TW201842038A - Interlayer for laminated glass, and laminated glass - Google Patents

Abstract

An interlayer for laminated glass is provided which is capable of improving the bending rigidity of a laminated glass over a wide range of temperatures, and which is capable of improving the penetration resistance of the laminated glass. An interlayer for laminated glass according to the present invention is provided with a phase separation structure which includes: a polyvinyl acetal resin; a polymer of a polymerizable component including a (meth)acrylate compound having two or more (meth)acryloyl groups; and a plasticizer. The content of the polymer is at least 85 but not more than 160 parts by weight per 100 parts by weight of the polyvinyl acetal resin. The content of the plasticizer is at least 3 but less than 15 parts by weight per a total of 100 parts by weight of the polyvinyl acetal resin and the polymer.

Description

Interlayer film for laminated glass and laminated glass

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

Even if the laminated glass is damaged by an external impact, the amount of scattered glass fragments is small and the safety is excellent. Therefore, the above-mentioned laminated glass is widely used in automobiles, rail vehicles, aircraft, ships, and buildings. The laminated glass is produced by sandwiching an interlayer film for laminated glass between two glass plates.

As an example of the above-mentioned interlayer film for laminated glass, Patent Literature 1 below discloses a sound insulation layer containing 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, an alkali At least one metal salt of the metal salt and the alkaline earth metal salt is 0.001 to 1.0 part by weight, and more than 30 parts by weight of a plasticizer. The sound insulation layer may be used as a single layer as an intermediate film.

Furthermore, Patent Document 1 described below also describes a multilayer interlayer film in which the above-mentioned soundproof layer and other layers are laminated. The other layers laminated on the sound insulation layer include: 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, at least one metal salt of an alkali metal salt and an alkaline earth metal salt, 0.001 to 1.0 part by weight, And 30 parts by weight or less of plasticizer.

An interlayer film disclosed in Patent Document 2 below is a polymer layer having a glass transition temperature of 33 ° C or higher. Patent Document 2 describes that the polymer layer is disposed between glass plates having a thickness of 4.0 mm or less. [Prior Art Literature] [Patent Literature]

[Patent Document 1] WO2014 / 050746A1 [Patent Document 2] US2013 / 0236711A1

[Problems to be solved by the invention]

The laminated glass using the conventional interlayer film described in Patent Documents 1 and 2 may have a low flexural rigidity at room temperature. Therefore, for example, when laminated glass is used as a window glass for a side door of a car, a frame without fixed laminated glass may have a deflection caused by the low rigidity of the laminated glass, which hinders the opening and closing of the window glass. Happening.

In addition, in recent years, in order to reduce the weight of laminated glass, it is required to reduce the thickness of a glass plate. The laminated glass formed by sandwiching an intermediate film between two glass plates has a problem that if the thickness of the glass plate is reduced, it is extremely difficult to maintain the flexural rigidity sufficiently high.

For example, even if the thickness of the glass plate is thin, as long as the flexural rigidity of the laminated glass can be improved by the interlayer film, the laminated glass can be made lighter. If the laminated glass is lightweight, the amount of materials used in the laminated glass can be reduced, and the environmental load can be reduced. Furthermore, when a lightweight laminated glass is used in an automobile, fuel efficiency can be improved, and as a result, the environmental load can be reduced.

Furthermore, the laminated glass used in automobiles and the like may reach an extremely high temperature of about 65 ° C. In addition, if the thickness of the glass plate is thin, the rigidity of the interlayer film is greatly affected, and the flexural rigidity of the laminated glass under high temperature is easily reduced. It is difficult for the prior interlayer film to sufficiently improve the flexural rigidity of laminated glass at a high temperature of about 65 ° C.

In addition, laminated glass using an interlayer film is expected to have high flexural rigidity and high penetration resistance.

It is difficult for the previous interlayer film to make not one of the higher flexural rigidity and the higher penetration resistance but both are good.

