JP6641144B2 - Interlayer for laminated glass and laminated glass - Google Patents

Description

  The present invention relates to an interlayer film for a laminated glass used for obtaining a laminated glass. The present invention also relates to a laminated glass using the interlayer film for a laminated glass.

  Even if the laminated glass is damaged by an external impact, the amount of glass fragments scattered is small and the laminated glass is excellent in safety. 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 interlayer film for laminated glass between two glass plates.

  Examples of the interlayer film for laminated glass include a single-layer interlayer film having a single-layer structure and a multilayer interlayer film having two or more layers.

  As an example of the interlayer film for laminated glass, Patent Literature 1 listed below discloses 100 parts by weight of a polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and at least one of an alkali metal salt and an alkaline earth metal salt. Discloses a sound insulating layer containing 0.001 to 1.0 parts by weight of a metal salt and a plasticizer exceeding 30 parts by weight. This sound insulation layer can be used as an interlayer in a single layer.

  Further, Patent Literature 1 below describes a multilayer interlayer in which the sound insulation layer and another layer are stacked. Other layers to be laminated on the sound insulation layer include 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 of 0.001 to 0.001. 1.0 part by weight and a plasticizer of 30 parts by weight or less.

  Patent Document 2 listed below discloses an intermediate film that is a polymer layer having a glass transition temperature of 33 ° C. or higher. Patent Literature 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 / 0236911A1

  Laminated glass using a conventional interlayer film as described in Patent Documents 1 and 2 may have low rigidity. For this reason, for example, when used for a side door of an automobile, there is no frame for fixing the laminated glass, and the opening and closing of the glass may be hindered due to bending caused by low rigidity of the laminated glass.

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

  Further, in order to obtain an intermediate film, it is desired to reuse a recovered material (recovered intermediate film) used at least once to obtain an intermediate film.

  An object of the present invention is to provide an interlayer film for laminated glass that can increase the rigidity of the laminated glass and enhance the recyclability of the interlayer film. Another object of the present invention is to provide a laminated glass using the interlayer film for laminated glass.

  According to a broad aspect of the present invention, the method includes a first layer and a second layer disposed on a first surface side of the first layer, wherein the first layer is derived from a polyvinyl acetal resin. The second layer comprising a copolymer having a skeleton derived from a second resin component and a skeleton derived from a second resin component, wherein the second layer comprises a polyvinyl acetal resin, and the second layer constituting the copolymer in the first layer Wherein the resin component is an acrylic polymer, a urethane polymer, a silicone polymer, a rubber, or a vinyl acetate polymer.

  In one specific aspect of the interlayer film for a laminated glass according to the present invention, a peak temperature of a loss tangent indicated by a skeleton derived from the second resin component in the copolymer in the first layer is −30 ° C. or higher. 10 ° C. or less.

  In a specific aspect of the interlayer film for a laminated glass according to the present invention, the skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer and the skeleton in the copolymer in the first layer. In a total of 100% by weight with the skeleton derived from the second resin component, the content of the skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer is 5% by weight or more and 60% by weight or less. The content of the skeleton derived from the second resin component in the copolymer in the first layer is 40% by weight or more and 95% by weight or less.

  In a specific aspect of the interlayer film for a laminated glass according to the present invention, the second resin component constituting the copolymer in the first layer is an acrylic polymer.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the interlayer film for laminated glass may include a third layer disposed on a second surface side of the first layer opposite to the first surface. And the third layer contains a polyvinyl acetal resin.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the second layer contains a plasticizer, and the third layer contains a plasticizer.

  According to a broad aspect of the present invention, it includes a first laminated glass member, a second laminated glass member, and the above-described interlayer film for laminated glass, wherein the first laminated glass member and the second laminated glass are provided. A laminated glass is provided, in which the interlayer film for a laminated glass is arranged between members.

  The interlayer film for laminated glass according to the present invention includes a first layer and a second layer disposed on the first surface side of the first layer, wherein the first layer is a polyvinyl acetal resin. Wherein the second layer comprises a polyvinyl acetal resin and comprises a copolymer having a skeleton derived from and a skeleton derived from a second resin component. Since the second resin component is an acrylic polymer, a urethane polymer, a silicone polymer, a rubber, or a vinyl acetate polymer, the rigidity of the laminated glass using the interlayer can be increased, and the interlayer can be recycled. Can be enhanced.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing one example of a laminated glass using the interlayer film for laminated glass shown in FIG. FIG. 3 is a schematic diagram for explaining a method of measuring bending stiffness.

  Hereinafter, the present invention will be described in detail.

(Interlayer for laminated glass)
The interlayer film for a laminated glass according to the present invention (in this specification, may be abbreviated as “interlayer film”) has a structure of two or more layers.

  The intermediate film according to the present invention includes a first layer, and a second layer disposed on the first surface side of the first layer. The second layer contains a polyvinyl acetal resin. The first layer includes a copolymer having a skeleton derived from a polyvinyl acetal resin (polyvinyl acetal resin unit) and a skeleton derived from a second resin component (second resin component unit). The second resin component constituting the copolymer in the first layer is an acrylic polymer, a urethane polymer, a silicone polymer, a rubber, or a vinyl acetate polymer. The second resin component is a resin different from the polyvinyl acetal resin. The copolymer has a skeleton derived from a polyvinyl acetal resin and a skeleton derived from a second resin component, and is a polyvinyl acetal resin-second resin component copolymer.

  Since the intermediate film according to the present invention has the above-described configuration, the rigidity of the laminated glass using the intermediate film can be increased, and the penetration resistance of the laminated glass can be increased. Further, in order to obtain a laminated glass, the interlayer film is disposed between the first laminated glass member and the second laminated glass member. Even if the thickness of the first laminated glass member is small, the rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. Further, even if both the first laminated glass member and the second laminated glass member are thin, the rigidity of the laminated glass can be sufficiently increased by using the intermediate film according to the present invention.

  For example, even if the thickness of the glass plate is thin, if the rigidity of the laminated glass can be increased due to the interlayer film, the weight of the laminated glass can be reduced. When the laminated glass is lightweight, the amount of material used for the laminated glass can be reduced, and the environmental load can be reduced. Furthermore, when a lightweight laminated glass is used for an automobile, fuel efficiency can be improved, and as a result, the environmental load can be reduced. In the present invention, since the rigidity of the interlayer film is high, the weight of the laminated glass can be reduced.

  When both the first laminated glass member and the second laminated glass member have a large thickness, the rigidity of the laminated glass can be considerably increased by using the interlayer film according to the present invention.

