JP6539313B2 - Intermediate film for laminated glass and laminated glass - Google Patents

Description

  The present invention relates to an interlayer for laminated glass used to obtain laminated glass. Moreover, this invention relates to the laminated glass using the said intermediate film for laminated glasses.

  Laminated glass is excellent in safety because the amount of scattered glass fragments is small even if it is broken due to external impact. For this reason, the laminated glass is widely used in automobiles, railway vehicles, aircraft, ships, buildings, and the like. The laminated glass is manufactured by sandwiching an intermediate film for laminated glass between two glass plates.

  The interlayer film for laminated glass includes a single layer interlayer film having a single layer structure and a multilayer interlayer film having a two or more layer structure.

  As an example of the interlayer film for laminated glass, Patent Document 1 below describes 100 parts by weight of polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and at least one of alkali metal salts and alkaline earth metal salts. A sound insulation layer is disclosed comprising 0.001 to 1.0 parts by weight of a metal salt of the formula (I) and more than 30 parts by weight of a plasticizer. This sound insulation layer can be used as an intermediate film in a single layer.

  Further, Patent Document 1 below also describes a multilayer intermediate film in which the above-mentioned sound insulation layer and other layers are laminated. Another layer laminated on the sound insulation layer is 100 parts by weight of polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and at least one metal salt of at least one of alkali metal salts and alkaline earth metal salts. It contains 1.0 part by weight and 30 parts by weight or less of a plasticizer.

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

JP 2007-070200 A US2013 / 02367711A1

  In the laminated glass using the conventional intermediate film as described in patent document 1, 2, bending rigidity may be low. For this reason, when it is used for a side door of an automobile, for example, there is no frame for fixing the laminated glass, and the bending due to the low rigidity of the laminated glass sometimes causes problems in opening and closing the glass.

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

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

  An object of the present invention is to provide an intermediate film for laminated glass which can increase the bending rigidity of the laminated glass. Another object of the present invention is to provide a laminated glass using the above interlayer film for laminated glass.

  According to a broad aspect of the present invention, an intermediate film for laminated glass having a structure of one layer or a structure of two or more layers, which comprises a polyvinyl acetal resin and a plasticizer as a surface layer in the intermediate film An interlayer for laminated glass is provided, which comprises a layer, and the polyvinyl acetal resin contained in the first layer is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the content rate of hydroxyl groups of the polyvinyl acetal resin contained in the first layer is 30 mol% or less.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the content of the plasticizer contained in the first layer is 100 parts by weight of the polyvinyl acetal resin contained in the first layer. 20 parts by weight or more, and in another specific aspect, the content of the plasticizer contained in the first layer is 40 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin contained in the first layer Part or less.

  In a specific aspect of the interlayer for laminated glass according to the present invention, the interlayer has a structure of two or more layers, and further comprises a second layer containing a polyvinyl acetal resin and a plasticizer, The first layer is disposed on the first surface side of the two layers.

  In a specific aspect of the interlayer for laminated glass according to the present invention, the interlayer has a structure of three or more layers, and a third layer containing a polyvinyl acetal resin and a plasticizer as a surface layer in the interlayer. The polyvinyl acetal further comprising a layer, wherein the third layer is disposed on a second surface side opposite to the first surface side of the second layer, the third layer being included in the third layer The resin is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film has a single layer structure, and includes only the first layer.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film is formed of a first glass plate and a second glass plate, using a first glass plate having a thickness of 1 mm or less. It is placed between and used to obtain laminated glass.

  In a specific aspect of the intermediate film for laminated glass according to the present invention, the intermediate film includes the first glass plate having a thickness of 1 mm or less and the second glass plate having a thickness of 1 mm or less. It is disposed between a first glass plate and the second glass plate and is used to obtain laminated glass.

  According to a broad aspect of the present invention, a first glass plate, a second glass plate, and the intermediate film for laminated glass described above are provided, and between the first glass plate and the second glass plate A laminated glass is provided, wherein the intermediate film for laminated glass is disposed.

  In a specific aspect of the laminated glass according to the present invention, the thickness of the first glass plate is 1 mm or less.

  In a specific aspect of the laminated glass according to the present invention, the thickness of the second glass plate is 1 mm or less.

  The interlayer for laminated glass according to the present invention has a structure of one layer or a structure of two or more layers, and as a surface layer in the interlayer, a first layer containing a polyvinyl acetal resin and a plasticizer, Since the polyvinyl acetal resin contained in the first layer is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms, the bending rigidity of the laminated glass using the intermediate film can be enhanced.

FIG. 1 is a cross-sectional view schematically showing an interlayer for laminated glass according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an intermediate film for laminated glass according to a second embodiment of the present invention. FIG. 3: is sectional drawing which shows typically an example of the laminated glass using the intermediate film for laminated glasses shown in FIG. FIG. 4: is sectional drawing which shows typically an example of the laminated glass using the intermediate film for laminated glasses shown in FIG. FIG. 5 is a schematic view for explaining a method of measuring bending stiffness.

  Hereinafter, the present invention will be described in detail.

  The interlayer for laminated glass according to the present invention (sometimes abbreviated as "interlayer" in the present specification) has a structure of one layer or a structure of two or more layers. The intermediate film according to the present invention may have a single layer structure or may have a two or more layer structure. The interlayer film concerning this invention is equipped with the 1st layer containing polyvinyl acetal resin and a plasticizer as a surface layer in an interlayer film. The intermediate film according to the present invention may be a single-layer intermediate film comprising only the first layer, or may be a multilayer intermediate film comprising the first layer and other layers.

  In the interlayer film according to the present invention, the polyvinyl acetal resin contained in the first layer is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms. The carbon number of the acetal group in the polyvinyl acetal resin contained in the first layer is 3 or less.

  The intermediate film according to the present invention is provided with the above-described configuration, so that the bending rigidity of the laminated glass using the intermediate film can be enhanced. Also, in order to obtain laminated glass, the intermediate film is disposed between the first glass plate and the second glass plate. Even if the thickness of the first glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by the use of the interlayer film according to the present invention. Moreover, even if the thickness of both the first glass plate and the second glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by the use of the intermediate film according to the present invention.

  The present inventors are a surface layer, when the above-mentioned polyvinyl acetal resin contained in the above-mentioned 1st layer which is a surface layer is obtained by acetalizing polyvinyl alcohol with the aldehyde whose carbon number is 3 or less. Compared with the case where the said polyvinyl acetal resin contained in the said 1st layer is obtained by acetalizing polyvinyl alcohol with the aldehyde which has carbon number 3, the bending rigidity of the laminated glass using an intermediate film is improved. I found out what I could do.