An object of the present invention is to provide an interlayer film for laminated glass that can improve the flexural rigidity of laminated glass and can improve the penetration resistance of laminated glass over a wide temperature range. Another object of the present invention is to provide a laminated glass using the above-mentioned interlayer film for laminated glass. [Technical means to solve the problem]

According to a wide aspect of the present invention, there is provided an interlayer film (hereinafter, sometimes referred to as an interlayer film) for laminated glass, which contains a polyvinyl acetal resin and contains an (2) or more (meth) acryl fluorenyl group. The polymer of the polymerizable component of the (meth) acrylate compound and the plasticizer are contained in an amount of 85 parts by weight or more and 160 parts by weight or less based on 100 parts by weight of the polyvinyl acetal resin. In the total of 100 parts by weight of the polyvinyl acetal resin and the polymer, the content of the plasticizer is 3 parts by weight to 15 parts by weight, and the interlayer film for laminated glass has a phase separation structure.

In a specific aspect of the interlayer film of the present invention, the (meth) acrylic acid ester compound having two or more (meth) acrylfluorenyl groups and the The total amount of two or more (meth) acrylfluorene-containing (meth) acrylic acid ester-containing compound having a (meth) acrylfluorene group is 50% by weight or more, and the polymer is an acrylic polymer Thing.

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

In a specific aspect of the intermediate film of the present invention, the content of the plasticizer is 8 parts by weight or less based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer.

In a specific aspect of the interlayer film of the present invention, the polyvinyl acetal resin is crosslinked with the polymer.

In a specific aspect of the interlayer film of the present invention, its thickness is 3 mm or less.

In a specific aspect of the interlayer film of the present invention, the interlayer film is used to obtain a laminated glass by using a first glass plate having a thickness of 1.6 mm or less and disposed between the first glass plate and the second glass plate. .

In a specific aspect of the interlayer film of the present invention, the interlayer film is used to obtain a laminated glass disposed between the first glass plate and the second glass plate, and the thickness of the first glass plate is the same as that of the second glass plate. The total thickness of the glass plate is 3.5 mm or less.

According to a wide aspect of the present invention, there is provided a laminated glass including a first laminated glass member, a second laminated glass member, and the aforementioned interlayer film for laminated glass, and the interlayer film for laminated glass is disposed on Between the first laminated glass member and the second laminated glass member.

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

The interlayer film for laminated glass of the present invention contains a polyvinyl acetal resin, a polymer containing a polymerizable component of a (meth) acrylate compound having two or more (meth) acrylfluorenyl groups, and a plasticizer. . In the interlayer film for laminated glass of 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 relative to the polyvinyl acetal resin. The total content of the plasticizer is 100 parts by weight and the content of the plasticizer is 3 parts by weight or more and less than 15 parts by weight. The interlayer film for laminated glass of the present invention has a phase separation structure. Since the interlayer film for laminated glass of the present invention has the above-mentioned structure, the flexural rigidity of the laminated glass using the interlayer film for laminated glass of the present invention can be improved over a wide temperature range, and the laminated glass can be improved. Resistance to penetration.

Hereinafter, the present invention will be described in detail.

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

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

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

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

The intermediate film of the present invention has a phase separation structure.

Since the interlayer film of the present invention has the above-mentioned structure, the flexural rigidity of the laminated glass using the interlayer film of the present invention at high temperatures can be improved. In particular, the flexural rigidity of the laminated glass using the interlayer film of the present invention at 65 ° C can be improved. Furthermore, the flexural rigidity of the laminated glass using the interlayer film of the present invention at 23 ° C can be improved. Further, in order to obtain a 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 flexural rigidity of the laminated glass can be sufficiently improved by using the interlayer film of the present invention. Moreover, even if the thickness of both the first glass plate and the second glass plate is thin, the flexural rigidity of the laminated glass can be sufficiently improved by using the interlayer film of the present invention. Further, if the thickness of both the first glass plate and the second glass plate is thick, the flexural rigidity of the laminated glass is further increased.

The conventional interlayer film has difficulty in sufficiently improving the flexural rigidity over a wide temperature range including normal temperature and high temperature. For example, even if the flexural rigidity at normal temperature is high, the flexural rigidity at high temperature is low, or even if the flexural rigidity at high temperature is high, the flexural rigidity at room temperature is low. In contrast, the present invention can improve the flexural rigidity in a wider temperature range (for example, 23 ° C and 65 ° C).

