Document 2 below, 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of 0.001 to 1 of an alkali metal salt and an alkaline earth metal salt A sound insulation layer containing 0.0 part by weight and 30 parts by weight or more of a plasticizer is disclosed. This sound insulation layer may be a single layer and used as an intermediate film.

  Further, Patent Document 2 below also describes a multilayer intermediate film in which the sound insulation layer and other layers are laminated. The other layer laminated on the sound insulation layer is composed of 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of an alkali metal salt and an alkaline earth metal salt 0.001 to 0.001. 1.0 part by weight and a plasticizer of 30 parts by weight or less are included.

JP 2001-097745 A JP 2007-070200 A

  When the laminated glass is formed using the interlayer film described in Patent Document 1, the sound insulation in the frequency region near 2000 Hz of the laminated glass is not sufficient, and therefore the sound insulation performance is inevitably lowered due to the coincidence effect. There is. In particular, the sound insulation properties at around 20 ° C. of this laminated glass may not be sufficient.

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

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

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

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

  An object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass capable of suppressing the occurrence of foaming and the growth of foam, and a multilayer interlayer film for laminated glass and a laminated glass using the interlayer film for laminated glass. It is to be.

  A limited object of the present invention is to use an interlayer film for laminated glass, which is excellent in sound insulation and can obtain a laminated glass capable of suppressing the occurrence of foaming and the growth of foam, and the interlayer film for laminated glass. It is providing the multilayer intermediate film for laminated glasses, and laminated glass.

According to a broad aspect of the present invention contains a polyvinyl acetal resin and a plasticizer, is 1.00 or less the maximum value of tanδ at 200 ° C. and the angular frequency omega is 10 ^-2 ≦ ω ≦ 10 ^0, combined An interlayer film for glass is provided.

  On the specific situation with the intermediate film for laminated glasses which concerns on this invention, the content rate of the hydroxyl group of the said polyvinyl acetal resin is 31 mol% or less.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer is 40 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin.

  The multilayer interlayer film for laminated glass according to the present invention includes the interlayer film for laminated glass configured according to the present invention as a first interlayer film for laminated glass, and is formed on the first surface of the interlayer film for first laminated glass. A second interlayer film for laminated glass that is laminated and contains a polyvinyl acetal resin and a plasticizer is further provided.

  On the specific situation with the multilayer intermediate film for laminated glasses which concerns on this invention, content of the said plasticizer with respect to 100 weight part of said polyvinyl acetal resins in the said intermediate film for laminated glasses is said 2nd laminated glass. More than the content of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin in the intermediate film.

  In another specific aspect of the multilayer interlayer film for laminated glass according to the present invention, the multilayer interlayer film is laminated on a second surface opposite to the first surface of the first interlayer film for laminated glass, and a polyvinyl acetal resin And a third interlayer film for laminated glass containing a plasticizer.

  In still another specific aspect of the multilayer interlayer film for laminated glass according to the present invention, the content of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin in the first interlayer film for laminated glass is the third interlayer film. The content of the plasticizer is more than 100 parts by weight of the polyvinyl acetal resin in the interlayer film for laminated glass.

  For example, the plasticizer may move between the first interlayer film for laminated glass and the second interlayer film for laminated glass. For example, the plasticizer may move between the first interlayer film for laminated glass and the third interlayer film for laminated glass.

  In another specific aspect of the multilayer interlayer film for laminated glass according to the present invention, the degree of acetylation of the polyvinyl acetal resin in the first interlayer film for laminated glass is 8 mol% or less, and the degree of acetalization is It is 70 mol% or more.

  In still another specific aspect of the multilayer interlayer film for laminated glass according to the present invention, the degree of acetylation of the polyvinyl acetal resin in the first interlayer film for laminated glass exceeds 8 mol%.

  The laminated glass according to the present invention includes first and second laminated glass constituent members, and an intermediate film or a multilayer intermediate film sandwiched between the first and second laminated glass constituent members, The interlayer film or multilayer interlayer film includes an interlayer film for laminated glass configured according to the present invention, or is a multilayer interlayer film for laminated glass configured according to the present invention.

Intermediate film for laminated glass according to the present invention contains a polyvinyl acetal resin and a plasticizer, the maximum value of tanδ is 1.00 or less at 200 ° C. and the angular frequency omega is 10 ^-2 ≦ ω ≦ 10 ⁰ Therefore, when used to construct a laminated glass, the occurrence of foaming and the growth of foaming in the laminated glass can be suppressed. Furthermore, the sound insulation of the obtained laminated glass can be improved.

FIG. 1 is a cross-sectional view schematically showing a multilayer interlayer film for laminated glass according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing an example of laminated glass using the multilayer interlayer film for laminated glass shown in FIG.

  Details of the present invention will be described below.

The interlayer film for laminated glass according to the present invention contains a polyvinyl acetal resin and a plasticizer. The maximum value of tanδ at 200 ° C. and the angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} intermediate film for laminated glass of the present invention is 1.00 or less. Laminated glass multilayer intermediate film according to the present invention, a first interlayer film for a laminated glass of which the maximum value of tanδ at 200 ° C. and the angular frequency omega is 10 ^-2 ≦ ω ≦ 10 ⁰ 1.00 or less, A second interlayer film for laminated glass that is laminated on the first surface of the first interlayer film for laminated glass and contains a polyvinyl acetal resin and a plasticizer. By using an intermediate film having a tan δ of not more than the above upper limit, a laminated glass capable of suppressing the generation of foam and the growth of foam can be obtained. Furthermore, it is also possible to obtain a laminated glass that is excellent in sound insulation and can suppress the generation of foam and the growth of foam.

