JP6985258B2 - Laminated glass interlayer film and laminated glass - Google Patents

Description

The present invention relates to a laminated glass interlayer film used to obtain a laminated glass. The present invention also relates to a laminated glass using the above-mentioned interlayer film for laminated glass.

Laminated glass is excellent in safety because the amount of scattered glass fragments is small even if it is damaged by an external impact. Therefore, the laminated glass is widely used in automobiles, railroad vehicles, aircraft, ships, buildings and the like. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between two glass plates.

As an example of the interlayer film for laminated glass, the following Patent Document 1 describes 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one of an alkali metal salt and an alkaline earth metal salt. A sound insulating layer containing 0.001 to 1.0 part by weight of the metal salt of the above and more than 30 parts by weight of a plasticizing agent is disclosed. This sound insulation layer is a single layer and can be used as an interlayer film.

Further, Patent Document 1 below also describes a multilayer interlayer film in which the sound insulation layer and another layer are laminated. The other layers laminated on the sound insulation layer include 100 parts by weight of a polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and 0.001 to 0.001 of at least one of an alkali metal salt and an alkaline earth metal salt. It contains 1.0 part by weight and 30 parts by weight or less of a plasticizing agent.

Patent Document 2 below discloses an interlayer 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 arranged between glass plates having a thickness of 4.0 mm or less.

WO2014 / 050746A1 US2013 / 0236711A1

Laminated glass using a conventional interlayer film as described in Patent Documents 1 and 2 may have low bending rigidity at room temperature. For this reason, for example, when laminated glass is used as a window glass for a side door of an automobile, there is no frame for fixing the laminated glass, and the bending caused by the low rigidity of the laminated glass causes the window glass to bend. It may interfere with opening and closing.

Further, 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 interlayer film is sandwiched between two glass plates, there is a problem that it is extremely difficult to maintain sufficiently high bending rigidity when the thickness of the glass plates is reduced.

For example, even if the thickness of the glass plate is thin, if the bending 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 the material used for the laminated glass can be reduced, and the environmental load can be reduced. Furthermore, when laminated glass, which is lightweight, is used in an automobile, fuel efficiency can be improved, and as a result, the environmental load can be reduced.

Further, the laminated glass used for automobiles and the like may have a considerably high temperature of about 65 ° C. Further, when the thickness of the glass plate is thin, the rigidity of the interlayer film has a great influence, and the bending rigidity of the laminated glass at a high temperature tends to be low. With the conventional interlayer film, it is difficult to sufficiently increase the bending rigidity of the laminated glass at a high temperature of about 65 ° C.

Further, it is desired that the laminated glass using the interlayer film has high bending rigidity and high penetration resistance.

With a conventional interlayer film, it is difficult to improve both of high bending rigidity and high penetration resistance, not just one.

An object of the present invention is to provide a laminated glass interlayer film capable of increasing the bending rigidity of a laminated glass over a wide temperature range and increasing the penetration resistance of the laminated glass. Another object of the present invention is to provide a laminated glass using the above-mentioned interlayer film for laminated glass.

According to a broad aspect of the present invention, the polyvinyl acetal resin 100 comprises a polyvinyl acetal resin, a polymer of a polymerizable component containing a (meth) acrylate compound having two or more (meth) acryloyl groups, and a plasticizer. The content of the polymer is 85 parts by weight or more and 160 parts by weight or less with respect to parts by weight, and the content of the plasticizer is 3 with respect to a total of 100 parts by weight of the polyvinyl acetal resin and the polymer. Provided is an interlayer film for laminated glass (hereinafter, may be referred to as an interlayer film) having a phase-separated structure, which is more than a part by weight and less than 15 parts by weight.

In a specific aspect of the interlayer film according to the present invention, a (meth) acrylate compound having two or more (meth) acryloyl groups and a (meth) acryloyl group in 100% by weight of the polymerizable component constituting the polymer are used. The total amount of the polymer compound having a (meth) acryloyl group other than the two or more (meth) acrylate compounds is 50% by weight or more, and the polymer is an acrylic polymer.

In a specific aspect of the interlayer film according to the present invention, the content of the plasticizer is 5 parts by weight or more with respect to 100 parts by weight of the total of the polyvinyl acetal resin and the polymer.

In a specific aspect of the interlayer film according to the present invention, the content of the plasticizer is 8 parts by weight or less with respect to 100 parts by weight of the total of the polyvinyl acetal resin and the polymer.

In a specific aspect of the interlayer film according to the present invention, the polyvinyl acetal resin and the polymer are crosslinked.

In certain aspects of the interlayer film according to the present invention, the thickness is 3 mm or less.

In a particular aspect of the interlayer film according to the present invention, the interlayer film uses a first glass plate having a thickness of 1.6 mm or less between the first glass plate and the second glass plate. It is placed and used to obtain laminated glass.

In certain aspects of the interlayer according to the present invention, the interlayer is placed between the first glass plate and the second glass plate and used to obtain a laminated glass, said first glass. The total of the thickness of the plate and the thickness of the second glass plate is 3.5 mm or less.

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

In a specific aspect of the laminated glass according to the present invention, the first laminated glass member is a first glass plate, and the thickness of the first glass plate is 1.6 mm or less.

In a specific aspect of the laminated glass according to the present invention, the first laminated glass member is a first glass plate, the second laminated glass member is a second glass plate, and the first glass. The total of the thickness of the plate and the thickness of the second glass plate is 3.5 mm or less.

The interlayer film for laminated glass according to the present invention contains a polyvinyl acetal resin, a polymer of a polymerizable component containing a (meth) acrylate compound having two or more (meth) acryloyl groups, and a plasticizer. In the interlayer film for laminated glass according to the present invention, the content of the polymer is 85 parts by weight or more and 160 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin, and the polyvinyl acetal resin and the polymer are contained. The content of the plasticizer is 3 parts by weight or more and less than 15 parts by weight with respect to 100 parts by weight in total. The laminated glass interlayer film according to the present invention has a phase-separated structure. Since the laminated glass interlayer film according to the present invention has the above-mentioned configuration, the bending rigidity of the laminated glass using the laminated glass interlayer film according to the present invention can be increased over a wide temperature range. Penetration resistance of laminated glass can be improved.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a second embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing an example of a laminated glass using the interlayer film for laminated glass shown in FIG. FIG. 4 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG. 2. FIG. 5 is a schematic diagram for explaining a method for measuring flexural rigidity.

Hereinafter, the present invention will be described in detail.

(Interlayer film for laminated glass)
The laminated glass interlayer film according to the present invention (hereinafter, may be referred to as an interlayer film) has a one-layer structure or a two-layer or more structure. The interlayer film according to the present invention may have a structure of one layer or may have a structure of two or more layers. The interlayer film according to the present invention may have a two-layer structure, may have a two-layer or more structure, or may have a three-layer structure, or may have a three-layer structure or more. May have. The interlayer film according to the present invention includes a first layer. The interlayer film according to the present invention may be a single-layer intermediate film including only the first layer, or may be a multi-layered intermediate film including the first layer and another layer.

The interlayer film according to the present invention is a polymer of a polymerizable component containing a polyvinyl acetal resin and a (meth) acrylate compound having two or more (meth) acryloyl groups (hereinafter, may be referred to as polymer X). , With plasticizers. The (meth) acrylate compound having two or more (meth) acryloyl groups is a polymerizable compound. The (meth) acrylate compound having two or more (meth) acryloyl groups is used as a part or all of the polymerizable component constituting the polymer X. In the interlayer film according to the present invention, the polymer X is used as a second resin other than the polyvinyl acetal resin.

In the interlayer film according to the present invention, the content of the polymer X is 85 parts by weight or more and 160 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin.