Furthermore, since the interlayer film of the present invention has the above-mentioned configuration, the penetration resistance of the laminated glass using the interlayer film of the present invention can be improved.

From the viewpoint of improving the flexural rigidity and penetration resistance over a wide temperature range, the content of the polymer X is 85 parts by weight or more and 160 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. the following. From the viewpoint of further improving the flexural rigidity and penetration resistance in a wider temperature range, the content of the polymer X is preferably 90 parts by weight or more relative to 100 parts by weight of the polyvinyl acetal resin. And is preferably 120 parts by weight or less.

From the viewpoint of improving the flexural rigidity and penetration resistance over a wide temperature range, the content of the plasticizer is 3 based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. It is not less than 15 parts by weight. From the viewpoint of further improving penetration resistance, the content of the plasticizer is preferably 4 parts by weight or more, and more preferably 5 parts by weight based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. the above. From the viewpoint of further improving the flexural rigidity over a wider temperature range, the content of the plasticizer is preferably 13 parts by weight relative to 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. Hereinafter, it is more preferably 8 parts by weight or less.

From the viewpoint of improving the flexural rigidity and penetration resistance over a wide temperature range, the intermediate film has a phase separation structure. From the viewpoint of further improving the flexural rigidity and penetration resistance in a wider temperature range, in the phase separation structure, the polymer X is preferably an island (region). In the present invention, as one of the factors that exert the above-mentioned effects, it is considered that the reason is that the energy distribution is smoothly performed by the phase separation structure.

The polyvinyl acetal resin is preferably a surrounding area, and the polyvinyl acetal resin is preferably a matrix. The phase separation structure is preferably a co-continuous structure or an island structure. The phase separation structure may be a co-continuous structure or an 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 separation structure. In the case of a sea-island structure, the polyvinyl acetal resin may be a sea part and the polymer X may be an island part, or the polymer X may be a sea part and the polyvinyl acetal resin may be an island part. In the phase separation structure, the polyvinyl acetal resin may be continuous (may have a continuous structure), the polymer X may be continuous (may have a continuous structure), or the polyvinyl acetal resin may be The aforementioned polymer X forms a co-continuous structure. In the phase separation structure, the polyvinyl acetal resin may exist in a network shape, or the polymer X may exist in a network shape. In terms of excellent effects of the present invention, 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 separation structure, the polyvinyl acetal resin and the polymer X preferably form a sea-island structure or a co-continuous structure.

In the phase separation structure described above, the average diameter of the island is preferably 10 nm or more, more preferably 15 nm or more, even more preferably 20 nm or more, even more preferably 30 nm or more, and more preferably 13 μm or less. It is more preferably 10 μm or less, even more preferably 2 μm or less, and even more preferably 1 μm or less. The diameter of each island portion indicates the maximum diameter, and the average of the diameters of the island portions is obtained by averaging the diameters (maximum diameters) of the plurality of island portions.

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

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

The surface of the second layer opposite to the first layer is preferably a surface on which a 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, and more preferably 1.3 mm or less. The second surface of the first layer opposite to the first surface (the surface on the second layer side) may be a surface on which a 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, and more preferably 1.3 mm or less. The surface of the third layer opposite to the first layer is preferably a surface on which a 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, and more preferably 1.3 mm or less.

The said intermediate film can be used conveniently to arrange | position between a 1st glass plate and a 2nd glass plate, and to obtain laminated glass. Since the flexural rigidity can be sufficiently improved by the interlayer film, the total thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, and more preferably 3 mm or less. The said intermediate film can be used conveniently to arrange | position between a 1st glass plate and a 2nd glass plate, and to obtain laminated glass. Since the interlayer film can sufficiently improve the flexural rigidity, the above-mentioned interlayer film can be suitably used for a first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less), and is arranged between the first glass plate and the Laminated glass was obtained between the second glass plates. The above-mentioned interlayer film can be more suitably used for the first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less) and the second glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). A laminated glass is obtained between the first glass plate and the second glass plate. In this case, it is also possible to sufficiently increase the flexural rigidity 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 a first embodiment of the present invention.