  The intermediate film may have a structure of two or more layers, and may have a second layer in addition to the first layer. The interlayer film preferably further includes a second layer containing a polyvinyl acetal resin and a plasticizer. When the intermediate film includes the second layer, the first layer is disposed on the first surface side of the second layer.

  The intermediate film may have a structure of three or more layers, and may include a third layer in addition to the first layer and the second layer. The interlayer film preferably further includes a third layer containing a polyvinyl acetal resin and a plasticizer. When the intermediate film includes the second layer and the third layer, the third layer is disposed on the second surface side opposite to the first surface side of the second layer. Be done.

  From the viewpoint of further increasing the bending rigidity of the laminated glass, the intermediate film includes the first layer as a surface layer in the intermediate film. The intermediate film may include the second layer as a surface layer of the intermediate film. When the second layer is a surface layer, the polyvinyl acetal resin contained in the second layer is preferably obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms. From the viewpoint of further increasing the bending rigidity of the laminated glass, the intermediate film preferably includes the third layer as a surface layer in the intermediate film. The interlayer preferably includes the first layer and the third layer as surface layers of the interlayer. When the third layer is a surface layer, the polyvinyl acetal resin contained in the third layer is preferably obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms.

  From the viewpoint of further enhancing the bending rigidity of the laminated glass, it is preferable that the hydroxyl group content of the polyvinyl acetal resin contained in the first layer is 30 mol% or less. When the second layer is a surface layer, the content of hydroxyl groups of the polyvinyl acetal resin contained in the second layer is preferably 30 mol% or less. When the said 3rd layer is a surface layer, it is preferable that the content rate of the hydroxyl group of the said polyvinyl acetal resin contained in the said 3rd layer is 30 mol% or less.

  It is preferable that the surface opposite to the said 2nd layer side of the said 1st layer is a surface where a glass plate is laminated | stacked. It is preferable that the thickness of the glass plate laminated | stacked on the said 1st layer is 1 mm or less. The surface (second surface) opposite to the first layer side of the second layer may be a surface on which a glass plate is laminated. It is preferable that the thickness of the glass plate laminated | stacked on the said 2nd layer is 1 mm or less. It is preferable that the surface opposite to the said 2nd layer side of the said 3rd layer is a surface where a glass plate is laminated | stacked. It is preferable that the thickness of the glass plate laminated | stacked on the said 3rd layer is 1 mm or less.

  Since the bending rigidity can be sufficiently enhanced due to the interlayer film, the interlayer film is made of the first glass plate and the second glass plate using the first glass plate having a thickness of 1 mm or less And preferably used to obtain laminated glass. Since the bending rigidity can be sufficiently enhanced due to the interlayer film, the interlayer film is formed by using the first glass plate having a thickness of 1 mm or less and the second glass plate having a thickness of 1 mm or less. It is disposed between the first glass plate and the second glass plate, and is more preferably used to obtain a laminated glass.

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

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

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

  Other layers may be disposed between the first layer 1 and the second layer 2 and between the second layer 2 and the third layer 3 respectively. The first layer 1 and the second layer 2 and the second layer 2 and the third layer 3 are preferably directly laminated. Other layers include layers containing polyethylene terephthalate and the like.

  The first layer 1 contains a polyvinyl acetal resin and a plasticizer. The polyvinyl acetal resin contained in the first layer 1 is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms. The second layer 2 preferably contains a polyvinyl acetal resin, and preferably contains a plasticizer. The third layer 3 preferably contains a polyvinyl acetal resin, and preferably contains a plasticizer.

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

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

  The interlayer film 11A (first layer) contains a polyvinyl acetal resin and a plasticizer. The polyvinyl acetal resin contained in the intermediate film 11A is obtained by acetalizing polyvinyl alcohol with an aldehyde having 3 or less carbon atoms.

  Hereinafter, details of the first layer (including a single layer intermediate film), the second layer and the third layer constituting the intermediate film according to the present invention, and the first layer, the second layer The details of each component contained in the third layer and the second layer will be described.

(Polyvinyl acetal resin or thermoplastic resin)
The first layer (including a single-layer intermediate film) contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)). The second layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (2)), and as the thermoplastic resin (2), a polyvinyl acetal resin (hereinafter, polyvinyl acetal resin (2) And the like) may be included. The third layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (3)), and as the thermoplastic resin (3), a polyvinyl acetal resin (hereinafter, a polyvinyl acetal resin It is preferable to include 3). The polyvinyl acetal resin (1), the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) may be the same or different. One type of each of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) may be used, or two or more types may be used in combination. The thermoplastic resin (2) and the thermoplastic resin (3) may be the same or different. The thermoplastic resin (2) and the thermoplastic resin (3) may be used alone or in combination of two or more.

  As said thermoplastic resin, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, a polyurethane resin, polyvinyl alcohol resin etc. are mentioned. Thermoplastic resins other than these may be used.

  The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol is obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally 70 to 99.9 mol%.

  The average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably 5000 or less, More preferably, it is 4000 or less, more preferably 3500 or less. The penetration resistance of laminated glass becomes it still higher that the said average degree of polymerization is more than the said minimum. Formation of an intermediate film becomes easy for the said average degree of polymerization to be below the said upper limit.

  The average degree of polymerization of the polyvinyl alcohol is determined by a method in accordance with JIS K 6726 "Polyvinyl alcohol test method".

  It is preferable that carbon number of the acetal group in the said polyvinyl acetal resin is 3-5, and it is preferable that it is 3 or 4. When the carbon number of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the intermediate film becomes sufficiently low. In the present invention, with respect to the polyvinyl acetal resin contained in the first layer, the number of carbon atoms in the acetal group is 3 or less.

  In general, aldehydes having 1 to 10 carbon atoms are preferably used as the aldehyde. Examples of the above-mentioned aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexyl aldehyde, n-octyl aldehyde, Examples include n-nonyl aldehyde, n-decyl aldehyde, and benzaldehyde. Among them, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexyl aldehyde or n-valeraldehyde is preferable, acetaldehyde, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable, and acetaldehyde or propionaldehyde is more preferable. preferable. However, in the present invention, an aldehyde having 3 or less carbon atoms is used for the polyvinyl acetal resin contained in the first layer. Regarding the aldehyde used for the polyvinyl acetal resin contained in the surface layer, the number of carbon atoms is 3 or less, and may be 2 or less. Only one type of aldehyde may be used, or two or more types may be used in combination.