In the interlayer film according to the present invention, the content of the plasticizer is 3 parts by weight or more and less than 15 parts by weight with respect to a total of 100 parts by weight of the polyvinyl acetal resin and the polymer.

The interlayer film according to the present invention has a phase-separated structure.

Since the interlayer film according to the present invention has the above-mentioned structure, it is possible to increase the bending rigidity of the laminated glass using the interlayer film according to the present invention at a high temperature. In particular, the bending rigidity at 65 ° C. can be increased. Further, the bending rigidity at 23 ° C. can be increased. Further, in order to obtain laminated glass, the interlayer film is often arranged 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 using the interlayer film according to the present invention. Further, 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 using the interlayer film according to the present invention. If the thickness of both the first glass plate and the second glass plate is thick, the bending rigidity of the laminated glass becomes even higher.

With conventional interlayer films, it is difficult to sufficiently increase the bending rigidity over a wide temperature range including normal temperature and high temperature. For example, even if the bending rigidity at room temperature is high, the bending rigidity at high temperature is low, or even if the bending rigidity at high temperature is high, the bending rigidity at room temperature is low. On the other hand, in the present invention, the bending rigidity can be increased over a wide temperature range (for example, 23 ° C. and 65 ° C.).

Further, since the interlayer film according to the present invention has the above-mentioned structure, the penetration resistance of the laminated glass using the interlayer film according to the present invention can be enhanced.

From the viewpoint of enhancing bending rigidity over a wide temperature range and penetration resistance, the content of the polymer X is 85 parts by weight or more and 160 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin. From the viewpoint of further enhancing the bending rigidity over a wide temperature range and the penetration resistance, the content of the polymer X is preferably 90 parts by weight or more, preferably 90 parts by weight or more, with respect to 100 parts by weight of the polyvinyl acetal resin. It is 120 parts by weight or less.

From the viewpoint of enhancing bending rigidity over a wide temperature range and penetration resistance, the content of the plasticizer is 3 parts by weight or more and 15 parts by weight with respect to 100 parts by weight in total of the polyvinyl acetal resin and the polymer. Less than a copy. From the viewpoint of further enhancing the penetration resistance, the content of the plasticizer is preferably 4 parts by weight or more, more preferably 5 parts by weight, based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. That is all. From the viewpoint of further increasing the bending rigidity over a wide temperature range, the content of the plasticizer is preferably 13 parts by weight or less, more preferably 13 parts by weight or less, based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. Is 8 parts by weight or less.

The interlayer film has a phase-separated structure from the viewpoint of enhancing bending rigidity over a wide temperature range and penetration resistance. From the viewpoint of further enhancing the bending rigidity over a wide temperature range and the penetration resistance, it is preferable that the polymer X is an island portion (domain) in the phase separation structure. It is considered that one of the factors for achieving the above effect in the present invention is that the energy distribution proceeds smoothly due to the phase separation structure.

It is preferable that the polyvinyl acetal resin surrounds the domain, and it is preferable that the polyvinyl acetal resin is a matrix. The phase-separated structure is preferably a co-continuous structure or a sea-island structure. The phase-separated structure may be a co-continuous structure or a sea-island structure. It is preferable that the polyvinyl acetal resin and the polymer X are contained in different phases. It is preferable that the polyvinyl acetal resin and the polymer X form a phase-separated structure. In the case of a sea-island structure, the polyvinyl acetal resin may be a sea portion and the polymer X may be an island portion, and the polymer X may be a sea portion and the polyvinyl acetal resin may be an island portion. good. In the phase-separated structure, the polyvinyl acetal resin may be continuous (may have a continuous structure), and the polymer X may be continuous (may have a continuous structure). ), The polyvinyl acetal resin and the polymer X may form a co-continuous structure. In the phase-separated structure, the polyvinyl acetal resin may be present in a mesh pattern, or the polymer X may be present in a network pattern. Since the effect of the present invention is excellent, it is preferable that the polyvinyl acetal resin and the polymer X have a sea-island structure or a co-continuous structure. That is, in the phase-separated structure, it is preferable that the polyvinyl acetal resin and the polymer X form a sea-island structure or a co-continuous structure.

In the phase separation structure, the average diameter of the islands is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, particularly preferably 30 nm or more, preferably 13 μm or less, more preferably 10 μm or less, still more preferable. Is 2 μm or less, particularly preferably 1 μm or less. The diameter of each island indicates the maximum diameter, and the average diameter of the islands is obtained by averaging the diameters (maximum diameters) of a plurality of islands.

The interlayer film may have a structure of two or more layers, and may include a second layer in addition to the first layer. It is preferable that the interlayer film further includes a second layer. When the interlayer film includes the second layer, the second layer is arranged on the first surface side of the first layer.

The interlayer 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. It is preferable that the interlayer film further includes a third layer. When the interlayer film includes the second layer and the third layer, the third layer is arranged on the second surface side opposite to the first surface of the first layer. Ru.

The surface of the second layer opposite to the first layer side is preferably a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the second layer is preferably 1.6 mm or less, more preferably 1.3 mm or less. The second surface opposite to the first surface of the first layer (the surface on the second layer side) may be a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the first layer is preferably 1.6 mm or less, more preferably 1.3 mm or less. The surface of the third layer opposite to the first layer side is preferably a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the third layer is preferably 1.6 mm or less, more preferably 1.3 mm or less.

The interlayer film is arranged between the first glass plate and the second glass plate, and is suitably used for obtaining laminated glass. Since the flexural rigidity can be sufficiently increased due to the interlayer film, the total of the thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, more preferably 3 mm. It is as follows. The interlayer film is arranged between the first glass plate and the second glass plate, and is suitably used for obtaining laminated glass. Since the bending rigidity can be sufficiently increased due to the interlayer film, the interlayer film is made by using a first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). It is arranged between the glass plate 1 and the glass plate 2 and is suitably used for obtaining a laminated glass. The interlayer film comprises a first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less) and a second glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). It is more preferably used to obtain laminated glass by being arranged between the first glass plate and the second glass plate. Also in this case, the bending rigidity can be sufficiently increased due to the interlayer film.

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

It should be noted that other layers may be arranged 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 directly laminated, respectively. Examples of the other layer include a layer containing polyethylene terephthalate and the like.

FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a second embodiment of the present invention.

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

Hereinafter, the details of the first layer, the second layer and the third layer constituting the interlayer film according to the present invention, and the first layer, the second layer and the third layer The details of each component contained will be described.

(resin)
The interlayer film contains a polyvinyl acetal resin and a polymer X as a polymerizable component containing a (meth) acrylate compound having two or more (meth) acryloyl groups. It is preferable that the first layer, the second layer and the third layer each contain a polyvinyl acetal resin. It is preferable that the first layer, the second layer and the third layer each contain the polymer X. As the polyvinyl acetal resin, only one kind may be used, or two or more kinds may be used in combination. As the polymer X, only one kind may be used, or two or more kinds may be used in combination.

From the viewpoint of effectively enhancing the affinity between the resin component and the plasticizer and effectively enhancing the penetration resistance, the polyvinyl acetal resin is a polyvinyl acetatetal resin, a polyvinyl butyral resin, a polyvinylbenzyl acetal resin or a polyvinylcumin acetal. It is preferably a resin. From the viewpoint of further increasing the bending rigidity at 40 ° C., a polyvinyl acetal acetal resin is preferable. As used herein, the polyvinyl acetal resin includes acetalized resins, benzyl acetalized resins and cumin acetalized resins.

From the viewpoint of further enhancing bending rigidity over a wide temperature range and penetration resistance, the interlayer film may be a polyolefin resin, an acrylic polymer, a urethane polymer, a silicone polymer, rubber, or acetic acid as the polymer X. It preferably contains a vinyl polymer, and more preferably contains an acrylic polymer. The acrylic polymer is a polymer obtained by using 50% by weight or more of a polymerizable compound having a (meth) acryloyl group as a polymerizable component.