  By the way, in order to obtain an intermediate film, a recovered material (recovered intermediate film) used at least once to obtain an intermediate film may be reused. As the recovered material (recovered intermediate film) used at least once to obtain the interlayer, unnecessary portions (ears) at both ends of the intermediate film generated in the manufacturing process of the intermediate film, and the intermediate material generated in the manufacturing process of the laminated glass are used. Unnecessary parts (trim) around the film, interlayer for laminated glass obtained by separating and removing the glass plate from defective laminated glass generated in the manufacturing process of laminated glass, and used vehicles and aging And an interlayer film obtained by separating and removing a glass plate from a laminated glass obtained by dismantling a building that has been dismantled. The unnecessary intermediate film generated in the manufacturing process of the intermediate film also corresponds to the recovered material used at least once to obtain the intermediate film. If the haze after re-kneading the intermediate film material is low, the intermediate film material can be reused. In the present invention, haze after re-kneading can be reduced, and recyclability can be improved.

  Since the effect of the present invention is more excellent, the peak temperature of the loss tangent of the skeleton derived from the second resin component in the copolymer in the first layer is preferably −30 ° C. or higher, more preferably The temperature is at least -15 ° C, more preferably at least -10 ° C, preferably at most 10 ° C, more preferably at most 3 ° C.

  The intermediate film may have a two-layer structure or a three-layer structure or more, and includes a third layer in addition to the first layer and the second layer. May be. It is preferable that the intermediate film includes a third layer disposed on a second surface side of the first layer opposite to the first surface.

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

  FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention.

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

  Note that other layers may be disposed between the second layer 2 and the first layer 1 and between the first layer 1 and the third layer 3, respectively. It is preferable that the second layer 2 and the first layer 1 and the first layer 1 and the third layer 3 are each directly laminated. As another layer, a layer containing polyethylene terephthalate or the like can be mentioned.

  The first layer 1 contains the above copolymer. The second layer 2 contains a polyvinyl acetal resin. The third layer 3 preferably contains a polyvinyl acetal resin.

  Hereinafter, details of each component that can be used for each layer (the first layer, the second layer, and the third layer) constituting the intermediate film according to the present invention will be described.

(Copolymer, second resin component and polyvinyl acetal resin)
The first layer contains the copolymer. The copolymer has a skeleton derived from a polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (1)) and a skeleton derived from the second resin component. The second layer contains a polyvinyl acetal resin (hereinafter, may be described as a polyvinyl acetal resin (2)). The third layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (3)). The polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different. Each of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be used alone or in combination of two or more. In this specification, the polyvinyl acetal resin includes an acetoacetalized resin.

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

  The average polymerization degree of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, further preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, and preferably 5000 or less. More preferably, it is 4000 or less, and still more preferably, 3500 or less. When the average degree of polymerization is equal to or higher than the lower limit, the penetration resistance of the laminated glass is further increased. When the average degree of polymerization is equal to or less than the upper limit, molding of the interlayer film becomes easy.

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

  The number of carbon atoms of the acetal group in the polyvinyl acetal resin is preferably 2 to 5, more preferably 2, 3 or 4. When the number of carbon atoms of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the interlayer becomes sufficiently low. Further, the number of carbon atoms of the acetal group in the polyvinyl acetal resin is preferably 2 or 4, and in this case, the production of the polyvinyl acetal resin is efficient.

  In general, an aldehyde having 1 to 10 carbon atoms is suitably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, Examples include n-nonylaldehyde, n-decylaldehyde, and benzaldehyde. Among them, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde are preferred, acetaldehyde, propionaldehyde, n-butyraldehyde or isobutyraldehyde are more preferred, and acetaldehyde, propionaldehyde or n -Butyraldehyde is more preferred. As the aldehyde, only one kind may be used, or two or more kinds may be used in combination.

  The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 17 mol% or more, more preferably 20 mol% or more, still more preferably 22 mol% or more, preferably 40 mol% or less, more preferably. Is less than 35 mol%, more preferably 30 mol% or less, particularly preferably 25 mol% or less. When the content of the hydroxyl group is equal to or more than the lower limit, the adhesive strength of the interlayer film is further increased. In particular, when the hydroxyl group content of the polyvinyl acetal resin (1) is at least 20 mol%, the reaction efficiency is high and the productivity is excellent, and when it is less than 35 mol%, the sound insulation of the laminated glass is further enhanced. . When the content of the hydroxyl group is equal to or less than the upper limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated.

  The content of each hydroxyl group in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, preferably 38 mol% or less, more preferably 35 mol% or less, and further preferably 32 mol% or less. %, Particularly preferably 30 mol% or less, most preferably 27.5 mol% or less. When the content of the hydroxyl group is equal to or more than the lower limit, the adhesive strength of the interlayer film is further increased. When the content of the hydroxyl group is equal to or less than the upper limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated. When the content of the hydroxyl group is equal to or less than the upper limit, the rigidity is effectively increased.

  The hydroxyl group content of the polyvinyl acetal resin is a value obtained by dividing the amount of ethylene groups to which the hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, and is expressed as a percentage. The amount of the ethylene group to which the hydroxyl group is bonded can be measured, for example, in accordance with JIS K6728 “Testing method for polyvinyl butyral”.

  The degree of acetylation (the amount of acetyl group) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, and further preferably 9 mol% or more. It is at least 30 mol%, preferably at most 30 mol%, more preferably at most 25 mol%, even more preferably at most 15 mol%. When the degree of acetylation is equal to or more than the lower limit, the sound insulation becomes high, and the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. When the acetylation degree is equal to or less than the upper limit, the interlayer film and the laminated glass have high moisture resistance. 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.

  The degree of acetylation of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably at least 0.01 mol%, more preferably at least 0.5 mol%, and preferably at most 10 mol%, more preferably Is not more than 2 mol%. When the acetylation degree is equal to or more than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the acetylation degree is equal to or less than the upper limit, the interlayer film and the laminated glass have high moisture resistance.

  The degree of acetylation is a value expressed as a percentage in terms of a mole fraction obtained by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain. The amount of the ethylene group to which the acetyl group is bonded can be measured, for example, in accordance with JIS K6728 “Testing method for polyvinyl butyral”.

  The degree of acetalization (in the case of polyvinyl butyral resin, the degree of butyralization) of the polyvinyl acetal resin (1) is preferably at least 47 mol%, more preferably at least 60 mol%, and preferably at most 80 mol%, more preferably 70 mol% or less. When the degree of acetalization is equal to or more than the lower limit, the interaction with the second resin component increases, the toughness increases, and the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing a polyvinyl acetal resin becomes short.

  The degree of acetalization (in the case of polyvinyl butyral resin, the degree of butyralization) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably at least 55 mol%, more preferably at least 67 mol%, preferably Is at most 75 mol%, more preferably at most 71 mol%. When the acetalization degree is equal to or more than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing a polyvinyl acetal resin becomes short.

  The degree of acetalization is obtained by subtracting the amount of ethylene groups bonded to hydroxyl groups and the amount of ethylene groups bonded to acetyl groups from the total amount of ethylene groups in the main chain, and calculating the total amount of ethylene groups in the main chain. Is a value expressed as a percentage of the molar fraction obtained by dividing by.