The maximum value of tanδ at 200 ° C. and the angular frequency omega is 10 ^-2 ≦ ω ≦ 10 ⁰ of the intermediate layer is a value measured by using a viscoelasticity measuring apparatus. As the viscoelasticity measuring device, “ARES-G2” manufactured by TAINSTRUMENTS is used.

As a method 200 ° C. and the angular frequency omega of the intermediate film is a maximum value of tanδ at 10 ^-2 ≦ ω ≦ 10 ⁰ to 1.00 or less, adjust the polymerization degree of the polyvinyl alcohol for obtaining a polyvinyl acetal resin And a method of increasing the proportion of a high molecular weight component having a relatively large molecular weight in the polyvinyl acetal resin, a method of increasing the cross-linking density between molecules in the polyvinyl acetal resin, and the like. The maximum value of tanδ at the 200 ° C. and the angular frequency omega is 10 ^-2 ≦ ω ≦ 10 ⁰ also becomes one index showing a degree of crosslinking of the intermediate layer.

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

  A multilayer intermediate film 1 shown in FIG. 1 includes a first intermediate film 2, a second intermediate film 3 laminated on a first surface 2a (one surface) of the first intermediate film 2, a first intermediate film 2 And a third intermediate film 4 laminated on the second surface 2b (the other surface) of the intermediate film 2. The multilayer interlayer film 1 is used to obtain a laminated glass. The multilayer interlayer film 1 is a multilayer interlayer film for laminated glass. The first to third intermediate films 2 to 4 are intermediate films for laminated glass.

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

Each of the first to third intermediate films 2 to 4 contains a polyvinyl acetal resin and a plasticizer. The maximum value of tanδ of the first 200 ° C. and the angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} of the intermediate layer 2 is 1.00 or less.

The compositions of the second and third intermediate films 3 and 4 are preferably different from the composition of the first intermediate film 2. Second, the maximum value of tanδ at 200 ° C. and the angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} of the third intermediate layer 3 and 4 may be 1.00 or less.

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

  The interlayer film for laminated glass 21 shown in FIG. 2 is a single-layer interlayer film. The intermediate film 21 is used to obtain a laminated glass. The intermediate film 21 is an intermediate film for laminated glass.

The intermediate film 21 contains a polyvinyl acetal resin and a plasticizer. The maximum value of tanδ at 200 ° C. and the angular frequency omega of the intermediate layer 21 is ^{10 -2} ≦ ω ≦ ^{10 0} is 1.00 or less.

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

Further, in the case of the multilayer intermediate film 1, the laminated glass tends to be foamed more easily than in the case of the single-layer intermediate film 21. In particular, the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first intermediate film 2 is more than the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the second and third intermediate films 3 and 4. If the amount is too large, foaming tends to occur more easily. Furthermore, once foaming occurs, the generated foam becomes a nucleus and the foam tends to grow. However, in the multilayer intermediate film 1 according to the present embodiment, since the maximum value of tanδ at 200 ° C. and the angular frequency omega of the first intermediate layer 2 is ^{10 -2} ≦ ω ≦ ^{10 0} is 1.00 or less, It can suppress that foaming arises in a laminated glass, and also can suppress that foaming grows.

The combined increase even more the sound insulation of the glass, and the occurrence and growth of the foam of the foam from more suppressing, 200 ° C. and the angular frequency omega of the intermediate layer 2, 21 is at 10 ^-2 ≦ ω ≦ 10 ⁰ The maximum value of tan δ is preferably 0.95 or less. When the tan δ is 0.95 or less, the sound insulating property of the laminated glass can be further improved, and the generation of foam and the growth of foam can be further suppressed. The lower limit of the maximum value of tanδ at 200 ° C. and the angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} intermediate layer 2, 21 is not particularly limited.

In view of facilitating the extrusion of the intermediate layer 2, 21, the maximum value of tanδ at 200 ° C. and the angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} intermediate layer 2, 21 is preferably 0 .10 or more and 1.00 or less, more preferably 0.50 or more, further preferably 0.55 or more, particularly preferably 0.58 or more, preferably 0.95 or less, more preferably 0.94 or less.

For example, the maximum value of tanδ at 200 ° C. and the angular frequency omega of the intermediate layer 2 is ^{10 -2} ≦ ω ≦ ^{10 0} can be determined as follows. The intermediate film is stored in a constant temperature and humidity chamber (humidity 30% (± 3%), temperature 23 ° C.) for 1 month, and immediately after storing for 1 month, the surface layer (second intermediate film) and the intermediate layer ( The intermediate layer (first intermediate film) is taken out by peeling off the first intermediate film) and the surface layer (third intermediate film). 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 intermediate layer press-molded is placed in a hand press set at 20 ° C. in advance, and cooled by pressing at 10 MPa for 10 minutes. A circular sample having a diameter of 8 mm is cut from the center of the obtained film, and the PET films on both sides of the sample are removed, followed by vacuum drying in an oven at 50 ° C. for 2 hours. Next, immediately after the completion of the vacuum drying, the maximum value of tan δ at 200 ° C. and the angular frequency ω in the intermediate film 2 is 10 ⁻² ≦ ω ≦ 100 ⁰ using the ARES-G2 manufactured by TAINSTRUMENTS under the following conditions. Can do.