A (meth) acrylate compound having two or more (meth) acryloyl groups and a (meth) acrylate compound having two or more (meth) acryloyl groups in 100% by weight of the polymerizable component constituting the polymer X (meth). Meta) The total amount with the polymerizable compound having an acryloyl group is defined as the total amount A. From the viewpoint of further enhancing the bending rigidity over a wide temperature range and the sound insulation property, the total amount A is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 70% by weight or more. Is 80% by weight or more, most preferably 90% by weight or more. When the total amount A is 50% by weight or more, the obtained polymer X is an acrylic polymer.

Examples of the (meth) acrylate compound having two or more (meth) acryloyl groups include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth). ) Acrylate, Tetraethylene glycol di (meth) acrylate, Tetrapropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, 3-Methyl-1,5-pentanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dimethylol-tri Bifunctional (meth) acrylate compounds such as cyclodecandi (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, tritetramethylene glycol di (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate; Pentaerythritol tri (meth) acrylate, trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate di (meth) acrylate, dipentaerythritol tri (meth) acrylate, ε-caprolactone-modified tris- (2- (2- ( Trifunctional (meth) acrylate compounds such as meta) acryloxyethyl) isocyanurate, tris phosphate [2-((meth) acryloyloxy) ethyl]; pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth). Examples thereof include tetrafunctional or higher functional (meth) acrylate compounds such as acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The (meth) acrylate compound having two or more (meth) acryloyl groups may be an epoxy (meth) acrylate compound and a urethane (meth) acrylate compound.

The polymer X is preferably a polymer of a polymerizable component containing a (meth) acrylic acid ester. The polymer X is preferably a poly (meth) acrylic acid ester.

The poly (meth) acrylic acid ester is not particularly limited. Examples of the poly (meth) acrylic acid ester include methyl poly (meth) acrylate, ethyl poly (meth) acrylate, n-propyl poly (meth) acrylate, i-propyl poly (meth) acrylate, and poly. N-butyl (meth) acrylate, i-butyl poly (meth) acrylate, t-butyl poly (meth) acrylate, 2-ethylhexyl poly (meth) acrylate, 2-hydroxyethyl poly (meth) acrylate, 2-Hydroxypropyl poly (meth) acrylate, 4-hydroxybutyl poly (meth) acrylate, glycidyl poly (meth) acrylate, octyl poly (meth) acrylate, propyl poly (meth) acrylate, poly (meth) 2-ethyloctyl acrylate, nonyl poly (meth) acrylate, isononyl poly (meth) acrylate, decyl poly (meth) acrylate, isodecyl poly (meth) acrylate, lauryl poly (meth) acrylate, poly (meth) ) Isotetradecyl acrylate, cyclohexyl poly (meth) acrylate, isobornyl poly (meth) acrylate, benzyl poly (meth) acrylate and the like. The (meth) acrylic acid having a polar group and the (meth) acrylic acid ester include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylic acid, 4-hydroxybutyl (meth) acrylic acid, and the like. Examples thereof include (meth) glycidyl acrylate. Polyacrylic acid ester is preferable because the temperature showing the maximum value of tan δ can be easily controlled within an appropriate range in the dynamic viscoelastic spectrum, and ethyl polyacrylate, n-butyl polyacrylate, and polyacrylic acid are preferable. 2-Ethylhexyl acid or octyl polyacrylate are more preferred. The use of these preferred poly (meth) acrylic acid esters further improves the balance between the productivity of the interlayer and the properties of the interlayer. Only one kind of the poly (meth) acrylic acid ester may be used, or two or more kinds thereof may be used in combination.

It is preferable that the polyvinyl acetal resin and the polymer X are crosslinked. The interlayer film may contain the polyvinyl acetal resin and the polymer X as a crosslinked product in which the polyvinyl acetal resin and the polymer X are crosslinked. The thermoplastic resin may have a crosslinked structure. With the crosslinked structure, the shear storage elastic modulus can be controlled, and an interlayer film having both excellent flexibility and high strength can be produced.

Examples of the method for cross-linking the resin include the following methods. A method in which functional groups that react with each other are introduced into the polymer structure of a resin to form crosslinks. A method of cross-linking using a cross-linking agent having two or more functional groups that react with the functional groups present in the polymer structure of the resin. A method of cross-linking a polymer using a radical generator having a hydrogen abstraction ability such as a peroxide. A method of cross-linking by electron beam irradiation. Since it is easy to control the shear storage elastic modulus and the productivity of the interlayer film is increased, a method of introducing functional groups that react with each other into the polymer structure of the resin to form a crosslink is preferable.

When the interlayer film contains a crosslinked product of the polyvinyl acetal resin and the polymer X, a polymerizable component containing a (meth) acrylate compound having two or more (meth) acryloyl groups in the presence of the polyvinyl acetal resin. It is preferable that the step of forming the polymer X by polymerizing and obtaining an interlayer film is performed. By this step, a structure in which the polyvinyl acetal resin and the polymer X are crosslinked is formed.

The first layer (including a single-layer interlayer film) preferably contains a thermoplastic resin (hereinafter, may be referred to as a thermoplastic resin (1)). The first layer preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (1)) as the thermoplastic resin (1). When the interlayer film is a single layer having only the first layer, the interlayer film contains a polyvinyl acetal resin (1). The second layer preferably contains a thermoplastic resin (hereinafter, may be referred to as a thermoplastic resin (2)). The second layer preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (2)) as the thermoplastic resin (2). The third layer preferably contains a thermoplastic resin (hereinafter, may be referred to as a thermoplastic resin (3)). The third layer preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (3)) as the thermoplastic resin (3). The polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different. It is preferable that the polyvinyl acetal resin (1) is different from the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) because the sound insulation property is further improved. The thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be the same or different. 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. Only one kind of the thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be used, or two or more kinds thereof may be used in combination.

Examples of the thermoplastic resin include polyvinyl acetal resin, polyacrylic resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, polyvinyl alcohol resin and the like. Thermoplastic resins other than these may be used.

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

The average degree of polymerization of the polyvinyl alcohol (PVA) 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 2700 or more. It is 5000 or less, more preferably 4000 or less, still more preferably 3500 or less. When the average degree of polymerization is at least the above lower limit, the penetration resistance and bending rigidity of the laminated glass are further increased. When the average degree of polymerization is not more than the above upper limit, molding of the interlayer film becomes easy.

The average degree of polymerization of polyvinyl alcohol is determined by a method based on JIS K6726 "polyvinyl alcohol test method".

The acetal group in the polyvinyl acetal resin preferably has 2 to 10 carbon atoms, more preferably 2 to 5, and even more preferably 2, 3 or 4. Further, it is preferable that the acetal group in the polyvinyl acetal resin has 2 or 4 carbon atoms, and in this case, the production of the polyvinyl acetal resin is efficient.

As the aldehyde, generally, an aldehyde having 1 to 10 carbon atoms is preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, n-barrel aldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, and n-octylaldehyde. Examples thereof include n-nonylaldehyde, n-decylaldehyde, cuminaldehyde, and benzaldehyde. Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexyl aldehyde or n-barrel aldehyde are preferred. Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutylaldehyde or n-barrelaldehyde are more preferred, and acetaldehyde, n-butyraldehyde or n-barrelaldehyde are even more preferred. Only one kind of the above aldehyde may be used, or two or more kinds may be used in combination.