  The hydroxyl content (hydroxyl content), acetalization degree (butyralization degree) and acetylation degree are preferably calculated from the results measured by a method based on JIS K6728 "Testing method for polyvinyl butyral". However, measurement according to ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl content (hydroxyl group content), the acetalization degree (butyralization degree) and the acetylation degree are determined according to JIS K6728 "Polyvinyl butyral test method". Can be calculated from the results measured by

  From the viewpoint of further improving the penetration resistance of the laminated glass, the polyvinyl acetal resin (1) has an acetylation degree (a) of 8 mol% or less and an acetalization degree (a) of 65 mol%. The polyvinyl acetal resin (A) described above or the polyvinyl acetal resin (B) having an acetylation degree (b) of more than 8 mol% is preferred. The polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) may be the polyvinyl acetal resin (A) or the polyvinyl acetal resin (B).

  The acetylation degree (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 at most 5 mol%, preferably at least 0.1 mol%, more preferably at least 0.5 mol%, further preferably at least 0.8 mol%, particularly preferably at least 1 mol%. When the acetylation degree (a) is equal to or less than the upper limit and equal to or greater than the lower limit, transfer of the plasticizer can be easily controlled, and the sound insulation of the laminated glass is further enhanced.

  The degree of acetalization (a) of the polyvinyl acetal resin (A) is 65 mol% or more, preferably 67 mol% or more, more preferably 70 mol% or more, still more preferably 70.5 mol% or more, and further preferably 71 mol% or more. Mol% or more, still more preferably 71.5 mol% or more, particularly preferably 72 mol% or more, preferably 85 mol% or less, more preferably 83 mol% or less, still more preferably 81 mol% or less, and particularly preferably 79 mol% or less. Mol% or less. When the acetalization degree (a) is equal to or more than the lower limit, the sound insulation of the laminated glass is further enhanced. When the degree of acetalization (a) is equal to or less than the upper limit, the reaction time required for producing the polyvinyl acetal resin (A) can be reduced.

  The hydroxyl group content (a) of the polyvinyl acetal resin (A) is preferably at least 18 mol%, more preferably at least 19 mol%, further preferably at least 20 mol%, particularly preferably at least 21 mol%, preferably at least 40 mol%. Mol% or less, more preferably 37 mol% or less, still more preferably 34 mol% or less, still more preferably 31 mol% or less, still more preferably 30 mol% or less, particularly preferably 29 mol% or less, and most preferably 28 mol% or less. Mol% or less. When the hydroxyl group content (a) is equal to or greater than the lower limit, the adhesive strength of the first layer is further increased. When the hydroxyl group content (a) is equal to or less than the upper limit, the sound insulation of the laminated glass is further enhanced.

  The acetylation degree (b) of the polyvinyl acetal resin (B) exceeds 8 mol%, preferably 9 mol% or more, more preferably 9.5 mol% or more, further preferably 10 mol% or more, and particularly preferably. It is at least 10.5 mol%, preferably at most 30 mol%, more preferably at most 28 mol%, further preferably at most 26 mol%, particularly preferably at most 24 mol%. When the acetylation degree (b) is equal to or more than the lower limit, the sound insulation of the laminated glass is further enhanced. When the acetylation degree (b) is equal to or less than the upper limit, the reaction time required for producing the polyvinyl acetal resin (B) can be reduced.

  The degree of acetalization (b) of the polyvinyl acetal resin (B) is preferably at least 50 mol%, more preferably at least 53 mol%, further preferably at least 55 mol%, particularly preferably at least 60 mol%, preferably at least 80 mol%. %, More preferably 78 mol% or less, further preferably 76 mol% or less, particularly preferably 74 mol% or less. When the acetalization degree (b) is equal to or more than the lower limit, the sound insulation of the laminated glass is further enhanced. When the degree of acetalization (b) is equal to or less than the upper limit, the reaction time required to produce the polyvinyl acetal resin (B) can be reduced.

  The hydroxyl group content (b) of the polyvinyl acetal resin (B) is preferably at least 18 mol%, more preferably at least 19 mol%, further preferably at least 20 mol%, particularly preferably at least 21 mol%, preferably at least 38 mol%. It is at most 35 mol%, more preferably at most 35 mol%, still more preferably at most 31 mol%, still more preferably at most 30 mol%, even more preferably at most 29 mol%, particularly preferably at most 28 mol%. When the content (b) of the hydroxyl group is equal to or more than the lower limit, the adhesive strength of the second layer is further increased. When the hydroxyl group content (b) is equal to or less than the upper limit, the sound insulating properties of the laminated glass are further enhanced.

  The polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) are each preferably a polyvinyl butyral resin, a polyvinyl acetoacetal resin, or a polyvinyl butyral-polyvinyl acetoacetal resin (a co-acetal resin), and a polyvinyl butyral resin. Is more preferable.

  The copolymer is obtained by mixing the polyvinyl acetal resin contained in the first layer and the second resin component contained in the first layer at the time of forming the first layer, and then mixing the polyvinyl acetal resin with a part of the polyvinyl acetal resin. It may be obtained by copolymerizing a part of the second resin component.

  The above-mentioned copolymer may be mixed or mixed with the polyvinyl acetal resin contained in the first layer and the second resin component contained in the first layer at the time of forming the first layer after being synthesized or prepared in advance. Good.

  From the viewpoint of further increasing the rigidity, further increasing the rigidity over a wider temperature range, and particularly further improving the sound insulation, the second resin component is preferably an acrylic polymer or a vinyl acetate polymer. Preferably, it is more preferably an acrylic polymer. The polymer includes a copolymer.

  From the viewpoint of further increasing the rigidity, further increasing the rigidity over a wider temperature range, and in particular, further improving the sound insulation, the acrylic polymer is a polymer of a polymer component containing a (meth) acrylic acid ester. Is preferred. The glass transition temperature of the skeleton derived from the second resin component can be easily controlled by selecting the type and the amount of the (meth) acrylate ester.

  From the viewpoint of further increasing the rigidity and further increasing the rigidity over a wider temperature range, the glass transition temperature of the skeleton derived from the second resin component in the copolymer in the first layer is as follows: The glass transition temperature of the skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer is preferably 30 ° C. or higher, more preferably 35 ° C. or higher. The glass transition temperature of the skeleton derived from the second resin component in the copolymer in the first layer and the glass transition temperature derived from the polyvinyl acetal resin in the copolymer in the first layer. The upper limit of the absolute value of the difference from the glass transition temperature of the skeleton is not particularly limited. The upper limit of this absolute value is preferably 100 ° C. or less.