It is preferable that the intermediate layer 2 at 200 ° C. and the angular frequency omega is the measurement of the maximum value of tanδ at 10 ^-2 ≦ ω ≦ 10 ⁰ using the jig of the parallel plates having a diameter of 8 mm. Measurement temperature is 200 ° C., strain is 8.0%, angular frequency at which measurement is performed (10 ² , 6.31 × 10 ¹ , 3.98 × 10 ¹ , 2.51 × 10 ¹ , 1.58 × 10 ¹ , 10 ¹ , 6.31 × 10 ⁰ , 3.98 × 10 ⁰ , 2.51 × 10 ⁰ , 1.58 × 10 ⁰ , 10 ⁰ , 6.31 × 10 ⁻¹ , 3.98 × 10 ⁻¹ , 2.51 × 10 ⁻¹ , 1.58 × 10 ⁻¹ , 10 ⁻¹ , 6.31 × 10 ⁻² , 3.98 × 10 ⁻² , 2.51 × 10 ⁻² , 1.58 × 10 ^{− 2} and 10 ⁻² ), the measurement is started from the high angular frequency side. Correlation delay time and Correlation delay cycle, which are setting values related to acquisition of measurement data, are 1.0 s and 0.5, respectively, and Sampling cycles are 2 half cycles. In order to prevent the measurement sample from being deteriorated, the measurement is preferably performed in a nitrogen atmosphere.

  From the viewpoint of further improving the penetration resistance of the laminated glass, the thickness of the multilayer intermediate film 1 and the single-layer intermediate film 21 is preferably 0.05 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably Is 1.5 mm or less. When the thickness of the multilayer intermediate film 1 and the single-layer intermediate film 21 is not less than the above lower limit and not more than the above upper limit, the penetration resistance and transparency of the laminated glass are further enhanced.

(Polyvinyl acetal resin)
The first to third interlayer films for laminated glass in the interlayer film for laminated glass according to the present invention and the multilayer interlayer film for laminated glass according to the present invention each contain a polyvinyl acetal resin and a plasticizer, whereby laminated glass The adhesive force of the interlayer film or multilayer interlayer film to the constituent member can be further increased.

Furthermore, when the resin contained in the interlayer film or the multilayer interlayer film is a polyvinyl acetal resin, the interlayer film or multilayer interlayer film is used compared to the case of a thermoplastic resin other than the polyvinyl acetal resin. Foaming tends to occur particularly in laminated glass. However, tan [delta at 200 ° C. and the angular frequency omega is 10 ^-2 ≦ ω ≦ 10 ⁰ of the first laminated glass intermediate film in laminated glass multilayer intermediate film according to the combined intermediate layer and the present invention for glass according to the present invention Since the maximum value of is 1.00 or less, the occurrence of foaming and the growth of foaming in the laminated glass using the interlayer film for laminated glass can be sufficiently suppressed.

  The said polyvinyl acetal resin contained in the intermediate films 2-4, 21 can be manufactured by acetalizing polyvinyl alcohol with an aldehyde, for example. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is generally in the range of 70 to 99.9 mol%, preferably in the range of 75 to 99.8 mol%, and in the range of 80 to 99.8 mol%. More preferably.

  The polymerization degree of polyvinyl alcohol for obtaining the polyvinyl acetal resin contained in the intermediate films 2 to 4 and 21 is preferably 200 or more, more preferably 500 or more, still more preferably more than 1700, and particularly preferably 2000 or more. More preferably, it is 3000 or less, More preferably, it is less than 3000, Most preferably, it is 2800 or less. The polyvinyl acetal resin contained in the intermediate films 2 to 4 and 21 is preferably a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a degree of polymerization of not less than the above lower limit and not more than the above upper limit. When the polymerization degree is equal to or higher than the lower limit, the penetration resistance of the laminated glass is further enhanced. When the polymerization degree is not more than the above upper limit, the intermediate film can be easily molded.

  From the viewpoint of further improving the sound insulation of the laminated glass and further suppressing the occurrence of foaming and the growth of foaming, the degree of polymerization of polyvinyl alcohol to obtain the polyvinyl acetal resin contained in the intermediate films 2 and 21 Is preferably greater than 1700, preferably greater than 2000, preferably less than 3000. Moreover, it is preferable that the said polyvinyl acetal resin in the intermediate films 2 and 21 is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol whose polymerization degree is more than the said minimum and below the said upper limit.

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

  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 contained in the interlayer film for laminated glass according to the present invention is preferably a polyvinyl butyral resin. The multilayer interlayer film for laminated glass according to the present invention preferably contains a polyvinyl butyral resin as the polyvinyl acetal resin contained in the first to third interlayer films for laminated glass. Synthesis of polyvinyl butyral resin is easy. Furthermore, the use of the polyvinyl butyral resin allows the interlayer film or multilayer interlayer film to be more appropriately developed with respect to the laminated glass component. Furthermore, the light resistance and weather resistance of the intermediate film or multilayer intermediate film are further enhanced.

  It is preferable that the content rate (hydroxyl amount) of the hydroxyl group of the polyvinyl acetal resin contained in the intermediate films 2 and 21 is 31 mol% or less. In this case, the sound insulation of the laminated glass is 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, As a result, the sound insulation of a laminated glass becomes still higher.

  The hydroxyl group content of the polyvinyl acetal resin contained in the intermediate films 2 and 21 is preferably 13 mol% or more, more preferably 18 mol% or more, still more preferably 20 mol% or more, and particularly preferably 21.5 mol. % Or more, more preferably 30 mol% or less, still more preferably 28 mol% or less, particularly preferably 26 mol% or less. When the hydroxyl group content is equal to or higher than the lower limit, the adhesive force of the intermediate films 2 and 21 is further increased. When the content of the hydroxyl group is not more than the above upper limit, the sound insulating property of the laminated glass is further enhanced. Furthermore, the flexibility of the multilayer intermediate film 1 and the intermediate film 21 is increased, and the handling properties of the multilayer intermediate film 1 and the intermediate film 21 are further improved.