When the polyvinyl acetal resin (1) is used as a part of the interlayer film of a single layer, the hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably in the following range. The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 25 mol% or more, more preferably 28 mol% or more, more preferably 30 mol% or more, still more preferably 31.5 mol%. The above is more preferably 32 mol% or more, and particularly preferably 33 mol% or more. The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 37 mol% or less, more preferably 36.5 mol% or less, still more preferably 36 mol% or less. When the content of the hydroxyl group is at least the above lower limit, the bending rigidity becomes higher and the adhesive force of the interlayer film becomes higher. Further, when the content of the hydroxyl group is not more than the above upper limit, the flexibility of the interlayer film is increased and the handling of the interlayer film becomes easy.

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 28 mol% or less, more preferably. Is 27 mol% or less, more preferably 25 mol% or less, and particularly preferably 24 mol% or less. When the polyvinyl acetal resin (1) is used as a part of the multilayer interlayer film, it is particularly preferable to satisfy the lower limit and the upper limit of the hydroxyl group content. When the content of the hydroxyl group is at least the above lower limit, the mechanical strength of the interlayer film is further increased. In particular, when the content of the hydroxyl group of the polyvinyl acetal resin (1) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and when it is 28 mol% or less, the sound insulation of the laminated glass is further improved. .. Further, when the content of the hydroxyl group is not more than the above upper limit, the flexibility of the interlayer film is increased and the handling of the interlayer film becomes easy. In particular, laminated glass using an interlayer film in which the hydroxyl group content of the polyvinyl acetal resin (1) is 28 mol% or less tends to have low bending rigidity, but the bending rigidity is remarkably increased by the configuration of the present invention. Can be improved.

The content of each hydroxyl group of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, more preferably 30 mol% or more, still more preferably. It is 31.5 mol% or more, more preferably 32 mol% or more, and particularly preferably 33 mol% or more. The hydroxyl group content of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 37 mol% or less, more preferably 36.5 mol% or less, still more preferably 36 mol% or less. When the content of the hydroxyl group is at least the above lower limit, the bending rigidity becomes higher and the adhesive force of the interlayer film becomes higher. Further, when the content of the hydroxyl group is not more than the above upper limit, the flexibility of the interlayer film is increased and the handling of the interlayer film becomes easy.

From the viewpoint of further enhancing the sound insulation property, it is preferable that the hydroxyl group content of the polyvinyl acetal resin (1) is lower than the hydroxyl group content of the polyvinyl acetal resin (2). From the viewpoint of further enhancing the sound insulation property, it is preferable that the hydroxyl group content of the polyvinyl acetal resin (1) is lower than the hydroxyl group content of the polyvinyl acetal resin (3). From the viewpoint of further enhancing the sound insulation property, the absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (2) is preferably 1 mol% or more. , More preferably 5 mol% or more, still more preferably 9 mol% or more, particularly preferably 10 mol% or more, and most preferably 12 mol% or more. From the viewpoint of further enhancing the sound insulation property, the absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (3) is preferably 1 mol% or more. , More preferably 5 mol% or more, still more preferably 9 mol% or more, particularly preferably 10 mol% or more, and most preferably 12 mol% or more. The absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (2) is preferably 20 mol% or less. The absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (3) is preferably 20 mol% or less.

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 the mole fraction is shown as a percentage. The amount of ethylene groups to which the hydroxyl groups are bonded can be measured, for example, in accordance with JIS K6728 “Polyvinyl butyral test method”.

The degree of acetylation (acetyl group amount) 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, still more preferably 9. It is mol% or more, preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 24 mol% or less. When the degree of acetylation is equal to or higher than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer or other thermoplastic resin becomes high, the sound insulation and penetration resistance are further improved, and the performance over a long period of time is further improved. Stabilize. When the degree of acetylation is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass becomes high. 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 further excellent.

The degree of acetylation of the polyvinyl acetal resin (2) 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 less than 2 mol%. When the degree of acetylation is at least the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. When the degree of acetylation is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass becomes high.

The degree of acetylation is a value indicating the 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 ethylene group to which the acetyl group is bonded can be measured, for example, in accordance with JIS K6728 “Polyvinyl butyral test method”.

The degree of acetalization (in the case of polyvinyl butyral resin, the degree of butyralization) of the polyvinyl acetal resin (1) is preferably 47 mol% or more, more preferably 60 mol% or more, still more preferably 68 mol% or more, preferably 68 mol% or more. It is 85 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less. When the degree of acetalization is at least the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. When the degree of acetalization is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin is shortened.

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 55 mol% or more, more preferably 60 mol% or more, preferably 60 mol% or more. Is 75 mol% or less, more preferably 71 mol% or less. When the degree of acetalization is at least the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. When the degree of acetalization is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin is shortened.

The degree of acetalization is determined as follows. First, the value obtained by subtracting the amount of ethylene groups to which the hydroxyl group is bonded and the amount of ethylene groups to which the acetyl group is bonded is obtained from the total amount of ethylene groups in the main chain. The obtained value is divided by the total ethylene group content of the main chain to obtain the mole fraction. The value obtained by expressing this mole fraction as a percentage is the degree of acetalization.

The hydroxyl group content (hydroxyl group amount), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from the results measured by a method based on JIS K 6728 "polyvinyl butyral test method". However, measurement by ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl group amount), the acetalization degree (butyralization degree), and the acetylation degree are based on JIS K6728 "polyvinyl butyral test method". Can be calculated from the results measured by.

(Plasticizer)
The interlayer film contains a plasticizer. The first layer (including a single-layer interlayer film) preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (3)). By using a plasticizer and by using a polyvinyl acetal resin and a plasticizer in combination, the penetration resistance is further improved, and the adhesive strength of the layer containing the polyvinyl acetal resin and the plasticizer to the laminated glass member or other layers is moderately high. Become. The plasticizer is not particularly limited. The plasticizer (1), the plasticizer (2), and the plasticizer (3) may be the same or different. The plasticizer (1), the plasticizer (2), and the plasticizer (3) 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 subphosphoric acid plasticizers. .. Organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.

Examples of the monobasic organic acid ester include glycol esters obtained by reacting glycol with a monobasic organic acid. Examples of the glycol include triethylene glycol, tetraethylene glycol, tripropylene glycol and the like. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octyl acid, 2-ethylhexic acid, n-nonyl 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, azelaic acid and the like.

Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, and triethylene glycol dicaprelate. 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-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprelate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, dibutyl maleate, Bis (2-butoxyethyl) adipate, dibutyl adipate, diisobutyl adipate, 2,2-butoxyethoxyethyl adipate, glycol ester benzoate, 1,3-butylene glycol polyester adipate, dihexyl adipate, dioctyl adipate , Hexylcyclohexyl adipate, mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, tributyl citrate, tributyl acetylcitrate, diethyl carbonate, dibutyl sebacate, oil-modified alkydic sebacate , And a mixture of a phosphate ester and an adipic acid ester. Organic ester plasticizers other than these may be used. Other adipate esters other than the above-mentioned adipate ester may be used.

Examples of the organophosphate plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, tricresyl phosphate, triisopropyl phosphate and the like.

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. .. Each of R1 and R2 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 preferably contains triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH) or triethylene glycol di-2-ethylpropanoate. .. The plasticizer more preferably contains triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and further preferably contains triethylene glycol di-2-ethylhexanoate. preferable.

In the second layer, 100 parts by weight of the thermoplastic resin (2) (100 parts by weight of the polyvinyl acetal resin (2) when the thermoplastic resin (2) is the polyvinyl acetal resin (2)). The content of the agent (2) is defined as the content (2). In the third layer, 100 parts by weight of the thermoplastic resin (3) (100 parts by weight of the polyvinyl acetal resin (3) when the thermoplastic resin (3) is the polyvinyl acetal resin (3)). The content of the agent (3) is defined as the content (3). The content (2) and the content (3) are preferably 10 parts by weight or more, more preferably 15 parts by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, still more preferably 32. By weight or less, particularly preferably 30 parts by weight or less. When the content (2) and the content (3) are at least the above lower limit, the flexibility of the interlayer film becomes high and the handling of the interlayer film becomes easy. When the content (2) and the content (3) are not more than the upper limit, the bending rigidity is further increased.