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

Further, other layers may be disposed between the second layer 2 and the first layer 1 and between the first layer 1 and the third layer 3, respectively. The second layer 2 and the first layer 1 and the first layer 1 and the third layer 3 are preferably laminated directly, respectively. Examples of the other layer include a layer containing polyethylene terephthalate and the like.

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 single-layer structure. The intermediate film 11A is a 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, details of the first layer, the second layer, and the third layer constituting the interlayer film of the present invention, and details of each component contained in the first layer, the second layer, and the third layer are described below. Contents are explained.

(Resin) The interlayer film contains a polyvinyl acetal resin and a polymer X containing a polymerizable component of a (meth) acrylate compound having two or more (meth) acrylfluorenyl groups. The first layer, the second layer, and the third layer preferably each contain a polyvinyl acetal resin. The first layer, the second layer, and the third layer preferably each contain the polymer X. The polyvinyl acetal resin may be used alone or in combination of two or more. The polymer X may be used alone or in combination of two or more.

From the viewpoint of effectively improving the affinity between the resin component and the plasticizer and effectively improving the penetration resistance, the polyvinyl acetal resin is preferably a polyvinyl acetal resin or a polyvinyl butyral resin. 2, polyvinyl formal resin or polyvinyl p-isopropyl benzaldehyde resin. From the viewpoint of further improving the flexural rigidity at 40 ° C, a polyvinyl acetal resin is preferred. In this specification, the polyvinyl acetal resin includes a resin acetalized, a resin acetalized, and a resin acetalized.

From the viewpoint of further improving the flexural rigidity and penetration resistance in a wider temperature range, the interlayer film preferably contains a polyolefin resin, an acrylic polymer, a urethane polymer, and a polysiloxane. A polymer, rubber, or vinyl acetate polymer is used as the polymer X, and an acrylic polymer is more preferably used as the polymer X. The acrylic polymer is a polymer obtained by using 50% by weight or more of a compound having a (meth) acrylfluorenyl group as a polymerizable component.

Among 100% by weight of the polymerizable component constituting the polymer X, a (meth) acrylate compound having two or more (meth) acrylfluorenyl groups and an ( The total amount of the superpositionable compound having a (meth) acrylfluorenyl group other than the meth) acrylate compound is referred to as the total amount A. From the viewpoint of further improving the flexural rigidity and sound insulation properties over a wider temperature range, the total amount A is preferably 50% by weight or more, more preferably 60% by weight or more, and even more preferably 70% by weight. Above, it is particularly preferably 80% by weight or more, and 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) acrylfluorenyl groups include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and triethyl Glycol di (meth) acrylate, 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-tricyclodecane bis (methyl) ) Acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, tritetramethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, etc. (Meth) acrylate compounds; caprolactone tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate di (methyl) ) Acrylate, Dicaprolactone tri (meth) acrylic acid , Ε-caprolactone-modified tri- (2- (meth) propenyloxyethyl) isocyanurate, tris [2-((meth) propenyloxy) ethyl] phosphate, etc. 3 Functional (meth) acrylate compounds; caprolactone tetra (meth) acrylate, dicaprolactone tetra (meth) acrylate, ethoxycaprolactone tetra (meth) acrylate, dicaprolactone Penta (meth) acrylate, dicaprolactone hexa (meth) acrylate and the like having more than four functional (meth) acrylate compounds and the like.

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

The polymer X is preferably a polymer containing a polymerizable component of a (meth) acrylate. The polymer X is preferably a poly (meth) acrylate.