  From the viewpoint of increasing the rigidity and sound insulation in a well-balanced manner, the skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer and the second skeleton in the copolymer in the first layer. In a total of 100% by weight of the skeleton derived from the resin component, the content of the skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer is preferably 5% by weight or more (preferably 10% by weight). % By weight, more preferably 15% by weight or more), 60% by weight or less (preferably 55% by weight or less, more preferably 50% by weight or less), and the second layer in the copolymer in the first layer. The content of the skeleton derived from the resin component is 40% by weight or more (preferably 45% by weight or more, more preferably 50% by weight or more), 95% by weight or less (preferably 90% by weight or less, Ri is preferably 85 wt% or less).

(Plasticizer)
The first layer does not contain or contains a plasticizer (hereinafter sometimes referred to as a plasticizer (1)). The first layer preferably contains 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 using the polyvinyl acetal resin and the plasticizer in combination, the adhesive strength of the layer containing the polyvinyl acetal resin and the plasticizer to the laminated glass member or another layer 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, an organic ester plasticizer is preferable. The plasticizer is preferably a liquid plasticizer.

  Examples of the monobasic organic acid ester include a glycol ester obtained by reacting a glycol with a monobasic organic acid. 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, heptyl acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decyl acid.

  Examples of the polybasic organic acid ester 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.

  Examples of the organic ester plasticizer include triethylene glycol di-2-ethyl propanoate, 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 Hexyl cyclohexyl acid, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl nonyl adipate, dibutyl sebacate, oil-modified sebacic alkyd, and a mixture of phosphate and adipate. No. Organic ester plasticizers other than these may be used. Other adipates other than the above-mentioned adipates may be used.

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

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

  In the above formula (1), R1 and R2 each represent an organic group having 2 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10. . R1 and R2 in the above formula (1) are each preferably an organic group having 5 to 10 carbon atoms, and more preferably an organic group having 6 to 10 carbon atoms.

  The plasticizer preferably contains triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH) or triethylene glycol di-2-ethyl propanoate. , Triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, more preferably triethylene glycol di-2-ethylhexanoate.

  The content of the plasticizer (2) with respect to 100 parts by weight of the polyvinyl acetal resin (2) (hereinafter, sometimes referred to as content (2)), and the plasticity with respect to 100 parts by weight of the polyvinyl acetal resin (3). The content of the agent (3) (hereinafter, sometimes referred to as content (3)) is preferably 1 part by weight or more, more preferably 3 parts by weight or more, further preferably 20 parts by weight or more, and particularly preferably. Is at least 25 parts by weight, preferably at most 40 parts by weight, more preferably at most 35 parts by weight, still more preferably at most 32 parts by weight, particularly preferably at most 30 parts by weight. When the content (2) and the content (3) are equal to or larger than the lower limit, the flexibility of the interlayer is increased, and the handling of the interlayer is facilitated. In particular, when the content (2) and the content (3) are 20 parts by weight or more, the rigidity is effectively increased. When the content (2) and the content (3) are equal to or less than the upper limit, the mechanical strength of the interlayer film is further increased, and the penetration resistance of the laminated glass is further increased. In particular, when the content (2) and the content (3) are 35 parts by weight or less, the penetration resistance of the laminated glass is effectively increased.

  The content of the plasticizer (1) relative to 100 parts by weight of the copolymer (hereinafter, sometimes referred to as content (1)) is preferably 0 parts by weight (unused) or more, more preferably 1 part by weight. Parts by weight, more preferably 3 parts by weight or more, preferably 80 parts by weight or less, more preferably 70 parts by weight or less, further preferably 50 parts by weight or less, particularly preferably 30 parts by weight or less. Since the first layer contains the second resin component or the copolymer, it is not necessary to use a plasticizer. Even when a plasticizer is used, the content of the plasticizer can be reduced. Since the plasticizer is relatively expensive, the cost of the interlayer can be reduced by reducing the amount of the plasticizer used.

  In order to lower the cost of the intermediate film, the content (2) is preferably larger than the content (1), and the content (3) is preferably larger than the content (1). preferable. In this case, from the viewpoint of reducing the cost of the intermediate film, the absolute value of the difference between the content (2) and the content (1), and the content (3) and the content (1) 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 (2) and the content (1), and the absolute value of the difference between the content (3) and the content (1) are preferably 40 parts by weight or less, respectively. More preferably 35 parts by weight or less, even more preferably 32 parts by weight or less, still more preferably 30 parts by weight or less, still more preferably 22 parts by weight or less, particularly preferably 20 parts by weight or less, most preferably 15 parts by weight or less. is there.

(Heat-blocking compound)
The intermediate film preferably contains a heat-shielding compound. The first layer preferably contains a heat-shielding compound. It is preferable that the second layer contains a heat shielding compound. The third layer preferably contains a heat-shielding compound. The heat-insulating compound may be used alone or in combination of two or more.

Component X:
The intermediate film preferably contains at least one component X of a phthalocyanine compound, a naphthalocyanine compound, and an anthocyanin 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. Component X is a thermal barrier 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 the component X, conventionally known phthalocyanine compounds, naphthalocyanine compounds, and anthocyanin compounds can be used.

  Examples of the component X include phthalocyanine, phthalocyanine derivatives, naphthalocyanine, naphthalocyanine derivatives, anthocyanin, and anthocyanin derivatives. Each of the phthalocyanine compound and the phthalocyanine derivative preferably has a phthalocyanine skeleton. The naphthalocyanine compound and the naphthalocyanine derivative each preferably have a naphthalocyanine skeleton. The anthocyanin compound and the anthocyanin derivative each preferably have an anthocyanin 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 phthalocyanine, a phthalocyanine derivative, naphthalocyanine, and a naphthalocyanine derivative. And more preferably at least one of phthalocyanine and a derivative of phthalocyanine.

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

  In 100% by weight of the layer containing the component X (first layer, second layer or third layer), the content of the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight or more. Wt% or more, more preferably 0.01 wt% or more, particularly preferably 0.02 wt% or more, preferably 0.2 wt% or less, more preferably 0.1 wt% or less, and even more preferably 0.05 wt% or less. %, Particularly preferably 0.04% by weight or less. When the content of the component X is equal to or higher than the lower limit and equal to or lower than the upper limit, the heat shielding property becomes sufficiently high and the visible light transmittance becomes sufficiently high. For example, the visible light transmittance can be 70% or more.

Thermal barrier particles:
It is preferable that the intermediate film contains heat shielding particles. The first layer preferably contains the heat shielding particles. The second layer preferably contains the heat shielding particles. The third layer preferably contains the heat shielding particles. The heat shielding particles are a heat shielding compound. By using the heat shielding particles, infrared rays (heat rays) can be effectively blocked. Only one kind of the heat shielding particles may be used, or two or more kinds thereof may be used in combination.

  From the viewpoint of further increasing 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.