  The hydroxyl group content of the polyvinyl acetal resin contained in the intermediate films 3 and 4 is preferably 26 mol% or more, more preferably 27 mol% or more, still more preferably 28 mol% or more, preferably 35 mol% or less. Preferably it is 33 mol% or less, More preferably, it is 32 mol% or less, Most preferably, it is 31.5 mol% or less. When the hydroxyl group content is equal to or higher than the lower limit, the adhesive strength of the intermediate films 3 and 4 is further increased. When the content of the hydroxyl group is not more than the above upper limit, the flexibility of the multilayer intermediate film 1 is increased, and the handleability of the multilayer intermediate film 1 is further improved.

  From the viewpoint of further improving the sound insulating properties of the laminated glass, the hydroxyl group content of the polyvinyl acetal resin contained in the intermediate film 2 is the respective hydroxyl group content of the polyvinyl acetal resin contained in the intermediate films 3 and 4. Is preferably lower. From the viewpoint of further improving the sound insulating properties of the laminated glass, the hydroxyl group content of the polyvinyl acetal resin contained in the intermediate film 2 is the respective hydroxyl group content of the polyvinyl acetal resin contained in the intermediate films 3 and 4. 1 mol% or less is preferable, 3 mol% or more is more preferable, 5 mol% or more is further preferable, and 7 mol% or less is particularly preferable.

  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 in accordance with JIS K6726 “Testing method for polyvinyl alcohol”. .

  The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin contained in the intermediate films 2 and 21 is preferably 0.1 mol% or more, more preferably 0.4 mol% or more, and still more preferably 0.8 mol%. % Or more, preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 20 mol% or less, and particularly preferably 15 mol% or less. The degree of acetylation of the polyvinyl acetal resin contained in the intermediate films 3 and 4 is preferably 0.1 mol% or more, more preferably 0.4 mol% or more, preferably 20 mol% or less, more preferably 5 mol%. Hereinafter, it is more preferably 2 mol% or less, particularly preferably 1.5 mol% or less. When the degree of acetylation is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further increased, and the glass transition temperatures of the multilayer intermediate film 1 and the intermediate film 21 are sufficiently lowered. When the degree of acetylation is less than or equal to the above upper limit, the moisture resistance of the multilayer intermediate film 1 and the intermediate film 21 is further increased.

  From the viewpoint of further improving the sound insulation of the laminated glass, the acetylation degree of the polyvinyl acetal resin contained in the intermediate film 2 is higher than the acetylation degree of the polyvinyl acetal resin contained in the intermediate films 3 and 4. It is preferable. From the viewpoint of further improving the sound insulation of the laminated glass, the degree of acetylation of the polyvinyl acetal resin contained in the intermediate film 2 is less than the degree of acetylation of the polyvinyl acetal resin contained in the intermediate films 3 and 4. It is preferably higher than 1 mol%, more preferably higher than 0.5 mol%, further preferably higher than 1 mol%, particularly preferably higher than 5 mol%, most preferably higher than 10 mol%. .

  Further, from the viewpoint of further improving the sound insulation of the laminated glass, the degree of acetalization of the polyvinyl acetal resin contained in the intermediate film 2 is greater than the degree of acetalization of the polyvinyl acetal resin contained in the intermediate films 3 and 4. Is preferably high.

  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 degree of acetalization of the polyvinyl acetal resin contained in the intermediate films 2 and 21 is preferably 50 mol% or more, more preferably 53 mol% or more, still more preferably 60 mol% or more, particularly preferably 63 mol% or more, preferably Is 85 mol% or less, more preferably 83 mol%, still more preferably 80 mol% or less, and particularly preferably 78 mol% or less. The degree of acetalization of the polyvinyl acetal resin contained in the intermediate films 3 and 4 is preferably 55 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, particularly preferably 67 mol% or more, preferably Is 80 mol% or less, more preferably 78 mol% or less, still more preferably 76 mol% or less. When the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further increased, and the glass transition temperatures of the multilayer intermediate film 1 and the intermediate film 21 are sufficiently lowered. The reaction time required in order to manufacture polyvinyl acetal resin as the said acetalization degree is below the said upper limit can be shortened.

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

  The degree of acetalization was determined by measuring the degree of acetylation (acetyl group content) and the hydroxyl group content (vinyl alcohol content) according to JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated by calculating the fraction and then subtracting the degree of acetylation and the hydroxyl content from 100 mol%.

  When the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the degree of acetylation are measured by a method based on JIS K6728 “Testing methods for polyvinyl butyral” or ASTM D1396-92. Can be calculated from the results. Measurement by a method according to ASTM D1396-92 is preferred.

  Since the sound insulating properties of the intermediate films 2 and 21 are further increased, the polyvinyl acetal resin contained in the intermediate films 2 and 21 has an acetylation degree a of 8 mol% or less and an acetalization degree a of The polyvinyl acetal resin A which is 70 mol% or more, or the polyvinyl acetal resin B whose acetylation degree b exceeds 8 mol% is preferable. The polyvinyl acetal resin may be a polyvinyl acetal resin A having an acetylation degree a of 8 mol% or less and an acetalization degree a of 70 mol% or more, and the acetylation degree b exceeds 8 mol%. Polyvinyl acetal resin B may be used.

  The degree of acetylation a of the polyvinyl acetal resin A is 8 mol% or less, preferably 7.5 mol% or less, more preferably 7 mol% or less, still more preferably 6.5 mol% or less, and particularly preferably 5 mol% or less. Preferably, it is 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 0.8 mol% or more, and particularly preferably 1 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 migration of the plasticizer can be easily controlled, and the sound insulation of the laminated glass can be further enhanced.