  The content (hydroxyl content) of the hydroxyl group of the polyvinyl acetal resin (2) is preferably 17 mol% or more, more preferably 20 mol% or more, still more preferably 22 mol% or more, preferably 30 mol% or less, more preferably Is less than 27 mol%, more preferably 25 mol% or less. The adhesive force of an intermediate film becomes it still higher that the content rate of the said hydroxyl group is more than the said minimum. In particular, when the hydroxyl content of the polyvinyl acetal resin (2) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and when it is less than 27 mol%, the sound insulation of the laminated glass is further enhanced. . Moreover, the softness | flexibility of an intermediate film becomes it high that the content rate of the said hydroxyl group is below the said upper limit, and the handling of an intermediate film becomes easy.

  The content of each hydroxyl group of the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, preferably 35 mol% or less, more preferably 32 mol % Or less, more preferably 30 mol% or less, particularly preferably 27.5 mol% or less, and most preferably 25 mol% or less. The adhesive force of an intermediate film becomes it still higher that the content rate of the said hydroxyl group is more than the said minimum. Moreover, the softness | flexibility of an intermediate film becomes it high that the content rate of the said hydroxyl group is below the said upper limit, and the handling of an intermediate film becomes easy. Moreover, bending rigidity becomes high effectively as the content rate of the said hydroxyl group is below the said upper limit.

  The hydroxyl group content of the polyvinyl acetal resin is a value indicating the molar fraction 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. The amount of ethylene groups to which the above hydroxyl groups are bonded can be determined, for example, by measurement in accordance with JIS K 6726 "Polyvinyl alcohol test method".

  The degree of acetylation (amount of acetyl group) of the polyvinyl acetal resin (2) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, still more preferably 9 It is at least mol%, preferably at most 30 mol%, more preferably at most 25 mol%, further preferably at most 15 mol%. The compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. The moisture resistance of an intermediate film and a laminated glass becomes it high that the said degree of acetylation is below the said upper limit. In particular, when the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol% or more and 25 mol% or less, the penetration resistance is excellent.

  Each acetylation degree of the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably Is 2 mol% or less. The compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. The moisture resistance of an intermediate film and a laminated glass becomes it high that the said degree of acetylation is below the said upper limit.

  The acetylation degree is a value 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 in the main chain, It is the value which showed the mole fraction calculated by dividing by a percentage. The amount of ethylene groups to which the acetal group is bonded can be measured, for example, in accordance with JIS K 6728 "Polyvinyl butyral test method".

  The degree of acetalization (butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (2) is preferably 47 mol% or more, more preferably 60 mol% or more, preferably 80 mol% or less, more preferably It is 70 mol% or less. The compatibility with polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin as the said degree of acetalization is below the said upper limit becomes short.

  The acetalization degree (butyralization degree in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is preferably 55 mol% or more, more preferably 67 mol% or more, preferably Is 75 mol% or less, more preferably 71 mol% or less. The compatibility with polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin as the said degree of acetalization is below the said upper limit becomes short.

  The degree of acetalization is a value indicating the molar fraction 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 as a percentage. The degree of acetalization can be calculated by a method in accordance with JIS K6728 "Test method for polyvinyl butyral".

  The hydroxyl group content (hydroxyl content), the degree of acetalization (butyralization) and the degree of acetylation are preferably calculated from the results measured by the method according to JIS K 6728 "Polyvinyl butyral test method". However, measurement according to ASTM D1396-92 JIS K6728 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the content of the hydroxyl group (hydroxyl content), the degree of acetalization (degree of butyralization) and the degree of acetylation are methods according to JIS K 6728 "Polyvinyl butyral test method" It can be calculated from the result measured by

  From the viewpoint of further improving the penetration resistance of the laminated glass, the polyvinyl acetal resin (2) has an acetylation degree (a) of 8 mol% or less and an acetalization degree (a) of 70 mol% It is preferable that it is polyvinyl acetal resin (A) which is the above, or it is polyvinyl acetal resin (B) whose acetylation degree (b) exceeds 8 mol%. The polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) may be the polyvinyl acetal resin (A) or the polyvinyl acetal resin (B).

  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, particularly preferably It is 5 mol% or less, preferably 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 degree of acetylation (a) is less than or equal to the upper limit and greater than or equal to the lower limit, migration of the plasticizer can be easily controlled, and the sound insulation of the laminated glass is further enhanced.

  The acetalization degree (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, particularly preferably It is 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. The sound insulation of a laminated glass becomes it still higher that the said degree of acetalization (a) is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin (A) as the said degree of acetalization (a) is below the said upper limit 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 It is at most mol%, more preferably at most 30 mol%, still more preferably at most 29 mol%, particularly preferably at most 28 mol%. The adhesive force of the said 2nd layer becomes it still higher that the content rate (a) of the said hydroxyl group is more than the said minimum. The sound insulation of a laminated glass becomes it still higher that the content rate (a) of the said hydroxyl group is below the said upper limit.

  The degree of acetylation (b) of the polyvinyl acetal resin (B) is more than 8 mol%, preferably 9 mol% or more, more preferably 9.5 mol% or more, still more preferably 10 mol% or more, particularly preferably It is 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. The sound insulation of a laminated glass becomes it still higher that the said degree of acetylation (b) is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin (B) as said acetylation degree (b) is below the said upper limit 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 78 mol% or less, still more preferably 76 mol% or less, particularly preferably 74 mol% or less. The sound insulation of a laminated glass becomes it still higher that the said degree of acetalization (b) is more than the said minimum. The reaction time required in order to manufacture polyvinyl acetal resin (B) as the said degree of acetalization (b) is below the said upper limit can be shortened.

  The hydroxyl group 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 It is at most mol%, more preferably at most 30 mol%, still more preferably at most 29 mol%, particularly preferably at most 28 mol%. The adhesive force of the said 2nd layer becomes it still higher that the content rate (b) of the said hydroxyl group is more than the said minimum. The sound insulation of a laminated glass becomes it still higher that the content rate (b) of the said hydroxyl group is below the said upper limit.

  The polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) are each preferably a polyvinyl butyral resin.

(Plasticizer)
The first layer (including a single-layer intermediate film) contains a plasticizer (hereinafter sometimes referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter sometimes referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter sometimes referred to as a plasticizer (3)). By the combined use of the polyvinyl acetal resin and the plasticizer, the adhesion of the layer containing the polyvinyl acetal resin and the plasticizer to the laminated glass member or other layers is appropriately increased. The plasticizer is not particularly limited. The plasticizer (1), the plasticizer (2) and the plasticizer (3) may be the same or different. The plasticizer may be used alone or in combination of two or more.