  Infrared light having a wavelength of 780 nm or longer longer than visible light has a smaller energy amount than ultraviolet light. However, infrared rays have a large thermal effect, and are emitted as heat when infrared rays are absorbed by a substance. For this reason, infrared rays are generally called heat rays. By using the above-mentioned heat shielding particles, infrared rays (heat rays) can be effectively blocked. Note that the heat shielding particles mean particles that can absorb infrared rays.

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

  The tungsten oxide particles are generally represented by the following formula (X1) or (X2). In the intermediate film, tungsten oxide particles represented by the following formula (X1) or (X2) are preferably 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 W is tungsten, O is oxygen, and x, y and z are 0.001 ≦ x / y ≦ 1 and 2.0 <z / y. Satisfies ≦ 3.0.

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

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. 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 size 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, more preferably 0.05 μm or less. When the average particle diameter is equal to or more than the above lower limit, the heat ray shielding property is sufficiently high. When the average particle diameter is equal to or less than the upper limit, the dispersibility of the heat shielding particles increases.

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

  In 100% by weight of the layer containing the heat shielding particles (first layer, second layer or third layer), the content of the heat shielding particles is preferably at least 0.01% by weight, more preferably 0% by weight. 0.1% by weight or more, more preferably 1% by weight or more, particularly preferably 1.5% by weight or more, preferably 6% by weight or less, more preferably 5.5% by weight or less, further preferably 4% by weight or less, particularly preferably Preferably it is at most 3.5% by weight, most preferably at most 3.0% by weight. When the content of the heat shielding particles is equal to or more than the lower limit and equal to or less than the upper limit, the heat shielding property is sufficiently increased, and the visible light transmittance is sufficiently increased.

The layer (the first layer, the second layer, or the third layer) containing the heat insulating particles may contain the heat insulating 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-insulating particles is within the above range, the heat-insulating properties are 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, further preferably 1.5 g / m ² or more, particularly preferably 3 g / m ² or more. Is 11 g / m ² or less, more preferably 10 g / m ² or less, still more preferably 9 g / m ² or less, and particularly preferably 7 g / m ² or less. When the above ratio is equal to or more than the above lower limit, the heat shielding property is further increased. When the ratio is equal to or less than the upper limit, the visible light transmittance is further increased.

(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. By using the metal salt M, it becomes easy to control the adhesiveness between the interlayer and the laminated glass member or the adhesiveness between the layers in the interlayer. As the metal salt M, only one kind may be used, or two or more kinds may be used in combination.

  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.

  Further, 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 potassium carboxylate having 2 to 16 carbon atoms.

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

  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, and still more preferably 20 ppm or more. , Preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less. When the total content of Mg and K is equal to or more than the lower limit and equal to or less than the upper limit, the adhesiveness between the interlayer and the laminated glass member or the adhesiveness between the layers in the interlayer can be more favorably controlled.

(UV shielding 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. By using the ultraviolet ray shielding agent, even if the interlayer film and the laminated glass are used for a long period of time, the visible light transmittance becomes more difficult to decrease. Only one kind of the ultraviolet shielding agent may be used, or two or more kinds may be used in combination.

  The ultraviolet ray shielding agent includes an ultraviolet ray absorbent. It is preferable that the ultraviolet shielding agent is an ultraviolet absorbing agent.

  Examples of the ultraviolet shielding agent include a metal-based ultraviolet shielding agent (an ultraviolet shielding agent containing a metal), a metal oxide-based ultraviolet shielding agent (an ultraviolet shielding agent containing a metal oxide), and a benzotriazole-based ultraviolet shielding agent ( UV shielding agent having a benzotriazole structure), benzophenone UV shielding agent (UV shielding agent having a benzophenone structure), triazine UV shielding agent (UV shielding agent having a triazine structure), malonic ester UV shielding agent (malonic acid) UV shielding agents having an ester structure), anilide anilide UV shielding agents (UV shielding agents having an oxalic anilide structure), and benzoate UV shielding agents (UV shielding agents having a benzoate structure).

  Examples of the metal-based ultraviolet shielding agent include platinum particles, particles whose surfaces are coated with silica, palladium particles, and particles whose surfaces are coated with silica. It is preferable that the ultraviolet shielding agent is not a heat shielding particle.

  The above-mentioned ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet shielding agent, a benzophenone-based ultraviolet shielding agent, a triazine-based ultraviolet shielding agent or a benzoate-based ultraviolet shielding agent, and more preferably a benzotriazole-based ultraviolet shielding agent or a benzophenone-based ultraviolet shielding agent. And more preferably a benzotriazole-based ultraviolet shielding agent.

  Examples of the metal oxide-based ultraviolet shielding agent include zinc oxide, titanium oxide, and cerium oxide. Further, the surface of the metal oxide-based ultraviolet shielding agent may be coated. Examples of the coating material on the surface of the metal oxide-based ultraviolet shielding agent include an insulating metal oxide, a hydrolyzable organosilicon compound, and a silicone compound.

  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 shielding agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“Tinuvin P” manufactured by BASF) and 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole (“Tinuvin 320” manufactured by BASF), 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF) Tinuvin 326 ") and benzotriazole-based ultraviolet shielding agents such as 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (" Tinuvin328 "manufactured by BASF). The ultraviolet ray shielding agent is preferably a benzotriazole-based ultraviolet ray shielding agent containing a halogen atom, and more preferably a benzotriazole-based ultraviolet ray shielding agent containing a chlorine atom, because of its excellent ability to absorb ultraviolet rays.

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

  Examples of the triazine-based ultraviolet shielding agent include “LA-F70” manufactured by ADEKA and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]. -Phenol (“Tinuvin 1577FF” manufactured by BASF) and the like.

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

  Commercial products of the above-mentioned malonic ester ultraviolet ray shielding agent include Hostavin B-CAP, Hostavin PR-25 and Hostavin PR-31 (all manufactured by Clariant).

  Examples of the oxalic acid anilide-based ultraviolet shielding agent include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide and N- (2-ethylphenyl) -N ′. Oxalic acid diamides having an aryl group substituted on a nitrogen atom, such as-(2-ethoxy-phenyl) oxalic acid diamide and 2-ethyl-2'-ethoxy-oxyanilide ("SandvorVSU" manufactured by Clariant), are mentioned. No.

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

  From the viewpoint of further suppressing the decrease in the visible light transmittance after the elapse of the period, the ultraviolet ray shielding in the 100% by weight of the layer (first layer, second layer or third layer) containing the ultraviolet ray shielding agent is used. The content of the agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, further preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably 2.5% by weight or more. % By weight, more preferably 2% by weight or less, further preferably 1% by weight or less, particularly preferably 0.8% by weight or less. In particular, when the content of the ultraviolet shielding agent is 0.2% by weight or more in 100% by weight of the layer containing the ultraviolet shielding agent, the visible light transmittance of the interlayer film and the laminated glass after the lapse of the period is reduced. It can be suppressed significantly.