  The degree of acetalization a of the polyvinyl acetal resin A is 70 mol% or more, preferably 70.5 mol% or more, more preferably 71 mol% or more, still more preferably 71.5 mol% or more, and particularly preferably 72 mol% or more. , Preferably 85 mol% or less, more preferably 83 mol% or less, still more preferably 81 mol% or less, particularly preferably 79 mol% or less. When the acetalization degree a is not less than the above lower limit, the sound insulation of the laminated glass is 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 18 mol% or more, more preferably 19 mol% or more, still more preferably 20 mol% or more, particularly preferably 21 mol% or more, preferably 31 mol% or less. More preferably, it is 30 mol% or less, More preferably, it is 29 mol% or less, Most preferably, it is 28 mol% or less. When the hydroxyl group content a is equal to or higher than the lower limit, the adhesive strength of the interlayer film is further increased. When the hydroxyl group content a is not more than the above upper limit, the sound insulation of the laminated glass is further enhanced.

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

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

  The acetalization degree b of the polyvinyl acetal resin B is preferably 50 mol% or more, more preferably 53 mol% or more, still more preferably 55 mol% or more, particularly preferably 60 mol% or more, preferably 80 mol% or less, more Preferably it is 78 mol% or less, More preferably, it is 76 mol% or less, Most preferably, it is 74 mol% or less. When the acetalization degree b is not less than the above lower limit, the sound insulating property of the laminated glass is 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 18 mol% or more, more preferably 19 mol% or more, still more preferably 20 mol% or more, particularly preferably 21 mol% or more, preferably 31 mol% or less. More preferably, it is 30 mol% or less, More preferably, it is 29 mol% or less, Most preferably, it is 28 mol% or less. When the hydroxyl group content b is equal to or higher than the lower limit, the adhesive strength of the interlayer film is further increased. When the hydroxyl group content b is not more than the above upper limit, the sound insulation of the laminated glass is further enhanced.

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

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

  The polyvinyl acetal resin A and the polyvinyl acetal resin B are preferably polyvinyl acetal resins obtained by acetalizing polyvinyl alcohol X having a polymerization degree of 1600 to 3000 with an aldehyde. Since the occurrence of foaming and the growth of foaming in the laminated glass using the interlayer film for laminated glass can be sufficiently suppressed, the degree of polymerization of the polyvinyl alcohol X is preferably 1700 or more, more preferably more than 1700, still more preferably. 1800 or more, still more preferably 2000 or more, particularly preferably 2100 or more, most preferably 2200 or more, preferably 2900 or less, more preferably 2800 or less.

(Plasticizer)
The said plasticizer contained in the 1st-3rd intermediate film for laminated glasses in the intermediate film for laminated glasses which concerns on this invention, and the multilayer intermediate film for laminated glasses which concerns on this invention is not specifically limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

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

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

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

  The organic ester plasticizer is not particularly limited, but is triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, tri-BR> G tylene 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-ethylbutyrate, 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 dicapryate, 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 preferably includes a diester plasticizer represented by the following formula (1). By using this diester plasticizer, the sound insulation of the laminated glass is further enhanced.

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

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

  The content of the plasticizer is not particularly limited. Regarding the interlayer film for laminated glass according to the present invention and the first interlayer film for laminated glass in the multilayer interlayer film for laminated glass according to the present invention, the content of the plasticizer is 100 parts by weight of the polyvinyl acetal resin. Preferably 40 parts by weight or more, more preferably 50 parts by weight or more, still more preferably 55 parts by weight or more, particularly preferably 60 parts by weight or more, preferably 80 parts by weight or less, more preferably 78 parts by weight or less, still more preferably 75 parts by weight. The amount is not more than parts by weight, particularly preferably not more than 72 parts by weight. When the content of the plasticizer is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the content of the plasticizer is not more than the above upper limit, the transparency of the interlayer film and the multilayer interlayer film is further enhanced.

  Regarding the second and third interlayer films for laminated glass in the multilayer interlayer film for laminated glass according to the present invention, the content of the plasticizer is preferably 25 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin. More preferably, it is 30 parts by weight or more, more preferably 35 parts by weight or more, preferably 50 parts by weight or less, more preferably 45 parts by weight or less, still more preferably 43 parts by weight or less, and particularly preferably 38 parts by weight or less. When the content of the plasticizer is not less than the above lower limit, the adhesive strength of the multilayer interlayer film is increased, and the penetration resistance of the laminated glass is further increased. When the content of the plasticizer is not more than the above upper limit, the transparency of the multilayer interlayer film is further enhanced.

  From the viewpoint of further improving the sound insulation of the laminated glass, the content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin of the first interlayer film for laminated glass is the polyvinyl acetal of the second and third interlayer films for laminated glass. It is preferable that the content of the plasticizer is more than 100 parts by weight of the resin. From the viewpoint of further enhancing the sound insulation of the laminated glass, the content of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin of the first interlayer film for laminated glass is the polyvinyl acetal of the second and third interlayer films for laminated glass. It is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and more preferably 20 parts by weight or more than the content of the plasticizer relative to 100 parts by weight of the resin. preferable.

(Other ingredients)
The interlayer film for laminated glass according to the present invention and the first to third interlayer films for laminated glass in the multilayered interlayer film for laminated glass according to the present invention are respectively an ultraviolet absorber, an antioxidant, and a light stabilizer, as necessary. It may contain additives such as an agent, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion modifier, a moisture-resistant agent, a fluorescent brightening agent, and an infrared absorber.

(Laminated glass)
Each of the interlayer film for laminated glass and the multilayer interlayer film for laminated glass according to the present invention is used to obtain a laminated glass.

  FIG. 3 is a cross-sectional view schematically showing an example of a laminated glass using the multilayer interlayer film 1 shown in FIG.