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

  As said monobasic organic acid ester, the glycol ester etc. which were obtained by reaction of glycol and monobasic organic acid are mentioned. Examples of the glycol include triethylene glycol, tetraethylene glycol and tripropylene glycol. Examples of the monobasic organic acids include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid and decylic acid.

  Examples of the polybasic organic acid ester include ester compounds 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 acids include adipic acid, sebacic acid and azelaic acid.

  Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl hexanoate, triethylene glycol dicaprylate, Triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl Xanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, adipine Hexylhexyl hexyl acid, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl nonyl adipate, dibutyl sebacate, oil-modified sebacic alkyd, and mixtures of phosphoric acid ester and adipic acid ester etc. It can be mentioned. Organic ester plasticizers other than these may be used. Other adipates may be used other than the adipates described above.

  Examples of the organic phosphoric acid plasticizer include tributoxyethyl phosphate, isodecyl phenyl phosphate and triisopropyl phosphate.

  The plasticizer is preferably a diester plasticizer represented by the following formula (1).

  In the above formula (1), R 1 and R 2 each represent an organic group having 2 to 10 carbon atoms, R 3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10 . Each of R 1 and R 2 in the above formula (1) is preferably an organic group having 5 to 10 carbon atoms, and more preferably an organic group having 6 to 10 carbon atoms.

  The plasticizer is preferably triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH) or triethylene glycol di-2-ethylpropanoate More preferred is triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethyl butyrate, and more preferred is triethylene glycol di-2-ethyl hexanoate.

  The content (hereinafter sometimes referred to as content (0) of the plasticizer) with respect to 100 parts by weight of the polyvinyl acetal resin in the surface layer, the content of the plasticizer (1) with respect to 100 parts by weight of the polyvinyl acetal resin (1) Content (hereinafter referred to as content (1)) and content (hereinafter referred to as content (3) of the plasticizer (3) with respect to 100 parts by weight of the polyvinyl acetal resin (3) Are each preferably 20 parts by weight or more, more preferably 25 parts by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, still more preferably 32 parts by weight or less, particularly preferably 30 parts by weight It is below. When the content (0), the content (1) and the content (3) are at least the lower limit, the flexibility of the intermediate film becomes high, and the handling of the intermediate film becomes easy. In particular, when the content (0), the content (1) and the content (3) are at least 20 parts by weight, bending stiffness is effectively enhanced. When the content (0), the content (1) and the content (3) are less than or equal to the upper limits, the mechanical strength of the interlayer is further increased, and the penetration resistance of the laminated glass is further enhanced. Become. In particular, when the content (0), the content (1) and the content (3) are 35 parts by weight or less, the penetration resistance of the laminated glass is effectively enhanced.

  The content of the plasticizer (2) (hereinafter sometimes referred to as content (2)) relative to 100 parts by weight of the polyvinyl acetal resin (2) is preferably 37 parts by weight or more, more preferably 38 parts by weight The amount is preferably 50 parts by weight or less, more preferably 45 parts by weight or less, still more preferably 42 parts by weight or less, and particularly preferably 41 parts by weight or less. The softness | flexibility of an intermediate film becomes it high that the said content (2) is more than the said lower limit, and the handling of an intermediate film becomes easy. The penetration resistance of laminated glass becomes it still higher that said content (2) is below the said upper limit.

  In order to enhance the penetration resistance of the laminated glass, the content (1) is preferably less than the content (2), and the content (3) is preferably less than the content (2). .

  From the viewpoint of further enhancing the penetration resistance of the laminated glass, the absolute value of the difference between the content (1) and the content (2), and the content (3) and the content (2) The absolute value of the difference is preferably 2 parts by weight or more, more preferably 5 parts by weight or more, and still more preferably 8 parts by weight or more. The absolute value of the difference between the content (1) and the content (2) and the absolute value of the difference between the content (3) and the content (2) are each preferably at most 22 parts by weight, More preferably, it is 20 parts by weight or less, still more preferably 15 parts by weight or less.

(Thermal barrier compound)
The intermediate film preferably contains a heat shielding compound. It is preferable that the first layer contains a heat shielding compound. The second layer preferably contains a heat shielding compound. The third layer preferably contains a heat shielding compound. As the heat shielding compound, only one type may be used, or two or more types may be used in combination.

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

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

  Examples of the component X include phthalocyanines, derivatives of phthalocyanines, naphthalocyanines, derivatives of naphthalocyanines, anthracyanines and derivatives of anthracyanines, and the like. It is preferable that the said phthalocyanine compound and the derivative of the said phthalocyanine have a phthalocyanine skeleton, respectively. Each of the naphthalocyanine compound and the derivative of the naphthalocyanine preferably has a naphthalocyanine skeleton. Each of the anthracyanine compound and the derivative of the anthracyanine preferably has an anthracyanine skeleton.

  From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X is preferably at least one selected from the group consisting of phthalocyanines, derivatives of phthalocyanines, naphthalocyanines and derivatives of naphthalocyanines And more preferably at least one of phthalocyanine and a derivative of phthalocyanine.

  From the viewpoint of effectively enhancing the heat shielding properties and maintaining the visible light transmittance at a higher level for a long time, the component X preferably contains a vanadium atom or a copper atom. The component X preferably contains a vanadium atom, and also preferably contains a copper atom. The component X is more preferably at least one of phthalocyanines containing a vanadium atom or a copper atom and derivatives of phthalocyanines containing a vanadium atom or a copper atom. From the viewpoint of further increasing the heat shielding properties of the interlayer and the laminated glass, the component X preferably has a structural unit in which an oxygen atom is bonded to a vanadium atom.

  The content of the component X is preferably 0.001% by weight or more, more preferably 0.005% in 100% by weight of the layer containing the component X (first layer, second layer or third layer). % By weight or more, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more, preferably 0.2% by weight or less, more preferably 0.1% by weight or less, still more preferably 0.05% by weight % Or less, particularly preferably 0.04% by weight or less. When the content of the component X is not less than the lower limit and not more than the upper limit, the heat shielding property becomes sufficiently high, and the visible light transmittance becomes sufficiently high. For example, it is possible to make the visible light transmittance 70% or more.

Heat shielding particles:
The interlayer film preferably contains heat shielding particles. The first layer preferably includes the heat shielding particles. The second layer preferably contains the heat shielding particles. The third layer preferably includes the heat shielding particles. The heat shielding particles are heat shielding compounds. The use of heat shielding particles can effectively block infrared rays (heat rays). The heat shielding particles may be used alone or in combination of two or more.