In the first layer, 100 parts by weight of the thermoplastic resin (1) (100 parts by weight of the polyvinyl acetal resin (1) when the thermoplastic resin (1) is the polyvinyl acetal resin (1)). The content of the agent (1) is defined as the content (1). The content (1) is preferably 1 part by weight or more, more preferably 2 parts by weight or more, still more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more, preferably 90 parts by weight or less, more preferably 90 parts by weight or less. It is 85 parts by weight or less, more preferably 80 parts by weight or less. When the content (1) is at least the above lower limit, the flexibility of the interlayer film becomes high and the handling of the interlayer film becomes easy. When the content (1) is not more than the upper limit, the penetration resistance of the laminated glass is further increased. The content (1) may be 50 parts by weight or more, 55 parts by weight or more, or 60 parts by weight or more. The content (1) may be 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

When the interlayer film has two or more layers, the content (1) is preferably higher than the content (2) in order to enhance the sound insulation of the laminated glass, and the content (1) is It is preferably higher than the above content (3). In particular, laminated glass using an interlayer film having a content (1) of 55 parts by weight or more tends to have a low bending rigidity, but the configuration of the present invention can significantly improve the bending rigidity.

From the viewpoint of further improving the sound insulation of the laminated glass, the absolute value of the difference between the above-mentioned content (2) and the above-mentioned content (1), and the difference between the above-mentioned content (3) and the above-mentioned content (1). The absolute value of each is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 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 80 parts by weight or less, respectively. It is more preferably 75 parts by weight or less, still more preferably 70 parts by weight or less.

(Heat-shielding substance)
The interlayer film preferably contains a heat-shielding substance (heat-shielding compound). The first layer preferably contains a heat-shielding substance. The second layer preferably contains a heat-shielding substance. The third layer preferably contains a heat-shielding substance. As the heat-shielding substance, only one kind may be used, or two or more kinds may be used in combination.

The heat-shielding substance preferably contains at least one component X of the phthalocyanine compound, the naphthalocyanine compound and the anthracyanine compound, or preferably contains heat-shielding particles. In this case, both the component X and the heat-shielding particles may be contained.

Ingredient X:
The interlayer film preferably contains at least one component X of the phthalocyanine compound, the naphthalocyanine compound and the 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 substance. As the component X, only one kind may be used, or two or more kinds may be used in combination.

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

From the viewpoint of further enhancing the heat-shielding property of the interlayer film and the laminated glass, the component X is preferably at least one selected from the group consisting of phthalocyanine, phthalocyanine derivative, naphthalocyanine and naphthalocyanine derivative. , Phthalocyanine and at least one of the derivatives of phthalocyanine are more preferable.

From the viewpoint of effectively enhancing 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 or a copper atom. The component X preferably contains a vanadium atom, and preferably contains a copper atom. The component X is more preferably at least one of a vanadium atom or a copper atom-containing phthalocyanine and a vanadium atom or a copper atom-containing phthalocyanine derivative. From the viewpoint of further improving the heat-shielding property of the interlayer film and the laminated glass, it is preferable that the component X 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, and particularly preferably 0.02% by weight or more. The content of the component X is preferably 0.2% by weight or less, more preferably 0.1 in 100% by weight of the layer containing the component X (first layer, second layer or third layer). It is 0% by weight or less, more preferably 0.05% by weight or less, and particularly preferably 0.04% by weight or less. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high. For example, the visible light transmittance can be 70% or more.

Heat shield particles:
The interlayer film preferably contains heat-shielding particles. The first layer (including a single-layer interlayer film) preferably contains the heat-shielding particles. The second layer preferably contains the heat shield particles. The third layer preferably contains the heat-shielding particles. The heat-shielding particles are heat-shielding substances. Infrared rays (heat rays) can be effectively blocked by using heat-shielding particles. Only one kind of the heat shield particles may be used, or two or more kinds may be used in combination.

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

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

Specific examples of the heat shield 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), niob-doped titanium oxide particles, sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, tallium-doped tungsten oxide particles, rubidium-doped tungsten oxide particles, tin-doped indium oxide particles (ITO particles). , Tin-doped zinc oxide particles, silicon-doped zinc oxide particles and other metal oxide particles, hexaborocarbonated lanthanum (LaB ₆ ) particles and the like. Heat-shielding particles other than these may be used. Metal oxide particles are preferable, 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, because the heat ray shielding function is high. 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.

From the viewpoint of further improving the heat-shielding property of the interlayer film and the laminated glass, the tungsten oxide particles are preferably metal-doped tungsten oxide particles. 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, rubidium-doped tungsten oxide particles, and the like.

Cesium-doped tungsten oxide particles are particularly preferable from the viewpoint of further increasing the heat-shielding property of the interlayer film and the laminated glass. From the viewpoint of further improving the heat-shielding property 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, and more preferably 0.05 μm or less. When the average particle size is at least the above lower limit, the heat ray shielding property becomes sufficiently high. When the average particle size is not more than the above upper limit, the dispersibility of the heat shield particles becomes high.

The above "average particle size" indicates a volume average particle size. The average particle size can be measured using a particle size distribution measuring device (“UPA-EX150” 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 containing the heat-shielding particles (first layer, second layer or third layer). .1% by weight or more, more preferably 1% by weight or more, and particularly preferably 1.5% by weight or more. The content of the heat-shielding particles is preferably 6% by weight or less, more preferably 5.5 in 100% by weight of the layer containing the heat-shielding particles (first layer, second layer or third layer). It is 0% by weight or less, more preferably 4% by weight or less, particularly preferably 3.5% by weight or less, and most preferably 3% by weight or less. When the content of the heat-shielding particles is not less than the above lower limit and not more than the above upper limit, the heat-shielding property is sufficiently high and the visible light transmittance is sufficiently high.

(Metal salt)
The interlayer film preferably contains at least one metal salt (hereinafter, may be referred to as metal salt M) among an alkali metal salt, an alkaline earth metal salt and a magnesium salt. 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 film and the laminated glass member or the adhesiveness between each layer in the interlayer film. 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 interlayer film preferably contains at least one of K and Mg.

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

Examples of the magnesium carboxylic acid salt having 2 to 16 carbon atoms and the potassium carboxylic acid salt having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, and 2-ethylbutanoic acid. Examples thereof include potassium, 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, still more preferably 20 ppm or more. It is 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 not less than the above lower limit and not more than the above upper limit, the adhesiveness between the interlayer film and the laminated glass member or the adhesiveness between each layer in the interlayer film can be controlled more satisfactorily.

(UV shielding agent)
The interlayer 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. Due to the use of the ultraviolet shielding agent, the visible light transmittance is less likely to decrease even if the interlayer film and the laminated glass are used for a long period of time. Only one kind of the above-mentioned ultraviolet shielding agent may be used, or two or more kinds thereof may be used in combination.

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

Examples of the ultraviolet shielding agent include an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure (benzotriazole compound), and an ultraviolet shielding agent having a benzophenone structure (benzophenone compound). ), An ultraviolet shielding agent having a triazine structure (triazine compound), an ultraviolet shielding agent having a malonic acid ester structure (malonic acid ester compound), an ultraviolet shielding agent having a oxalic acid anilide structure (a oxalic acid anilide compound), and a benzoate structure. Examples thereof include an ultraviolet shielding agent (benzoate compound).

Examples of the ultraviolet shielding agent containing a metal atom include platinum particles, particles in which the surface of platinum particles is coated with silica, palladium particles, particles in which the surface of palladium particles is coated with silica, and the like. The UV shielding agent is preferably not heat-shielding particles.

The ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure, an ultraviolet shielding agent having a benzophenone structure, an ultraviolet shielding agent having a triazine structure, or an ultraviolet shielding agent having a benzoate structure. The ultraviolet shielding agent is more preferably an ultraviolet shielding agent having a benzotriazole structure or an ultraviolet shielding agent having a benzophenone structure, and further preferably an ultraviolet shielding agent having a benzotriazole structure.

Examples of the ultraviolet shielding agent containing the metal oxide include zinc oxide, titanium oxide, cerium oxide and the like. Further, the surface of the ultraviolet shielding agent containing the metal oxide may be coated. Examples of the coating material on the surface of the ultraviolet shielding agent containing the metal oxide include insulating metal oxides, hydrolyzable organosilicon compounds, silicone compounds and the like.

Examples of the ultraviolet shielding agent having a benzotriazole structure include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole ("TinuvinP" manufactured by BASF), 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole (BASF "Tinuvin320"), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (BASF) "Tinuvin 326" manufactured by BASF), 2- (2'-hydroxy-3', 5'-di-amylphenyl) benzotriazole ("Tinuvin 328" manufactured by BASF) and the like. Since the ultraviolet shielding agent is excellent in the ability to absorb ultraviolet rays, the ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure containing a halogen atom, and may be an ultraviolet shielding agent having a benzotriazole structure containing a chlorine atom. More preferred.

Examples of the ultraviolet shielding agent having a benzophenone structure include octabenzone (“Chimassorb81” manufactured by BASF) and the like.

Examples of the ultraviolet shielding agent having the above triazine structure include "LA-F70" manufactured by ADEKA and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl). Oxy] -phenol (“Tinuvin1577FF” manufactured by BASF) and the like can be mentioned.

Examples of the ultraviolet shielding agent having a malonic acid ester structure include 2- (p-methoxybenzylidene) dimethyl malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismaronate, and 2- (p-methoxybenzylidene). -Bis (1,2,2,6,6-pentamethyl4-piperidinyl) malonate and the like can be mentioned.

Examples of commercially available products of the ultraviolet shielding agent having a malonic acid ester structure include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).

Examples of the ultraviolet shielding agent having an oxalic acid anilides structure include N- (2-ethylphenyl) -N'-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide and N- (2-ethylphenyl)-. A oxalic acid diamide having an aryl group substituted on a nitrogen atom such as N'-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("SanduvorVSU" manufactured by Clariant). Kind is mentioned.

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

The content of the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0 in 100% by weight of the layer containing the ultraviolet shielding agent (first layer, second layer or third layer). .2% by weight or more, more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight or more. The content of the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2 in 100% by weight of the layer containing the ultraviolet shielding agent (first layer, second layer or third layer). It is 0% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is not less than the above lower limit and not more than the above upper limit, the decrease in the visible light transmittance after the elapse of the period can be further suppressed. 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 a period of time is lowered. It can be significantly suppressed.

(Antioxidant)
The interlayer film 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. Only one kind of the above-mentioned antioxidant may be used, or two or more kinds may be used in combination.

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

The above-mentioned antioxidant is preferably a phenol-based antioxidant or a phosphorus-based antioxidant.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butyl hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, and 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 , Tetrakiss [methylene-3- (3', 5'-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydroxy-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) ethylene bis (oxyethylene) and the like. One or more of these antioxidants are preferably used.

Examples of the phosphorus-based antioxidant include tridecylphosphite, tris (tridecyl) phosphite, triphenylphosphite, trinonylphenylphosphite, bis (tridecyl) pentaerythritol diphosphite, and bis (decyl) pentaerythritol diphos. Fight, Tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, and 2,2'-methylenebis (4) , 6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorous and the like. One or more of these antioxidants are preferably used.

Examples of commercially available products of the above-mentioned antioxidants include "IRGANOX 245" manufactured by BASF, "IRGAFOS 168" manufactured by BASF, "IRGAFOS 38" manufactured by BASF, "Smilizer BHT" manufactured by Sumitomo Chemical Co., Ltd., and "Smilizer BHT" manufactured by Sakai Chemical Industry Co., Ltd. Examples thereof include "H-BHT" and "IRGANOX 1010" manufactured by BASF.

In order to maintain the high visible light transmittance of the interlayer film and laminated glass for a long period of time, a layer (first layer, second layer or third layer) containing 100% by weight of the interlayer film or an antioxidant. ) The content of the antioxidant is preferably 0.1% by weight or more in 100% by weight. Further, 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 interlayer film, the first layer, the second layer, and the third layer are each a coupling agent containing silicon, aluminum, or titanium, a dispersant, a surfactant, a flame retardant, as required. It may contain additives such as antistatic agents, fillers, pigments, dyes, adhesive strength modifiers, moisture resistant agents, fluorescent whitening agents and infrared absorbers. Only one of these additives may be used, or two or more of these additives may be used in combination.

In order to control the shear storage modulus to a suitable range, the interlayer film, the first layer, the second layer and the third layer may contain a filler. Examples of the filler include calcium carbonate particles and silica particles. Silica particles are preferable from the viewpoint of effectively increasing the bending rigidity and effectively suppressing the decrease in transparency.

The content of the filler in 100% by weight of the layer containing the filler (first layer, second layer or third layer) is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably. It is 10 parts by weight or more, preferably 60% by weight or less, and more preferably 50% by weight or less.

(Other details of laminated glass interlayer)
The thickness of the interlayer film is not particularly limited. From the viewpoint of practical use, and from the viewpoint of sufficiently enhancing the penetration resistance and bending rigidity of the laminated glass, the thickness of the interlayer film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, and more. It is preferably 1.5 mm or less. When the thickness of the interlayer film is at least the above lower limit, the penetration resistance and bending rigidity of the laminated glass are further increased. When the thickness of the interlayer film is not more than the above upper limit, the transparency of the interlayer film becomes even better.

Let T be the thickness of the interlayer film. The thickness of the first layer is preferably 0.035 T or more, more preferably 0.0625 T or more, still more preferably 0.1 T or more, preferably 0.4 T or less, still more preferably 0.375 T or less, still more preferably. It is 0.25T or less, particularly preferably 0.15T or less. When the thickness of the first layer is 0.4 T or less, the bending rigidity becomes even better.

The thickness of each of the second layer and the third layer is preferably 0.3 T or more, more preferably 0.3125 T or more, further preferably 0.375 T or more, preferably 0.97 T or less, and more preferably 0. It is .9375T or less, more preferably 0.9T or less. The thickness of each of the second layer and the third layer may be 0.46875 T or less, or may be 0.45 T or less. Further, when the thicknesses of the second layer and the third layer are not less than the lower limit and not more than the upper limit, the rigidity and sound insulation of the laminated glass are further increased.

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, still more preferably 0.85 T or more, preferably 0.97 T or less, more preferably 0.97 T or less. It is 0.9375T or less, more preferably 0.9T 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 and sound insulation of the laminated glass are further increased.

The interlayer film may be an interlayer film having a uniform thickness or an interlayer film having a variable thickness. The cross-sectional shape of the interlayer film may be rectangular or wedge-shaped.

The method for producing the interlayer film according to the present invention is not particularly limited. Examples of the method for producing an interlayer film according to the present invention include a method of extruding a resin composition using an extruder in the case of a single-layer interlayer film. As a method for producing an interlayer film according to the present invention, in the case of a multilayer interlayer film, for example, each layer is formed by using each resin composition for forming each layer, and then the obtained layers are laminated. , And a method of laminating each layer by co-extruding each resin composition for forming each layer using an extruder. Since it is suitable for continuous production, a manufacturing method of extrusion molding is preferable.