  A laminated glass 11 shown in FIG. 3 includes a first laminated glass constituting member 12, a second laminated glass constituting member 13, and the multilayer intermediate film 1. The multilayer intermediate film 1 is sandwiched between the first and second laminated glass constituent members 12 and 13.

  The first laminated glass constituting member 12 is laminated on the outer surface 3 a of the second intermediate film 3. The second laminated glass constituting member 13 is laminated on the outer surface 4 a of the third intermediate film 4. Therefore, the laminated glass 11 includes the first laminated glass constituting member 12, the second intermediate film 3, the first intermediate film 2, the third intermediate film 4, and the second laminated glass constituting member 13. Are stacked in this order.

  Examples of the first and second laminated glass constituent members include glass plates and PET (polyethylene terephthalate) films. In laminated glass, not only laminated glass with an interlayer film or multilayer interlayer film sandwiched between two glass plates, but also an interlayer film or multilayer interlayer film sandwiched between a glass plate and a PET film, etc. Glass is also included. Laminated glass is a laminated body provided with a glass plate, and preferably at least one glass plate is used.

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

  The thickness of the 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 a laminated glass structural member is a glass plate, the thickness of this glass plate becomes like this. Preferably it is 1 mm or more, Preferably it is 3 mm or less. When the laminated glass component is a PET film, the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.

  The manufacturing method of the said laminated glass is not specifically limited. For example, the intermediate film or the multilayer 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, so that the first and second The air remaining between the laminated glass constituent member and the intermediate film or multilayer intermediate film is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained.

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

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

  The butyralization degree (acetalization degree), the acetylation degree, and the hydroxyl group content of the polyvinyl butyral resins used in Examples and Comparative Examples were measured by a method based on ASTM D1396-92. In addition, also when measured by JIS K6728 “Testing method for polyvinyl butyral”, the same numerical values as the method based on ASTM D1396-92 were shown.

Example 1
(1) Synthesis of polyvinyl butyral resin used in the intermediate layer In a reactor equipped with a stirrer, 2860 ml of ion-exchanged water, 300 g of polyvinyl alcohol having a polymerization degree of 2310 and a saponification degree of 87.1 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 0.6% by weight of 35% by weight hydrochloric acid as a catalyst was added to this solution, and the temperature of the solution was adjusted to 15 ° C. Then, 15.8 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 190 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.9% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 44 ° C., and the mixture was aged at 44 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried, and the polyvinyl butyral resin used for the intermediate | middle layer of Example 1 was obtained.

(2) Preparation of multilayer interlayer film Polyvinyl butyral resin (using n-butyraldehyde, using polyvinyl alcohol having an average polymerization degree of 2310, butyralization degree 64.2 mol%, acetylation degree 12.9 mol%, hydroxyl group Content of 22.9 mol%) 100 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer was added, and kneaded thoroughly with a mixing roll for intermediate layer use. A resin composition was obtained. Furthermore, 100 parts by weight of polyvinyl butyral resin (using n-butyraldehyde, butyralization degree 68.8 mol%, acetylation degree 0.8 mol%, hydroxyl group content 30.4 mol%) is a plasticizer. 37.5 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) was added and sufficiently kneaded with a mixing roll to obtain a resin composition for a surface layer.

  By co-extrusion using the obtained resin composition for intermediate layer and resin composition for surface layer, the surface layer (second intermediate film, thickness 350 μm) and the intermediate layer (first intermediate film, thickness 100 μm) ) And a surface layer (third intermediate film, thickness 350 μm) were sequentially laminated.

(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 The obtained multilayer interlayer film was 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. 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 5 mm) was used.

(5) Production of laminated glass used for foaming test The obtained multilayer interlayer film was cut into a size of 30 cm in length and 15 cm in width and stored in an environment at a temperature of 23 ° C. for 10 hours. In addition, embossing was formed on both surfaces of the obtained multilayer intermediate film, and the ten-point average roughness of the embossing was 30 μm. In the cut multilayer intermediate film, an intersection 4 between a position 8 cm inward in the vertical direction from the end of the multilayer intermediate film and a position 5 cm inward in the lateral direction from the end of the multilayer intermediate film. A through-hole with a diameter of 6 mm was produced at the location.

  A multilayer intermediate film having a through hole was sandwiched between two transparent float glasses (length 30 cm × width 15 cm × thickness 2.5 mm) to obtain a laminate. The outer peripheral edge of the laminate was sealed with a sealing agent having a width of 2 cm from the end portion 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.

(Example 2)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 3090 ml of ion-exchanged water, 300 g of polyvinyl alcohol having a polymerization degree of 2320 and a saponification degree of 98.8 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution in an amount of 0.5 wt% relative to the total system, the temperature of the solution was adjusted to 15 ° C., and 12.7 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 182 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.8% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 44 ° C., and the mixture was aged at 44 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of Example 2 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

(Example 3)
(1) Synthesis of polyvinyl butyral resin used in the intermediate layer In a reactor equipped with a stirrer, 2550 ml of ion-exchanged water, 250 g of polyvinyl alcohol having a polymerization degree of 2400 and a saponification degree of 94.4 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 0.6% by weight of 35% by weight hydrochloric acid as a catalyst was added to this solution, and the temperature of the solution was adjusted to 15 ° C. Then, 9.3 g of n-butyraldehyde was added as an aldehyde with stirring. Then, when 158g of n-butyraldehyde was added, white particulate resin precipitated. 15 minutes after the precipitation, 3.9% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 44 ° C., and the mixture was aged at 44 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried, and the polyvinyl butyral resin used for the intermediate | middle layer of Example 3 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