(Antioxidant)
The intermediate film preferably contains an antioxidant. The first layer preferably contains an antioxidant. Preferably, the second layer contains an antioxidant. The third layer preferably contains an antioxidant. One of the above antioxidants may be used alone, or two or more thereof may be used in combination.

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

  The antioxidant is preferably a phenolic antioxidant or a phosphorus antioxidant.

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

  Examples of the phosphorus antioxidants include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonyl phenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, and bis (decyl) pentaerythritol diphosphite. Phytite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphite, tris (2,4-di-t-t -Butylphenyl) phosphite and 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus. One or more of these antioxidants are preferably used.

  Commercially available antioxidants include, for example, “IRGANOX 245” manufactured by BASF, “IRGAFOS 168” manufactured by BASF, “IRGAFOS 38” manufactured by BASF, “Sumilyzer BHT” manufactured by Sumitomo Chemical Co., Ltd. IRGANOX 1010 "and the like.

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

(Other ingredients)
The intermediate film, the first layer, the second layer, and the third layer may include, as necessary, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive strength adjuster, a moisture resistant agent, and a fluorescent enhancer. It may contain additives such as whitening agents and infrared absorbers. One of these additives may be used alone, or two or more thereof may be used in combination.

(Other details of interlayer for laminated glass)
From the viewpoint of further increasing the rigidity of the laminated glass, the glass transition temperatures of the second layer and the third layer are each preferably 31 ° C or higher, more preferably 33 ° C or higher, and even more preferably 35 ° C or higher. It is. The upper limit of the glass transition temperature of the second layer and the third layer is not particularly limited. In order to further enhance the sound insulation of the interlayer, the glass transition temperature of the second layer and the third layer may be 60 ° C or lower.

  The thickness of the intermediate film is not particularly limited. From the viewpoint of practical use, and from the viewpoint of sufficiently enhancing the penetration resistance and rigidity of the laminated glass, the thickness of the interlayer is preferably 0.1 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 interlayer is equal to or more than the above lower limit, the penetration resistance and rigidity of the laminated glass are increased. When the thickness of the interlayer is not more than the above upper limit, the transparency of the interlayer is further improved.

  Let T be the thickness of the intermediate film. The thickness of the first layer is preferably 0.0625T or more, more preferably 0.1T or more, preferably 0.375T or less, more preferably 0.25T or less.

  The thickness of each of the second 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, and more preferably 0.9 T or less. Each thickness of the second layer and the third layer may be 0.46875T or less, or may be 0.45T or less. When the thickness of each of the second layer and the third layer is not less than the lower limit and not more than the upper limit, the rigidity of the laminated glass is further increased, and bleed out of the plasticizer can be suppressed.

  The total thickness of the second 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. Further, when the total thickness of the second layer and the third layer is not less than the lower limit and not more than the upper limit, the rigidity of the laminated glass is further increased, and bleed out of the plasticizer can be suppressed.

  The method for producing the intermediate film according to the present invention is not particularly limited. As a method of manufacturing an intermediate film according to the present invention, after each layer is formed using each resin composition for forming each layer, for example, a method of laminating each obtained layer, and for forming each layer A method of laminating each layer by co-extrusion of each resin composition using an extruder and the like can be mentioned. Since it is suitable for continuous production, a production method of extrusion molding is preferred.

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

  It is preferable that the intermediate film has an uneven shape on at least one of the surfaces on both sides. More preferably, the intermediate film has irregularities on both surfaces. The method for forming the above-mentioned uneven shape is not particularly limited, and examples thereof include an emboss roll method, a calender roll method, and a profile extrusion method. Among them, the embossing roll method is preferable since embosses having a large number of uneven shapes having a constant uneven pattern can be formed quantitatively.

(Laminated glass)
FIG. 2 is a cross-sectional view schematically showing one example of a laminated glass using the interlayer film for laminated glass shown in FIG.

  The laminated glass 31 shown in FIG. 2 includes a first laminated glass member 21, a second laminated glass member 22, and the intermediate film 11. The intermediate film 11 is disposed between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched therebetween.

  On the first surface 11a of the intermediate film 11, a first laminated glass member 21 is laminated. A second laminated glass member 22 is laminated on a second surface 11b of the intermediate film 11 opposite to the first surface 11a. The first laminated glass member 21 is laminated on the outer surface 2 a of the second layer 2. The second laminated glass member 22 is laminated on the outer surface 3a of the third layer 3.

  As described above, the laminated glass according to the present invention includes the first laminated glass member, the second laminated glass member, and the intermediate film, and the intermediate film is an intermediate film for laminated glass according to the present invention. It is. In the laminated glass according to the present invention, the intermediate film is disposed between the first laminated glass member and the second laminated glass member.

  Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. The laminated glass includes not only a laminated glass having an interlayer film sandwiched between two glass plates, but also a laminated glass having an interlayer film sandwiched between a glass plate and a PET film or the like. The laminated glass is a laminate having a glass plate, and it is preferable that at least one glass plate is used.

  Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include a float plate glass, a heat ray absorption plate glass, a heat ray reflection plate glass, a polished plate glass, a template plate glass, a mesh plate glass, and a line plate glass. The organic glass is a synthetic resin glass substituted for the inorganic glass. Examples of the organic glass include a polycarbonate plate and a poly (meth) acrylic resin plate. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

  The thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. When the laminated glass member is a glass plate, 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. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more, preferably 0.5 mm or less.

  By using the interlayer film according to the present invention, the rigidity of the laminated glass can be kept high even if the thickness of the laminated glass is small. From the viewpoint of reducing the weight of the laminated glass, reducing the environmental load by reducing the material of the laminated glass, and improving the fuel efficiency of automobiles by reducing the weight of the laminated glass, and reducing the environmental load, The thickness of the laminated glass member is preferably 2 mm or less, more preferably 1.8 mm or less, still more preferably 1.6 mm or less, even more preferably 1.5 mm or less, even more preferably 1.4 mm or less, and even more. It is preferably at most 1.3 mm, more preferably at most 1.2 mm, even more preferably at most 1.1 mm, further preferably at most 1 mm, still more preferably at most 0.8 mm, particularly preferably at most 0.7 mm. From the viewpoint of improving the fuel efficiency of the automobile by reducing the weight of the laminated glass and reducing the environmental load, the total thickness of the two glass plates and the total thickness of the two laminated glass members in the laminated glass are preferably Is not more than 4 mm, more preferably not more than 3.6 mm, still more preferably not more than 3.2 mm, still more preferably not more than 3 mm, still more preferably not more than 2.8 mm, still more preferably not more than 2.6 mm, and still more preferably. It is 2.4 mm or less, still more preferably 2.2 mm or less, still more preferably 2 mm or less, even more preferably 1.6 mm or less, and particularly preferably 1.4 mm or less.