  From the viewpoint of further enhancing the heat shielding properties of the laminated glass, the heat shielding particles are more preferably metal oxide particles. The heat shielding particles are preferably particles (metal oxide particles) formed of a metal oxide.

  An infrared ray having a wavelength of 780 nm or more, which is longer than visible light, has a smaller amount of energy than ultraviolet rays. However, the infrared radiation has a large thermal effect, and is released as heat when the infrared radiation is absorbed by the substance. For this reason, infrared rays are generally called heat rays. By the use of the heat shielding particles, infrared rays (heat rays) can be effectively blocked. The heat shielding particles mean particles capable of absorbing 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 them, metal oxide particles are preferable because they have 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 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 intermediate film, tungsten oxide particles represented by the following formula (X1) or the following formula (X2) are suitably used.

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

M _x W _y O _z Formula (X2)
In the above formula (X2), M is H, He, an alkali metal, an alkaline earth metal, a 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 Re, W is tungsten, O is oxygen, x, y and z are 0.001 ≦ x / y ≦ 1, and 2.0 <z / y ≦ 3.0 is satisfied.

  The tungsten oxide particles are preferably metal-doped tungsten oxide particles from the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass. The above-mentioned "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 average particle diameter of the heat shielding particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.1 μm or less, and more preferably 0.05 μm or less. When the average particle diameter is equal to or more than the above lower limit, the shielding property of the heat ray becomes sufficiently high. When the average particle size is equal to or less than the above upper limit, the dispersibility of the heat shielding particles becomes high.

  The above "average particle diameter" indicates a volume average particle diameter. The average particle size can be measured using a particle size distribution measuring apparatus ("UPA-EX 150" manufactured by Nikkiso Co., Ltd.) or the like.

  The content of the heat shielding particles is preferably 0.01% by weight or more, more preferably 0% in 100% by weight of the layer (the first layer, the second layer or the third layer) containing the heat shielding particles. .1 wt% or more, more preferably 1 wt% or more, particularly preferably 1.5 wt% or more, preferably 6 wt% or less, more preferably 5.5 wt% or less, still more preferably 4 wt% or less Preferably it is 3.5 wt% or less, most preferably 3.0 wt% or less. When the content of the heat shielding particles is not less than the lower limit and not more than the upper limit, the heat shielding property becomes sufficiently high, and the visible light transmittance becomes sufficiently high.

The layer (the first layer, the second layer, or the third layer) containing the heat shielding particles may contain the heat shielding particles at a ratio of 0.1 g / m ² or more and 12 g / m ² or less preferable. When the ratio of the heat shielding particles is in the above range, the heat shielding property is sufficiently high, and the visible light transmittance is sufficiently high. The ratio of the heat shielding particles is preferably 0.5 g / m ² or more, more preferably 0.8 g / m ² or more, still more preferably 1.5 g / m ² or more, particularly preferably 3 g / m ² or more Is preferably 11 g / m ² or less, more preferably 10 g / m ² or less, still more preferably 9 g / m ² or less, particularly preferably 7 g / m ² or less. When the ratio is equal to or more than the lower limit, the heat shielding property is further enhanced. The visible light transmittance becomes still higher as the above-mentioned ratio is below the above-mentioned upper limit.

(Metal salt)
The intermediate film preferably contains at least one metal salt of an alkali metal salt and an alkaline earth metal salt (hereinafter sometimes referred to as a metal salt M). The first layer preferably contains the metal salt M. The second layer preferably contains the metal salt M. The third layer preferably contains the metal salt M. The use of the metal salt M makes it easy to control the adhesion between the interlayer and the glass plate or between the layers in the interlayer. The metal salt M may be used alone or in combination of two or more.

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

  The metal salt M is 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.

  The carboxylic acid magnesium salt having 2 to 16 carbon atoms and the potassium salt having 2 to 16 carbon atoms are not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, and 2-ethylbutyric acid. Magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like can be mentioned.

  The total content of Mg and K in the layer containing the metal salt M (first layer, second layer or third layer) is preferably 5 ppm or more, more preferably 10 ppm or more, still more preferably 20 ppm or more Preferably it is 300 ppm or less, More preferably, it is 250 ppm or less, More preferably, it is 200 ppm or less. The adhesiveness of an intermediate film and a glass plate as the sum total of content of Mg and K is below the said lower limit and the said upper limit can be controlled still more favorably the adhesiveness between each layer in an intermediate film.

(UV screening agent)
The intermediate film preferably contains an ultraviolet shielding agent. The first layer preferably contains an ultraviolet shielding agent. The second layer preferably contains an ultraviolet shielding agent. The third layer preferably contains an ultraviolet shielding agent. The use of the ultraviolet shielding agent makes it more difficult to reduce the visible light transmittance even when the interlayer and the laminated glass are used for a long time. The ultraviolet screening agent may be used alone or in combination of two or more.

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

  Examples of the UV screening agent include metal UV screening agents, metal oxide UV screening agents, benzotriazole UV screening agents, benzophenone UV screening agents, triazine UV screening agents, malonic acid ester UV screening agents, Examples thereof include oxalic acid anilide type ultraviolet screening agents and benzoate type ultraviolet screening agents.

  Examples of the metal-based ultraviolet absorber include platinum particles, particles in which the surface of platinum particles is coated with silica, palladium particles, and particles in which the surfaces of palladium particles are coated with silica. Preferably, the UV screening agent is not a thermal barrier particle.

  The UV screening agent is preferably a benzotriazole UV screening agent, a benzophenone UV screening agent, a triazine UV screening agent or a benzoate UV screening agent, more preferably a benzotriazole UV screening agent or a benzophenone UV shielding agent More preferably, they are benzotriazole type ultraviolet absorbers.

  Examples of the metal oxide ultraviolet absorber include zinc oxide, titanium oxide and cerium oxide. Furthermore, the surface may be coated as the metal oxide UV absorber. As a coating material of the surface of the said metal oxide type ultraviolet absorber, an insulating metal oxide, a hydrolysable organosilicon compound, a silicone compound, etc. are mentioned.

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

  Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“Tinuvin P” manufactured by BASF Corp.), 2- (2′-hydroxy-3 ′, 5 ′ -Di-t-butylphenyl) benzotriazole ("Tinuvin 320" manufactured by BASF Corp.), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF Corp.) Benzotriazole-based ultraviolet absorbers such as Tinuvin 326 ′ ′) and 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinuvin 328” manufactured by BASF Corp.) can be mentioned. It is preferable that it is a benzotriazole type ultraviolet absorber containing a halogen atom, and it is more preferable that it is a benzotriazole type ultraviolet absorber containing a chlorine atom, since it is excellent in the performance which absorbs an ultraviolet-ray.