Example 4
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2370 ml of ion-exchanged water, 250 g of polyvinyl alcohol having a polymerization degree of 2450 and a saponification degree of 87.7 were charged, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to the solution in an amount of 0.6 wt% relative to the total system, the temperature of the solution was adjusted to 15 ° C., and 11.8 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 153 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.7% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 42 ° C., and the mixture was aged at 42 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of Example 4 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

(Example 5)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2940 ml of ion-exchanged water, 300 g of polyvinyl alcohol having a polymerization degree of 2500 and a saponification degree of 87.0 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 0.6% by weight of 35% by weight hydrochloric acid as a catalyst was added to this solution to adjust the temperature of the solution to 15 ° C., and then 14.1 g of n-butyraldehyde was added as an aldehyde with stirring. Then, when 198g of n-butyraldehyde was added, white particulate resin precipitated. 15 minutes after the precipitation, 4.0% by weight of 35% by weight hydrochloric acid was added to the entire system, the temperature was raised to 40 ° C., and the mixture was aged at 40 ° C. for 2.5 hours. Then, it cooled, neutralized, washed with water, and dried, and the polyvinyl butyral resin used for the intermediate | middle layer of Example 5 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

(Example 6)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2190 ml of ion-exchanged water, 250 g of polyvinyl alcohol having a polymerization degree of 2500 and a saponification degree of 98.9 were charged, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution in an amount of 0.6 wt% relative to the total system, the temperature of the solution was adjusted to 15 ° C., and then 10.6 g of n-butyraldehyde was added as an aldehyde with stirring. Then, when 158g of n-butyraldehyde was added, white particulate resin precipitated. 15 minutes after the precipitation, 3.8% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 42 ° C., and the mixture was aged at 42 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of Example 6 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

(Example 7)
(1) Synthesis of polyvinyl butyral resin used in the intermediate layer In a reactor equipped with a stirrer, 250 g of polyvinyl alcohol having 2560 ml of ion-exchanged water, a polymerization degree of 2550, and a saponification degree of 92.5 was added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to the solution in an amount of 0.6 wt% relative to the total system, the temperature of the solution was adjusted to 15 ° C., and 11.1 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 164 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.8% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 42 ° C., and the mixture was aged at 42 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried, and the polyvinyl butyral resin used for the intermediate | middle layer of Example 7 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

(Example 8)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2830 ml of ion-exchanged water, 300 g of polyvinyl alcohol having a polymerization degree of 2550 and a saponification degree of 87.6 were charged, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 0.6% by weight of 35% by weight hydrochloric acid as a catalyst was added to this solution to adjust the temperature of the solution to 15 ° C., and then 14.1 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 184 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.9% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 40 ° C., and the mixture was aged at 40 ° C. for 2.5 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of Example 8 was obtained.

  A multilayer interlayer film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and plasticizer used for the interlayer and protective layer were set as shown in Table 1 below. .

(Comparative Example 1)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2820 ml of ion-exchanged water, 300 g of polyvinyl alcohol having a polymerization degree of 2320 and a saponification degree of 98.9 were charged, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 0.6% by weight of 35% by weight hydrochloric acid as a catalyst was added to this solution, and the temperature of the solution was adjusted to 15 ° C. Then, 12.7 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 190 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.9% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 54 ° C., and the mixture was aged at 54 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of the comparative example 1 was obtained.

  A multilayer intermediate film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and the plasticizer used for the intermediate layer and the protective layer were set as shown in Table 2 below. .

(Comparative Example 2)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2180 ml of ion-exchanged water, 250 g of polyvinyl alcohol having a polymerization degree of 2100 and a saponification degree of 93.1 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution in an amount of 0.6 wt% relative to the total system, the temperature of the solution was adjusted to 15 ° C., and 11.2 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 165 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.8% by weight of 35% by weight hydrochloric acid was added to the entire system, the temperature was raised to 54 ° C., and the mixture was aged at 54 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried, and the polyvinyl butyral resin used for the intermediate | middle layer of the comparative example 2 was obtained.

  A multilayer intermediate film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and the plasticizer used for the intermediate layer and the protective layer were set as shown in Table 2 below. .

(Comparative Example 3)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2030 ml of ion-exchanged water, 250 g of polyvinyl alcohol having a polymerization degree of 1780 and a saponification degree of 98.8 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 35 wt% hydrochloric acid as a catalyst was added to this solution in an amount of 0.6 wt% relative to the total system, the temperature of the solution was adjusted to 15 ° C., and then 10.6 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 155 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 3.9% by weight of 35% by weight hydrochloric acid was added to the whole system, the temperature was raised to 55 ° C., and the mixture was aged at 55 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of the comparative example 3 was obtained.

  A multilayer intermediate film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and the plasticizer used for the intermediate layer and the protective layer were set as shown in Table 2 below. .

(Comparative Example 4)
(1) Synthesis of polyvinyl butyral resin used for the intermediate layer In a reactor equipped with a stirrer, 2430 ml of ion-exchanged water, 300 g of polyvinyl alcohol having a polymerization degree of 1700 and a saponification degree of 87.0 were added, and the polyvinyl alcohol was heated while stirring. Dissolved to obtain a solution. Next, 0.6% by weight of 35% by weight hydrochloric acid as a catalyst was added to this solution to adjust the temperature of the solution to 15 ° C., and then 14.1 g of n-butyraldehyde was added as an aldehyde with stirring. Thereafter, when 180 g of n-butyraldehyde was added, a white particulate resin was precipitated. 15 minutes after the precipitation, 4.0% by weight of 35% by weight hydrochloric acid was added to the entire system, the temperature was raised to 56 ° C., and the mixture was aged at 56 ° C. for 3 hours. Then, it cooled, neutralized, washed with water, and dried and the polyvinyl butyral resin used for the intermediate | middle layer of the comparative example 4 was obtained.