  The method for producing the laminated glass is not particularly limited. For example, the intermediate film is interposed between the first laminated glass member and the second laminated glass member, passed through a pressing roll, or placed in a rubber bag and suctioned under reduced pressure to form the first laminated glass member. The air remaining between the laminated glass member, the second laminated glass member and the interlayer film is degassed. Thereafter, pre-adhesion is performed at about 70 to 110 ° C. to obtain a laminate. Next, the laminate is placed in an autoclave or pressed, and pressure-bonded at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. Thus, a laminated glass can be obtained. When manufacturing the laminated glass, the first layer, the second layer, and the third layer may be laminated.

  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 for other purposes. The intermediate film and the laminated glass are preferably an intermediate film and a laminated glass for a vehicle or a building, and more preferably an intermediate film and a laminated glass for a vehicle. The interlayer film and the laminated glass can be used for a windshield, a side glass, a rear glass, a roof glass, and the like of an automobile. The interlayer film and the laminated glass are suitably used for automobiles. The interlayer is used to obtain laminated glass for automobiles.

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

  The following materials were prepared.

(Polyvinyl acetal resin)
Polyvinyl acetal resin (A): using n-butyraldehyde, average polymerization degree of polyvinyl alcohol (PVA) 1700, hydroxyl content 30.6 mol%, acetylation degree 0.9 mol%, acetalization degree (butyralization) Degree) 68.5 mol%
Polyvinyl acetal resin (B): using n-butyraldehyde, average polymerization degree of polyvinyl alcohol (PVA) 800, hydroxyl content 34 mol%, acetylation degree 0.9 mol%, acetalization degree (butyralization degree) 65.1 mol%
Polyvinyl acetal resin (C): using n-butyraldehyde, average polymerization degree of polyvinyl alcohol (PVA) 1700, hydroxyl content 34 mol%, acetylation degree 5 mol%, acetalization degree (butyralization degree) 61 mol %
Polyvinyl acetal resin (D): using n-butyraldehyde, average polymerization degree of polyvinyl alcohol (PVA) 1700, hydroxyl content 34 mol%, acetylation degree 10 mol%, acetalization degree (butyralization degree) 56 mol %

  Regarding the polyvinyl acetal resin, the degree of acetalization (degree of butyralization), the degree of acetylation, and the content of hydroxyl groups were measured by a method based on JIS K6728 "Testing method for polyvinyl butyral". In addition, when it measured by ASTM D1396-92, the same numerical value as the method based on JISK6728 "test method for polyvinyl butyral" was shown.

(Second resin component)
Acrylic monomer (A): Acrylic monomer containing 20% by weight of ethyl acrylate, 30% by weight of butyl acrylate, 20% by weight of benzyl acrylate, and 30% by weight of 2-hydroxyethyl acrylate Acrylic monomer (B): Acrylic monomer containing 28% by weight of ethyl acrylate, 22% by weight of butyl acrylate, 30% by weight of benzyl acrylate, and 20% by weight of 2-hydroxyethyl acrylate Acrylic monomer (C): 75% by weight of ethyl acrylate And an acrylic monomer containing benzyl acrylate 25% by weight Acrylic monomer (D): ethyl acrylate 25% by weight, butyl acrylate 22% by weight, benzyl acrylate 23% by weight, and 2-hydroxyethyl acrylate 30 Weight% acrylic monomer containing acrylic monomer ( E): 40% by weight of ethyl acrylate, 10% by weight of butyl acrylate, and 50% by weight of 2-ethylhexyl acrylate
Acrylic monomer (F): an acrylic monomer containing 40% by weight of ethyl acrylate, 20% by weight of butyl acrylate, 10% by weight of 2-ethylhexyl acrylate, and 30% by weight of 2-hydroxyethyl acrylate ): An acrylic monomer containing 50% by weight of ethyl acrylate, 10% by weight of benzyl acrylate, and 40% by weight of 2-hydroxyethyl acrylate Acrylic monomer (H): 45% by weight of ethyl acrylate and 30% of butyl acrylate Acrylic monomer containing 20% by weight and 25% by weight of benzyl acrylate Vinyl acetate monomer (I): Vinyl acetate monomer which is 100% by weight of vinyl acetate

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

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

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

(Example 1)
Preparation of the composition for forming the first layer:
The copolymer (A) is copolymerized by using 100 parts by weight of the polyvinyl acetal resin (A) (at the time of copolymer synthesis) and 300 parts by weight of the acrylic monomer (A) (at the time of copolymer synthesis). Formed. 400 parts by weight of this copolymer (A), 0.2 parts by weight of an ultraviolet shielding agent (Tinuvin 326) and 0.2 parts by weight of an antioxidant (BHT) are mixed to form a first layer. A composition was obtained.

Preparation of the composition for forming the second layer and the third layer:
100 parts by weight of a polyvinyl acetal resin (A), 20 parts by weight of a plasticizer (3GO), 0.2 parts by weight of an ultraviolet shielding agent (Tinuvin 326), and 0.2 parts by weight of an antioxidant (BHT) are mixed, A composition for forming the second layer and the third layer was obtained.

Preparation of interlayer:
The composition for forming the first layer and the composition for forming the second layer and the third layer are co-extruded using a co-extruder to form a second layer (thickness). An intermediate film (760 μm in thickness) having a laminated structure of (330 μm) / first layer (100 μm in thickness) / third layer (330 μm in thickness) was produced.

Preparation of laminated glass:
Two washed and dried glass plates (first laminated glass member and second laminated glass member, clear float glass, 25 cm long × 10 cm wide × 2.5 mm thick) were prepared. The obtained intermediate film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was put in a rubber bag and degassed at a vacuum of 2660 Pa (20 torr) for 20 minutes. Thereafter, the laminate was vacuum-pressed while being kept degassed at 90 ° C. for 30 minutes in an autoclave. The laminate preliminarily pressed in this manner was pressed in an autoclave at 135 ° C. under a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

(Examples 2 to 9, Reference Examples 10 to 13, and Comparative Examples 1 and 2)
The types and amounts of the components used in the composition for forming the first layer, the types and the amounts of the components used in the compositions for forming the second layer and the third layer, Except for setting the thickness of the layer, the thickness of the second layer, the thickness of the third layer, the thickness of the first laminated glass member and the thickness of the second laminated glass member as shown in Tables 1 to 3 below. In the same manner as in Example 1, an interlayer film and a laminated glass were obtained. The copolymers (A) to (I) shown in the table are obtained by copolymerizing the polyvinyl acetal resin and the second resin component shown in the table, and have a skeleton and a second resin component derived from the polyvinyl acetal resin. It is a copolymer having a derived skeleton. In Comparative Examples 1 and 2, no copolymer was used. In Comparative Example 3, a polyvinyl acetal resin and an acrylic polymer were used, and no acrylic monomer was copolymerized with the polyvinyl acetal resin. In all Examples , Reference Examples, and Comparative Examples, the same type of ultraviolet shielding agent and antioxidant as in Example 1 were blended in the same amount (0.2 parts by weight) as in Example 1. If an intermediate film cannot be produced by co-extrusion, the first layer, the second layer, and the third layer can be easily formed by forming the first layer, the second layer, and the third layer by a solution casting method or a hot pressing method and then laminating the layers. was gotten.