  Examples of the benzophenone series ultraviolet absorber include octabenzone ("Chimassorb 81" manufactured by BASF Corporation).

  Examples of the triazine-based UV absorber include “LA-F70” manufactured by ADEKA Corporation and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]. -Phenol ("Tinuvin 1577FF" by BASF Corporation) etc. are mentioned.

  As the above-mentioned malonic acid ester-based ultraviolet screening agent, dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylene dimethylidene) bismalonate, 2- (p-methoxybenzylidene) -bis (1,2,2,6,6-pentamethyl 4-piperidinyl) malonate etc. are mentioned.

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

  N- (2-ethylphenyl) -N '-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl) -N' as the above oxalic acid anilide type ultraviolet screening agent Oxalic acid diamides having an aryl group or the like substituted on a nitrogen atom, such as-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("Sanduvor VSU" manufactured by Clariant) It can be mentioned.

  As said benzoate series ultraviolet absorber, the 2, 4- di-tert- butylphenyl- 3, 5- di- tert- butyl- 4-hydroxy benzoate (BASF company make "Tinuvin 120") etc. are mentioned, for example.

  From the viewpoint of further suppressing the reduction of the visible light transmittance after the lapse of time, the UV shielding in 100% by weight of the layer (the first layer, the second layer or the third layer) containing the above-mentioned UV shielding agent The content of the agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, still more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably 2.5% by weight or more. It is at most weight%, more preferably at most 2 weight%, even more preferably at most 1 weight%, particularly preferably at most 0.8 weight%. In particular, when the content of the ultraviolet ray shielding agent is 0.2% by weight or more in 100% by weight of the layer containing the ultraviolet ray shielding agent, a decrease in visible light transmittance after a lapse of time of the interlayer film and the laminated glass It can be significantly suppressed.

(Antioxidant)
The interlayer preferably contains an antioxidant. The first layer preferably contains an antioxidant. The second layer preferably contains an antioxidant. The third layer preferably contains an antioxidant. As the above-mentioned antioxidant, only 1 type may be used and 2 or more types may be used together.

  As said antioxidant, a phenol type antioxidant, a sulfur type antioxidant, phosphorus type antioxidant etc. are mentioned. The said phenolic antioxidant is an antioxidant which has a phenol frame. The sulfur-based antioxidant is a sulfur atom-containing antioxidant. The phosphorus-based antioxidant is a phosphorus atom-containing antioxidant.

  It is preferable that the said antioxidant is a phenolic antioxidant or phosphorus type antioxidant.

  Examples of the above-mentioned phenolic antioxidants 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-tert-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) Roxy-5-tert-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,3'-) t-Butylphenol) butyric acid glycol ester and bis (3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene) and the like can be mentioned. One or more of these antioxidants are preferably used.

  The above-mentioned phosphorus-based antioxidants include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, torinylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphos Phytos, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, tris (2,4-di-t And -butylphenyl) phosphite, and 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus and the like. One or more of these antioxidants are preferably used.

  As a commercial item of the above-mentioned antioxidant, for example, Sumitomo Chemical Co., Ltd. "Sumilyzer BHT", Ciba-Geigy "IRGANOX 1010" etc. are mentioned.

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

(Other ingredients)
Each of the first layer, the second layer, and the third layer is, if necessary, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive regulator, a moisture resistant agent, a fluorescent brightener, and an infrared ray. An additive such as an absorbent may be included. One of these additives may be used alone, or two or more thereof may be used in combination.

(Other details of interlayer film for laminated glass)
The glass transition temperatures of the first layer and the third layer are preferably 31 ° C. or more, more preferably 33 ° C. or more, and still more preferably 35 ° C., from the viewpoint of further enhancing the bending rigidity of the laminated glass. It is above. The upper limit of the glass transition temperature of the first layer and the third layer is not particularly limited. The glass transition temperature of the first layer and the third layer may be 60 ° C. or less from the viewpoint of further enhancing the sound insulation of the interlayer.

  The thickness of the intermediate film is not particularly limited. The thickness of the intermediate film is preferably 0.1 mm or more, more preferably 0.25 mm or more, and preferably 3 mm or less, from the viewpoint of practical use and from the viewpoint of sufficiently enhancing the penetration resistance and bending rigidity of laminated glass. More preferably, it is 1.5 mm or less. The penetration resistance and bending rigidity of laminated glass become it high that the thickness of an intermediate film is more than the said minimum. When the thickness of the interlayer is less than or equal to the above upper limit, the transparency of the interlayer is further improved.

  Let T be the thickness of the intermediate film. In the case of a multilayer intermediate film, the thickness of the second layer is preferably 0.0625 T or more, more preferably 0.1 T or more, preferably 0.375 T or less, more preferably 0.25 T or less.

  The thickness of each of the first layer and the third layer is preferably 0.3125 T or more, more preferably 0.375 T or more, preferably 0.9375 T or less, more preferably 0.9 T or less. The thickness of each of the first layer and the third layer may be 0.46875 T or less, or may be 0.45 T or less. Moreover, the bending rigidity of laminated glass becomes it still higher that each thickness of a said 1st layer and a said 3rd layer is more than the said minimum and below the said upper limit, and it can suppress the bleed-out of a plasticizer.

  The total thickness of the first layer and the third layer is preferably 0.625 T or more, more preferably 0.75 T or more, preferably 0.9375 T or less, more preferably 0.9 T or less. In addition, when the total thickness of the first layer and the third layer is not less than the lower limit and not more than the upper limit, the bending rigidity of the laminated glass is further enhanced, and the bleed out of the plasticizer can be suppressed.

  It does not specifically limit as a manufacturing method of the intermediate film which concerns on this invention. As a method for producing an interlayer film according to the present invention, in the case of a monolayer interlayer film, a method of extruding a resin composition using an extruder can be mentioned. In the case of a multi-layered intermediate film, the method for producing an intermediate film according to the present invention is, for example, a method of laminating the obtained layers after forming each layer using each resin composition for forming each layer. And a method of laminating the respective layers by coextrusion of the respective resin compositions for forming the respective layers using an extruder. Extrusion is preferred because it is suitable for continuous production.