  A multilayer intermediate film and a laminated glass were produced in the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and the plasticizer used for the intermediate layer and the protective layer were set as shown in Table 2 below. .

(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 and 2 below, where “◯” indicates a case where the TL value is 35 dB or more and “X” indicates a case where the TL value is less than 35 dB.

(2) Foaming test (foaming condition)
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 being left, the presence or absence of foaming and the size of foaming were visually observed in plan view, and the state of foaming was judged according to the following criteria.

[Criteria for foaming condition in foaming test]
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) 200 ° C. and the angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} at the maximum value Examples and Comparative Examples of the multilayer intermediate film constant temperature and humidity chamber of tan [delta (humidity 30% (± 3%), the 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. A circular sample having a diameter of 8 mm was cut from the center of the obtained film, and the PET films on both sides of the sample were removed, followed by vacuum drying in an oven at 50 ° C. for 2 hours.

Under the following conditions using a ARES-G2 vacuum drying after the end immediately TAINSTRUMENTS Co., 200 ° C. and the angular frequency omega of the first intermediate layer has the maximum value of tanδ at ^{10 -2} ≦ ω ≦ ^{10 0} .

  For the measurement, a parallel plate type jig having a diameter of 8 mm was used. The measurement temperature is 200 ° C., the strain is 8.0%, the angular frequency at which the measurement is performed is as follows, and the measurement was started from the high angular frequency side. Correlation delay time and Correlation delay cycle, which are setting values related to the acquisition of measurement data, were set to 1.0 s and 0.5, respectively, and Sampling cycles were set to 2 half cycles. The measurement was performed under a nitrogen atmosphere.

Value the angular frequency omega from the tanδ obtained from measurements were read a value that is a maximum value in the range of 10 ^-2 ≦ ω ≦ 10 ^0. In addition, the measured angular frequency is 10 ² , 6.31 × 10 ¹ , 3.98 × 10 ¹ , 2.51 × 10 ¹ , 1.58 × 10 ¹ , 10 ¹ , 6.31 × 10 ^0. , 3.98 × 10 ⁰ , 2.51 × 10 ⁰ , 1.58 × 10 ⁰ , 10 ⁰ , 6.31 × 10 ⁻¹ , 3.98 × 10 ⁻¹ , 2.51 × 10 ⁻¹ , 1 It was .58 × 10 ⁻¹ , 10 ⁻¹ , 6.31 × 10 ⁻² , 3.98 × 10 ⁻² , 2.51 × 10 ⁻² , 1.58 × 10 ⁻² and 10 ⁻² .

  The results are shown in Tables 1-2 below. In Tables 1 and 2 below, “PVA” indicates polyvinyl alcohol and “3GO” indicates triethylene glycol di-2-ethylhexanoate.

DESCRIPTION OF SYMBOLS 1 ... Multilayer intermediate film 2 ... 1st intermediate film 2a ... 1st surface 2b ... 2nd surface 3 ... 2nd intermediate film 3a ... Outer surface 4 ... 3rd intermediate film 4a ... Outer surface 11 ... Laminated glass 12 ... first laminated glass constituent member 13 ... second laminated glass constituent member 21 ... intermediate film

Claims (12)

Containing a polyvinyl acetal resin and a plasticizer,
200 ° C. and a maximum value of tanδ at angular frequency omega is ^{10 -2} ≦ ω ≦ ^{10 0} is 1.00 or less, interlayer film for laminated glass.   The interlayer film for laminated glass according to claim 1, wherein the content of hydroxyl groups in the polyvinyl acetal resin is 31 mol% or less.   The interlayer film for laminated glass according to claim 2, wherein the content of hydroxyl groups in the polyvinyl acetal resin is 26 mol% or less.   The interlayer film for laminated glass according to any one of claims 1 to 3, wherein a content of the plasticizer is 40 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin. The intermediate film for laminated glass according to any one of claims 1 to 4 is provided as a first intermediate film for laminated glass,
A multilayer interlayer film for laminated glass, further comprising a second interlayer film for laminated glass which is laminated on the first surface of the first interlayer film for laminated glass and contains a polyvinyl acetal resin and a plasticizer.   Content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first interlayer film for laminated glass is that of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the second interlayer film for laminated glass. The multilayer interlayer film for laminated glass according to claim 5, wherein the multilayer interlayer film is more than the content.   A third laminated glass interlayer film laminated on a second surface opposite to the first surface of the first laminated glass interlayer film and further comprising a polyvinyl acetal resin and a plasticizer is further provided. The multilayer interlayer film for laminated glass according to claim 5 or 6.   Content of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the first interlayer film for laminated glass is that of the plasticizer with respect to 100 parts by weight of the polyvinyl acetal resin in the third interlayer film for laminated glass. The multilayer interlayer film for laminated glass according to claim 7, wherein the multilayer interlayer film is more than the content.   The degree of acetylation of the polyvinyl acetal resin in the first interlayer film for laminated glass is 8 mol% or less, and the degree of acetalization is 70 mol% or more. The multilayer interlayer film for laminated glass as described.   The multilayer interlayer film for laminated glass according to any one of claims 5 to 8, wherein the degree of acetylation of the polyvinyl acetal resin in the first interlayer film for laminated glass exceeds 8 mol%. First and second laminated glass components;
An intermediate film sandwiched between the first and second laminated glass constituent members,
The laminated glass in which the said intermediate film contains the intermediate film for laminated glasses of any one of Claims 1-4. First and second laminated glass components;
A multilayer interlayer film sandwiched between the first and second laminated glass constituent members,
Laminated glass, wherein the multilayer interlayer film is the multilayer interlayer film for laminated glass according to any one of claims 5 to 10.

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