(Evaluation)
(1) Glass transition temperature / peak temperature of loss tangent A kneaded product having each composition of the first layer in the examples , reference examples and comparative examples was prepared. The obtained kneaded material 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 left at 25 ° C. and a relative humidity of 30% for 2 hours. After standing for 2 hours, viscoelasticity was measured using “ARES-G2” manufactured by TAINSTRUMMENTS. A parallel plate having a diameter of 8 mm was used as a jig. The measurement was carried out under conditions of lowering the temperature from 100 ° C. to −50 ° C. at a temperature lowering rate of 3 ° C./min, and at a frequency of 1 Hz and a strain of 1%. In the measurement results obtained, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). In the copolymer, the peak on the high temperature side is derived from the skeleton derived from the polyvinyl acetal resin in the copolymer, and the peak on the low temperature side is derived from the skeleton derived from the second resin component in the copolymer. Originated.

(2) Flexural rigidity The obtained laminated glass was prepared. The flexural rigidity was evaluated by a test method schematically shown in FIG. As a measuring device, a universal material testing machine 5966 manufactured by Instron Japan Company Limited equipped with a static three-point bending test jig 2810 was used. The measurement conditions were as follows: the measurement temperature was 20 ± 3 ° C., the distance D1 was 18 cm, the distance D2 was 25 cm, and the glass was deformed in the direction of F at a displacement speed of 1 mm / min and a displacement of 1.5 mm was applied. The stress was measured and the bending stiffness was calculated. The bending stiffness was determined based on the following criteria.

[Bending stiffness criteria]
：: stress is 5 MPa or more Δ: stress is 2 MPa or more and less than 5 MPa ×: stress is less than 2 MPa

(3) Tensile properties (rigidity) of the first layer at 25 ° C
A composition for forming a first layer having a thickness of about 400 μm was prepared, and a tensile test was performed at a tensile speed of 200 mm / min using an autograph (“AG-IS” manufactured by Shimadzu Corporation). Of each was evaluated. Tensile properties were determined according to the following criteria.

[Criteria for determining tensile properties (rigidity)]
○: Young's modulus is 2 MPa or more ：: Young's modulus is 1 MPa or more and less than 2 MPa Δ: Young's modulus is 0.5 MPa or more and less than 1 MPa X: Young's modulus is less than 0.5 MPa

(4) Sound insulation The laminated glass is vibrated by a vibration generator for vibration damping ("Vibrator G21-005D" manufactured by Shinken Co., Ltd.), and the vibration characteristics obtained from the vibration are measured by a mechanical impedance measuring device (manufactured by Lion Corporation). Amplification was performed using “XG-81”, and the vibration spectrum was analyzed using an FFT spectrum analyzer (“FFT Analyzer HP3582A” manufactured by Yokogawa Hewlett-Packard Company). The peak frequency of the loss coefficient was determined, and the loss coefficient of the laminated glass at 3000 Hz at 20 ° C. was further calculated. The sound insulation was determined from the loss coefficient according to the following criteria. When the loss coefficient is 0.1 or more, the sound insulation is excellent, and when the loss coefficient is 0.2 or more, the sound insulation is more excellent.

[Sound insulation criterion]
：: loss coefficient of 0.2 or more Δ: loss coefficient of 0.1 or more, less than 0.2 ×: loss coefficient of less than 0.1

(5) Measurement of haze after re-kneading A composition for forming the first layer was prepared. The composition for forming the first layer was re-kneaded at 130 ° C. for 10 minutes to obtain a re-kneaded composition. The haze of the obtained laminated glass was measured using a haze meter (“TC-HIDIPK” manufactured by Tokyo Denshoku Co., Ltd.) in accordance with JIS K6714. The haze after re-kneading was determined according to the following criteria.

：: Haze after remixing is less than 0.5% Δ: Haze after remixing is 0.5% or more and less than 0.8% X: Haze after remixing is 0.8% or more

  Details and results are shown in Tables 1 to 3 below. In Tables 1 to 3 below, descriptions of the components other than the polyvinyl acetal resin, the copolymer, the acrylic copolymer, and the plasticizer are omitted.

DESCRIPTION OF SYMBOLS 1 ... 1st layer 1a ... 1st surface 1b ... 2nd surface 2 ... 2nd layer 2a ... Outer surface 3 ... 3rd layer 3a ... Outer surface 11 ... Interlayer 11A ... Interlayer ( 1 layer)
11a first surface 11b second surface 21 first laminated glass member 22 second laminated glass member 31 laminated glass

Claims (7)

A first layer; a second layer disposed on a first surface side of the first layer; and a second layer disposed on a second surface side of the first layer opposite to the first surface. A third layer ,
The first layer includes a copolymer having a skeleton derived from a polyvinyl acetal resin and a skeleton derived from a second resin component,
The second layer includes a polyvinyl acetal resin,
The second resin component constituting the copolymer of the first layer is selected from the group consisting of acrylic polymers, urethane polymers, silicone polymers, rubbers, or a vinyl acetate polymer der is,
The thickness of the intermediate layer when T, the thickness of the first layer is not more than 0.375T, each thickness of the second layer and the third layer is Ru der than 0.3125T, laminated glass For intermediate film.   The laminated glass according to claim 1, wherein a peak temperature of a loss tangent of a skeleton derived from the second resin component in the copolymer in the first layer is from -30 ° C to 10 ° C. Interlayer.   In a total of 100% by weight of a skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer and a skeleton derived from the second resin component in the copolymer in the first layer. The content of the skeleton derived from the polyvinyl acetal resin in the copolymer in the first layer is not less than 5% by weight and not more than 60% by weight, and the content of the second skeleton in the copolymer in the first layer is not more than 60% by weight. 3. The interlayer film for laminated glass according to claim 1, wherein the content of the skeleton derived from the resin component is 40% by weight or more and 95% by weight or less.   The interlayer film for laminated glass according to any one of claims 1 to 3, wherein the second resin component constituting the copolymer in the first layer is an acrylic polymer. Before Symbol third layer comprises a polyvinyl acetal resin, the interlayer film for a laminated glass according to any one of claims 1 to 4. The second layer comprises a plasticizer,
The interlayer for laminated glass according to any one of claims 1 to 5, wherein the third layer contains a plasticizer. A first laminated glass member;
A second laminated glass member;
An interlayer film for laminated glass according to any one of claims 1 to 6,
A laminated glass, wherein the interlayer film for a laminated glass is disposed between the first laminated glass member and the second laminated glass member.

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