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

The interlayer film preferably has an uneven shape on at least one of the surfaces on both sides. It is more preferable that the interlayer film has an uneven shape on both surfaces. The method for forming the uneven shape is not particularly limited, and examples thereof include a lip embossing method, an embossing roll method, a calendar roll method, and a deformed extrusion method. The embossing roll method is preferable because it is possible to form embossing of a large number of uneven shapes which are quantitatively constant uneven patterns.

(Laminated glass)
FIG. 3 is a cross-sectional view schematically showing an example of a laminated glass using the interlayer film for laminated glass shown in FIG.

The laminated glass 31 shown in FIG. 3 includes a first laminated glass member 21, a second laminated glass member 22, and an interlayer film 11. The interlayer film 11 is arranged between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched therein.

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

FIG. 4 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG. 2.

The laminated glass 31A shown in FIG. 4 includes a first laminated glass member 21, a second laminated glass member 22, and an interlayer film 11A. The interlayer film 11A is arranged between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched therein.

The first laminated glass member 21 is laminated on the first surface 11a of the interlayer film 11A. The second laminated glass member 22 is laminated on the second surface 11b opposite to the first surface 11a of the interlayer film 11A.

As described above, the laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and an interlayer film, and the interlayer film is an interlayer film for laminated glass according to the present invention. Is. In the laminated glass according to the present invention, the interlayer film is arranged between the first laminated glass member and the second laminated glass member.

The first laminated glass member is preferably a first glass plate. The second laminated glass member is preferably a second glass plate.

Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. The laminated glass includes not only laminated glass in which an interlayer film is sandwiched between two glass plates, but also laminated glass in which an interlayer film is sandwiched between a glass plate and a PET film or the like. The laminated glass is a laminated body provided with a glass plate, and it is preferable that at least one glass plate is used. The first laminated glass member and the second laminated glass member are glass plates or PET films, respectively, and the laminated glass is the first laminated glass member and the second laminated glass member. It is preferable to provide a glass plate as at least one of them.

Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, template glass, and wire-filled plate glass. The organic glass is a synthetic resin glass that replaces 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, and 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, and 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 bending rigidity of the laminated glass can be maintained high even if the thickness of the laminated glass is thin. The thickness of the glass plate is preferably 2 mm or less, more preferably 1.8 mm or less, still more preferably 1.6 mm or less, still more preferably 1.5 mm or less, still more preferably 1.4 mm or less, still more preferably 1. It is 0.3 mm or less, more preferably 1.0 mm or less, and particularly preferably 0.7 mm or less. In this case, it is possible to reduce the weight of the laminated glass, reduce the material of the laminated glass to reduce the environmental load, and improve the fuel efficiency of the automobile by reducing the weight of the laminated glass to reduce the environmental load. .. The total of the thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, more preferably 3.2 mm or less, still more preferably 3 mm or less, and particularly preferably 2.8 mm or less. Is. In this case, it is possible to reduce the weight of the laminated glass, reduce the material of the laminated glass to reduce the environmental load, and improve the fuel efficiency of the automobile by reducing the weight of the laminated glass to reduce the environmental load. ..

The method for producing the laminated glass is not particularly limited. First, an interlayer film is sandwiched between the first laminated glass member and the second laminated glass member to obtain a laminated body. Next, for example, by passing the obtained laminated body through a pressing roll or putting it in a rubber bag and sucking it under reduced pressure, the first laminated glass member, the second laminated glass member, and the interlayer film are subjected to each other. Degas the air remaining in between. Then, it is pre-bonded at about 70 to 110 ° C. to obtain a pre-bonded laminate. Next, the pre-crimped laminate is placed in an autoclave or pressed, and crimped at a pressure of about 120 to 150 ° C. and 1 to 1.5 MPa. In this way, laminated glass can be obtained. At the time of 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, railroad vehicles, aircraft, ships, buildings and the like. The interlayer film and the laminated glass can be used for other purposes. The interlayer film and the laminated glass are preferably an interlayer film and a laminated glass for a vehicle or a building, and more preferably an interlayer film and a laminated glass for a vehicle. The interlayer film and the laminated glass can be used for windshields, side glasses, rear glasses, roof glasses and the like of automobiles. The interlayer film and the laminated glass are preferably used for automobiles. The interlayer film is used to obtain laminated glass for automobiles.

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

The following materials were prepared.

(Polyvinyl acetal resin)
The polyvinyl acetal resins shown in Tables 1 to 3 below were appropriately used.

For the polyvinyl acetal resin, the degree of acetalization, the degree of acetylation and the content of hydroxyl groups were measured by a method according to JIS K6728 "Polyvinyl butyral test method". In addition, when measured by ASTM D1396-92, the same numerical value as the method based on JIS K6728 "polyvinyl butyral test method" was shown. When the type of acetal is acet acetal, benzyl acetal or cumin acetal, the degree of acetalization is similarly measured by measuring the degree of acetylation and the content of hydroxyl groups, and the molar fraction is calculated from the obtained measurement results. It is calculated and then calculated by subtracting the degree of acetylation and the content of hydroxyl groups from 100 mol%.

(Second resin)
The acrylic polymers shown in Tables 1 to 3 below were appropriately used.

The acrylic polymer shown in Tables 1 to 3 below is an acrylic polymer obtained by polymerizing a polymerizable component containing the following compounds at the contents shown in Tables 1 to 3 below.

Ethyl Acrylate Butyl Acrylate Benzyl Acrylate 2-Hydroxyethyl Acrylate Tripropylene Glycol Diacrylate (“APG-200” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Polypropylene glycol (# 700) diacrylate ("APG-700" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Ethoxylated bisphenol A diacrylate ("A-BPE-20" manufactured by Shin-Nakamura Chemical Co., Ltd.)
ε-Caprolactone-modified tris- (2-acryloxyethyl) isocyanurate ("A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Tris Phosphate [2- (Acryloyloxy) Ethyl]
Ethoxylated pentaerythritol tetraacrylate ("ATM-35E" manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

(Example 1)
A polyvinyl acetal resin (average degree of polymerization 560, acetalization degree 74.0 mol%, hydroxyl group content 25.0 mol%, acetylation degree 0.9 mol%) was prepared. 100 parts by weight of the polymerizable component (60 parts by weight of ethyl acrylate, 14.4 parts by weight of butyl acrylate, 25 parts by weight of benzyl acrylate, 0.6 parts by weight of tripropylene glycol diacrylate) was prepared. In a reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, 100 parts by weight of the polyvinyl acetal resin as a raw material, 100 parts by weight of the polymerizable component, and 300 parts by weight of ethyl acetate as a polymerization solvent are placed. In addition, the polyvinyl acetal resin was dissolved with stirring. Next, nitrogen gas was blown into the reaction vessel for 30 minutes to replace the inside of the reaction vessel with nitrogen, and then the inside of the reaction vessel was heated to 80 ° C. with stirring. After 30 minutes, 0.5 part by weight of t-butylperoxy-2-ethylhexanoate (1 hour half-life temperature: 92.1 ° C., 10 hour half-life temperature: 72.1 ° C.) as a polymerization initiator was added. The polymerization initiator solution obtained by diluting with 5 parts by weight of ethyl acetate was added dropwise into the reaction vessel over 6 hours. Then, the reaction was further carried out at 80 ° C. for 6 hours, and then the reaction solution was cooled to obtain a solution containing a modified polyvinyl acetal resin.

To the obtained solution, add 5 parts by weight of 3GO as a plasticizer to a total of 100 parts by weight of the polyvinyl acetal resin and the polymer (second resin), and add a diluting solvent (mixed solvent of methanol and toluene, methanol and toluene). The weight ratio was 1: 2) to obtain a solution having a solid content of 20% by weight. Next, this solution was applied to a PET film that had been mold-released to a thickness of 50 μm after drying using a coater, and dried at 80 ° C. for 1 hour to obtain a resin film. The obtained resin films having a thickness of 50 μm were laminated and heat-bonded at 150 ° C. and 20 MPa to obtain an interlayer film having a thickness of 780 μm.