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

  The intermediate film preferably has an uneven shape on at least one of the surfaces on both sides. The intermediate film more preferably has an uneven shape on the surfaces on both sides. It does not specifically limit as a method to form said uneven | corrugated shape, For example, the embossing roll method, the calender roll method, the profile extrusion method etc. are mentioned. Among them, the emboss roll method is preferable because it can form a large number of concavo-convex embossments which are a constant concavo-convex pattern quantitatively.

(Laminated glass)
FIG. 3: is sectional drawing which shows typically an example of the laminated glass using the intermediate film for laminated glasses shown in FIG.

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

  The first glass plate 21 is stacked on the first surface 11 a of the intermediate film 11. A second glass plate 22 is stacked on a second surface 11 b opposite to the first surface 11 a of the intermediate film 11. The first glass plate 21 is laminated on the outer surface 1 a of the first layer 1. The second glass plate 22 is laminated on the outer surface 3 a of the third layer 3.

  FIG. 4: is sectional drawing which shows typically an example of the laminated glass using the intermediate film for laminated glasses shown in FIG.

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

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

  Thus, the laminated glass according to the present invention includes the first glass plate, the second glass plate, and the intermediate film, and the intermediate film is the intermediate film for laminated glass according to the present invention. . In the laminated glass according to the present invention, the intermediate film is disposed between the first glass plate and the second glass plate.

  Inorganic glass and organic glass are mentioned as said glass plate. As said inorganic glass, float plate glass, heat ray absorption plate glass, heat ray reflective plate glass, polished plate glass, template glass, netted plate glass, lined plate glass etc. are mentioned. The organic glass is a synthetic resin glass substituted for inorganic glass. As said organic glass, a polycarbonate board, a poly (meta) acrylic resin board, etc. are mentioned. As said poly (meth) acryl resin board, a polymethyl (meth) acrylate board etc. are mentioned.

  The thickness of the glass plate is preferably 0.5 mm or more, more preferably 0.7 mm or more, preferably 5 mm or less, more preferably 3 mm or less.

  By using the interlayer film according to the present invention, the bending rigidity of the laminated glass can be maintained high even if the thickness of the laminated glass is thin. From the viewpoint of reducing the environmental load by reducing the weight of the laminated glass, reducing the material of the laminated glass, and improving the fuel efficiency of the car by reducing the weight of the laminated glass and reducing the environmental load, The thickness is preferably 2 mm or less, more preferably 1.8 mm or less, still more preferably 1.5 mm or less, still more preferably 1 mm or less, still more preferably 0.8 mm or less, particularly preferably 0.7 mm or less.

  The manufacturing method of the said laminated glass is not specifically limited. For example, an intermediate film is interposed between the first glass plate and the second glass plate, and the intermediate film is passed through a pressure roll or placed in a rubber bag and suctioned under reduced pressure, or the first glass The air remaining between the plate and the second glass plate and the intermediate film is degassed. Thereafter, pre-adhesion is performed at about 70 to 110 ° C. to obtain a laminate. The laminate is then crimped in an autoclave or pressed at a pressure of about 120-150 ° C. and 1-1.5 MPa. In this way, laminated glass can be obtained. The first layer, the second layer and the third layer may be laminated at the time of production of the laminated glass.

  The interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings and the like. The interlayer film and the laminated glass can be used other than these applications. The interlayer film and the laminated glass are preferably an interlayer film and laminated glass for a vehicle or a building, and more preferably an interlayer and a laminated glass for a vehicle. The interlayer film and the laminated glass can be used as a front glass, a side glass, a rear glass, a roof glass, etc. of an automobile. The interlayer film and the laminated glass are suitably used in automobiles. The interlayer film is used to obtain laminated glass of a car.

  The present invention will be described in more detail by way of the following examples. The present invention is not limited to these examples.

  The following materials were prepared.

(Polyvinyl acetal resin)
Polyvinyl acetal resin A (using acetaldehyde having 2 carbon atoms, average polymerization degree of polyvinyl alcohol (PVA) 2000, hydroxyl group content 24.5 mol%, acetylation degree 1.5 mol%, acetalization degree 74.0 mol %)
Polyvinyl acetal resin X (using n-butyraldehyde having 4 carbon atoms, average polymerization degree of polyvinyl alcohol (PVA) 3000, hydroxyl group content 34.5 mol%, degree of acetylation 0.7 mol%, degree of acetalization 64 .8 mol%)

  With respect to polyvinyl acetal (PVA) resin, the degree of acetalization (butyralization), the degree of acetylation and the hydroxyl group content were measured by a method according to JIS K 6728 "Polyvinyl butyral test method". In addition, when it measured by ASTMD1396-92, the numerical value similar to the method based on JISK6728 "polyvinyl butyral test method" was shown.

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

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

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

Example 1
Preparation of composition to form first layer:
100 parts by weight of polyvinyl acetal resin A, 35 parts by weight of plasticizer (3GO), 0.2 parts by weight of ultraviolet shielding agent (Tinuvin 326) and 0.2 parts by weight of antioxidant (BHT) The composition for forming a layer was obtained.

Preparation of interlayer:
The composition for forming the first layer was extruded using an extruder to produce a single layer intermediate film (760 μm in thickness) of only the first layer (760 μm in thickness).

Preparation of laminated glass A:
Two glass plates (clear float glass, 25 cm long × 10 cm wide × 2.5 mm thick) which were cleaned and dried were prepared. The obtained intermediate film was sandwiched between the two glass plates to obtain a laminate. The resulting laminate was placed in a rubber bag and degassed for 20 minutes at a vacuum of 2660 Pa (20 torr). Thereafter, the laminate was vacuum pressed while maintaining the degassing for 30 minutes at 90 ° C. in an autoclave. The laminate thus pressure-bonded was pressure-bonded in an autoclave under the conditions of 135 ° C. and a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass A.

Preparation of laminated glass B:
One glass plate (clear float glass, 25 cm long × 10 cm wide × 2.5 mm thick) washed and dried was prepared. One glass plate (Gorilla glass, 25 cm long × 10 cm wide × 0.7 mm thick) washed and dried was prepared. A laminated glass B was obtained in the same manner as the laminated glass A except that the two glass plates were used.

Preparation of laminated glass C:
Two glass plates (Gorilla glass, 25 cm long × 10 cm wide × 0.7 mm thick) washed and dried were prepared. Laminated glass C was obtained in the same manner as laminated glass A except that these two glass plates were used.

(Examples 2 to 3 and Comparative Example 1)
The types of polyvinyl acetal resin and plasticizer used in the composition for forming the first layer and the blending amount of the plasticizer with respect to 100 parts by weight of polyvinyl acetal resin are set as shown in Table 1 below. In the same manner as in Example 1, an interlayer film, laminated glass A, laminated glass B and laminated glass C were obtained.