Laminated glass production:
Two washed and dried glass plates (first laminated glass member and second laminated glass member, clear float glass, bending rigidity evaluation: length 25 mm x width 200 mm x thickness 1 mm, falling ball evaluation: length 300 mm x width 300 mm x thickness 1 mm) was prepared. The obtained interlayer film was sandwiched between the two glass plates to obtain a laminated body. The obtained laminate was placed in a rubber bag and degassed at a vacuum degree of 2660 Pa (20 torr) for 20 minutes. Then, the laminate was vacuum-pressed while being held in an autoclave at 90 ° C. for 30 minutes while being degassed. The laminated body pre-crimped in this manner was crimped in an autoclave at 135 ° C. and a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

(Examples 2 to 15 and Comparative Examples 1 to 10)
An interlayer film and a laminated glass were obtained in the same manner as in Example 1 except that the composition of the composition for forming the interlayer film was set as shown in Tables 1 to 3 below.

(evaluation)
(1) Observation of phase structure The obtained interlayer film was treated with a microtome to prepare a section having a thickness of 100 nm. The obtained sections were stained with osmium tetroxide and observed with a transmission electron microscope. The presence or absence of a phase-separated structure was determined.

[Criteria for determining the presence or absence of a phase-separated structure]
◯: With phase separation structure ×: Without phase separation structure

Further, when there is a phase-separated structure and there is a matrix, it was confirmed whether the resin component constituting the matrix and the island (domain) is a polyvinyl acetal resin or a second resin.

[Criteria for determining resin components constituting the matrix and islands]
A: The component constituting the matrix is a polyvinyl acetal resin and the component constituting the island portion is the second resin. B: The component constituting the matrix is the second resin and the component constituting the island portion is the polyvinyl acetal resin.

Further, when there was a phase-separated structure and there was an island portion (domain), the diameter (maximum diameter) of the island portion was observed at 3000 times or 5000 times, and the average value was obtained. The average diameter of the islands was determined according to the following criteria.

[Criteria for averaging island diameters]
A: The average diameter of the islands is 10 nm or more and 1 μm or less. B: Does not correspond to the standard of A.

(2) Flexural rigidity The flexural rigidity was evaluated by the test method schematically shown in FIG. As a measuring device, a UTA-500 manufactured by Orientec Co., Ltd. equipped with a three-point bending test jig was used. The measurement conditions are a measurement temperature of 23 ° C. (23 ° C. ± 3 ° C.) or 65 ° C. (65 ° C. ± 3 ° C.), a distance D1 of 12 cm, a distance D2 of 20 cm, and a displacement speed of 1 mm / min. The bending rigidity was calculated by measuring the stress when the displacement of 1.5 mm was applied. The flexural rigidity was judged according to the following criteria. The higher the value of flexural rigidity, the better the flexural rigidity.

[Criteria for flexural rigidity]
○ ○: Flexural rigidity is 60 N / mm or more ○: Flexural rigidity is 50 N / mm or more and less than 60 N / mm Δ: Flexural rigidity is 40 N / mm or more and less than 50 N / mm ×: Flexural rigidity is less than 40 N / mm

(3) Penetration resistance The obtained laminated glass was adjusted so that the surface temperature was 20 ° C. Then, from a height of 2.0 m, a hard sphere having a mass of 2260 g and a diameter of 82 mm was dropped onto the central portion of the laminated glass, respectively, for each of the six laminated glasses. For all six laminated glasses, the case where the hard sphere did not penetrate within 5 seconds after the hard sphere collided was regarded as acceptable. If the number of laminated glasses that the hard sphere did not penetrate within 5 seconds after the hard sphere collided was 3 or less, it was rejected. In the case of 4 sheets, the penetration resistance of 6 new laminated glasses was evaluated. In the case of 5 sheets, a new laminated glass was additionally tested, and the case where the hard sphere did not penetrate within 5 seconds after the hard sphere collided was regarded as a pass. In the same way, raise the height by 25 cm, and drop a hard ball with a mass of 2260 g and a diameter of 82 mm on each of the six laminated glasses to the center of the laminated glass to improve the penetration resistance (maximum height) of the laminated glass. evaluated. Penetration resistance was judged according to the following criteria.

[Penetration resistance criteria]
○ ○: Maximum height is 6 m or more ○: Maximum height is 5 m or more and 5.75 m or less ○: Maximum height is 4 m or more and 4.75 m or less ×: Maximum height is 3.75 m or less

Details and results are shown in Tables 1 to 3 below.

1 ... 1st layer 1a ... 1st surface 1b ... 2nd surface 2 ... 2nd layer 2a ... outer surface 3 ... 3rd layer 3a ... outer surface 11 ... intermediate film 11A ... intermediate film (first) 1 layer)
11a ... 1st surface 11b ... 2nd surface 21 ... 1st laminated glass member 22 ... 2nd laminated glass member 31 ... laminated glass 31A ... laminated glass

Claims (10)

It contains a polyvinyl acetal resin, a polymer of a polymerizable component containing a (meth) acrylate compound having two or more (meth) acryloyl groups, and a plasticizer.
The content of the polymer is 85 parts by weight or more and 160 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin.
The content of the plasticizer is 3 parts by weight or more and less than 15 parts by weight with respect to a total of 100 parts by weight of the polyvinyl acetal resin and the polymer.
Have a phase separation structure,
A (meth) acrylate compound having two or more (meth) acryloyl groups and a (meth) acrylate compound having two or more (meth) acryloyl groups in 100% by weight of the polymerizable component constituting the polymer. ) The total amount with the polymerizable compound having an acryloyl group is 50% by weight or more, and the amount is 50% by weight or more.
An interlayer film for laminated glass , wherein the polymer is an acrylic polymer. The interlayer film for laminated glass according to claim 1, wherein the content of the plasticizer is 5 parts by weight or more with respect to a total of 100 parts by weight of the polyvinyl acetal resin and the polymer. The interlayer film for laminated glass according to claim 1 or 2 , wherein the content of the plasticizer is 8 parts by weight or less with respect to a total of 100 parts by weight of the polyvinyl acetal resin and the polymer. The interlayer film for laminated glass according to any one of claims 1 to 3 , wherein the polyvinyl acetal resin and the polymer are crosslinked. The interlayer film for laminated glass according to any one of claims 1 to 4 , wherein the thickness is 3 mm or less. Claims 1 to 2, wherein a first glass plate having a thickness of 1.6 mm or less is arranged between the first glass plate and the second glass plate and used to obtain a laminated glass. 5. The interlayer film for laminated glass according to any one of 5. It is placed between the first glass plate and the second glass plate and used to obtain laminated glass.
The interlayer film for laminated glass according to any one of claims 1 to 6 , wherein the total thickness of the first glass plate and the thickness of the second glass plate is 3.5 mm or less. The first laminated glass member and
With the second laminated glass member,
The laminated glass interlayer film according to any one of claims 1 to 7 is provided.
A laminated glass in which the laminated glass interlayer film is arranged between the first laminated glass member and the second laminated glass member. The first laminated glass member is a first glass plate, and the first laminated glass member is a first glass plate.
The laminated glass according to claim 8 , wherein the thickness of the first glass plate is 1.6 mm or less. The first laminated glass member is a first glass plate, and the first laminated glass member is a first glass plate.
The second laminated glass member is a second glass plate.
The laminated glass according to claim 8 or 9 , wherein the total of the thickness of the first glass plate and the thickness of the second glass plate is 3.5 mm or less.

Images