(Evaluation)
(1) Glass transition temperature The kneaded material which has a composition of the 1st layer in an Example and a comparative example was prepared. The obtained kneaded product was press-molded by a press molding machine to obtain a resin film A having a thickness of 0.35 mm. The obtained resin film A was allowed to stand for 2 hours at 25 ° C. and 30% relative humidity. After leaving for 2 hours, the viscoelasticity was measured using "ARES-G2" manufactured by TAINSTRUMENTS. A parallel plate with a diameter of 8 mm was used as a jig. The measurement was performed under the conditions of temperature decrease from 100 ° C. to −10 ° C. at the temperature decrease rate of 3 ° C./min, and the conditions of frequency 1 Hz and strain 1%. In the obtained measurement results, the peak temperature of the loss tangent was taken as the glass transition temperature Tg (° C.).

(2) Flexural rigidity The obtained laminated glass A, laminated glass B and laminated glass C were prepared. The following glass plates are used in the laminated glass A, the laminated glass B and the laminated glass C.

Laminated glass A: 2 glass plates (clear float glass, 25 cm long x 10 cm wide x 2.5 mm thick)
Laminated glass B: One glass plate (clear float glass, 25 cm long x 10 cm wide x 2.5 mm thick) and one glass plate (Gorilla glass, 25 cm long x 10 cm wide x 0.7 mm thick)
Laminated glass C: 2 glass plates (gorilla glass, 25 cm long x 10 cm wide x 0.7 mm thick)

  The bending elasticity was evaluated by the test method schematically shown in FIG. As a measuring apparatus, a universal material tester 5966 manufactured by Instron Japan Company Limited having a static three-point bending test jig 2810 was used. As measurement conditions, measurement temperature is 20 ± 3 ° C., distance D1 is 18 cm, distance D2 is 25 cm, deformation speed is 1 mm / min in the direction of F, glass is deformed, and displacement of 1.5 mm is applied. The stress was measured and the bending stiffness was calculated. The flexural rigidity was determined according to the following criteria.

[Criteria for judging bending stiffness]
1: Measured value with laminated glass C is less than 0.002 mm / N 2: Measured value with laminated glass C is equivalent to the judgment standard of 0.002 mm / N or more and less than 0.005 mm / N 3: 1, 2 No, the measured value in laminated glass B is less than 0.005 mm / N, which does not correspond to the judgment criteria of 4: 1-3, and the measured value in laminated glass C is less than 0.11 mm / N, judgment of 5: 1 to 3 Not equivalent to the standard, measured value with laminated glass C is 0.11 mm / N or more

  Details and results are shown in Table 1 below. In addition, in following Table 1, description of compounding components other than polyvinyl acetal resin and a plasticizer was abbreviate | omitted.

DESCRIPTION OF SYMBOLS 1 ... 1st layer 1a ... outer surface 2 ... 2nd layer 2a ... 1st surface 2b ... 2nd surface 3 ... 3rd layer 3a ... outer surface 11 ... intermediate film 11 A ... intermediate film (1st film) 1 layer)
11a: first surface 11b: second surface 21: first glass plate 22: second glass plate 31: laminated glass 31A: laminated glass

Claims (15)

An interlayer for laminated glass having a structure of one layer or a structure of two or more layers,
A first layer containing a polyvinyl acetal resin and a plasticizer as a surface layer in an interlayer film,
The polyvinyl acetal resin contained in the first layer is an acetalized product by aldehyde having a carbon number of polyvinyl alcohol of 3 or less,
Ri Der glass transition temperature of 31 ° C. or more of said first layer,
Using a first glass plate thickness is 2mm or less, the first glass plate and is disposed between the second glass plate, Ru used to obtain laminated glass, for laminated glass interlayer film .   The interlayer film for laminated glass according to claim 1, wherein the glass transition temperature of the first layer is 40 ° C. or higher.   The interlayer film for laminated glass according to claim 1 or 2, wherein a content rate of a hydroxyl group of the polyvinyl acetal resin contained in the first layer is 30 mol% or less. The hydroxyl group content of the polyvinyl acetal resin contained in the first layer is 30 mol% or less,
The combination according to claim 1 or 2, wherein the content of the plasticizer contained in the first layer is 20 parts by weight or more with respect to 100 parts by weight of the polyvinyl acetal resin contained in the first layer. Intermediate film for glass. The hydroxyl group content of the polyvinyl acetal resin contained in the first layer is 30 mol% or less,
The content of the said plasticizer contained in the said 1st layer is 40 parts by weight or less with respect to 100 parts by weight of the said polyvinyl acetal resin contained in the said 1st layer. Interlayer film for laminated glass. An intermediate film for laminated glass having a structure of two or more layers,
And a second layer containing a polyvinyl acetal resin and a plasticizer,
The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the first layer is disposed on the first surface side of the second layer. An interlayer for laminated glass having a structure of three or more layers,
And a third layer containing a polyvinyl acetal resin and a plasticizer as a surface layer in the interlayer film,
The third layer is disposed on a second surface side opposite to the first surface side of the second layer,
The interlayer film for laminated glass according to claim 6, wherein the polyvinyl acetal resin contained in the third layer is an acetalized product by an aldehyde having a carbon number of polyvinyl alcohol of 3 or less. An interlayer for laminated glass having a single-layer structure,
The interlayer for laminated glass according to any one of claims 1 to 5, wherein only the first layer is provided. The interlayer for laminated glass according to any one of claims 1 to 8 , wherein the thickness of the first glass plate is 1 mm or less. Between the first glass plate and the second glass plate, the first glass plate having a thickness of 2 mm or less and the second glass plate having a thickness of 2 mm or less are used. The interlayer film for laminated glass according to any one of claims 1 to 8, which is used to obtain a glass. The interlayer for laminated glass according to claim 10 , wherein the thickness of the first glass plate is 1 mm or less, and the thickness of the second glass plate is 1 mm or less. A first glass plate having a thickness of 2 mm or less ,
A second glass plate,
And an interlayer for laminated glass according to any one of claims 1 to 8.
Laminated glass, wherein the intermediate film for laminated glass is disposed between the first glass plate and the second glass plate. The laminated glass of Claim 12 whose thickness of a said 1st glass plate is 1 mm or less. The laminated glass of Claim 12 or 13 whose thickness of a said 2nd glass plate is 2 mm or less. The laminated glass of Claim 14 whose thickness of a said 2nd glass plate is 1 mm or less.

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