The poly (meth) acrylate is not particularly limited. Examples of the poly (meth) acrylate include poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, and isopropyl (meth) acrylate. Ester, poly (meth) acrylate n-butyl, polyiso (meth) acrylate, poly (meth) acrylate tert-butyl, poly (meth) acrylate 2-ethylhexyl, poly (meth) ) 2-hydroxyethyl acrylate, 2-hydroxypropyl poly (meth) acrylate, 4-hydroxybutyl poly (meth) acrylate, glycidyl poly (meth) acrylate, octyl poly (meth) acrylate Polypropyl (meth) acrylate, 2-ethyloctyl (meth) acrylate, nonyl (meth) acrylate, polynonon (meth) acrylate, decyl poly (meth) acrylate , Polyisodecyl (meth) acrylate, polylauryl (meth) acrylate, polyisotetradecyl (meth) acrylate, cyclohexyl (meth) acrylate, poly (meth) acrylate Esters, and polybenzyl (meth) acrylate. Examples of the (meth) acrylic acid and (meth) acrylic acid ester having a polar group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , And glycidyl (meth) acrylate. To the extent that the temperature showing the maximum value of tanδ can be easily controlled within a moderate range in the dynamic viscoelasticity spectrum, polyacrylate is preferred, and polyethyl acrylate, poly-n-butyl acrylate, Poly 2-ethylhexyl acrylate or poly octyl acrylate. By using these preferred poly (meth) acrylates, the balance between the productivity of the intermediate film and the characteristics of the intermediate film is further improved. The poly (meth) acrylate may be used alone or in combination of two or more.

The polyvinyl acetal resin and the polymer are preferably crosslinked. The intermediate film may contain the polyvinyl acetal resin and the polymer X in the form of a crosslinked product obtained by crosslinking the polyvinyl acetal resin and the polymer X. The thermoplastic resin may have a crosslinked structure. With the above-mentioned crosslinked structure, the shear storage modulus can be controlled, and an intermediate film having both excellent flexibility and high strength can be produced.

Examples of the method for crosslinking the resin include the following methods. A method for introducing cross-linking functional groups into a polymer structure of a resin in advance to form a crosslink. A method of performing cross-linking using a cross-linking agent having two or more functional groups that react with a functional group existing in a polymer structure of a resin. A method of crosslinking a polymer by using a radical generator having a hydrogen abstraction ability such as a peroxide. A method of crosslinking by electron beam irradiation. From the viewpoint of easily controlling the shear storage modulus and increasing the productivity of the intermediate film, a method of introducing a functional group that reacts with each other in the polymer structure of the resin in advance to form a crosslink is preferred.

In the case where the interlayer film contains a cross-linked product of the polyvinyl acetal resin and the polymer X, it is preferable to perform the following steps: in the presence of the polyvinyl acetal resin, the The polymerizable component of the (meth) acrylic acid-based (meth) acrylate compound is polymerized to form polymer X, and an intermediate film is obtained. By this step, a structure obtained by crosslinking the polyvinyl acetal resin and the polymer X is formed.

The first layer (including a single-layer intermediate film) preferably contains a thermoplastic resin (hereinafter, sometimes referred to as a thermoplastic resin (1)). The first layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)) as the thermoplastic resin (1). When there is only a single-layer interlayer film of the first layer, the interlayer film contains a polyvinyl acetal resin (1). The second layer preferably contains a thermoplastic resin (hereinafter, sometimes referred to as a thermoplastic resin (2)). The second layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (2)) as the thermoplastic resin (2). The third layer preferably contains a thermoplastic resin (hereinafter, sometimes referred to as a thermoplastic resin (3)). The third layer preferably contains a polyvinyl acetal resin (hereinafter sometimes 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. The polyvinyl acetal resin (1) is preferably different from the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) in terms of further improving sound insulation. 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. The thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be used alone or in combination of two or more.

Examples of the thermoplastic resin include polyvinyl acetal resin, polyacrylic resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin. Other thermoplastic resins can also be used.

The polyvinyl acetal resin is preferably an acetal compound of polyvinyl alcohol. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the above-mentioned 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, even more preferably 1500 or more, even more preferably 1600 or more, particularly preferably 2600 or more, and most preferably 2700 or more, and It is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3500 or less. When the average polymerization degree is greater than or equal to the above lower limit, the penetration resistance and flexural rigidity of the laminated glass are further increased. When the average polymerization degree is equal to or less than the above upper limit, the formation of the intermediate film becomes easy.

The average degree of polymerization of the polyvinyl alcohol is determined by a method in accordance with JIS K6726 "Test method for polyvinyl alcohol".

The carbon number of the acetal group in the polyvinyl acetal resin is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2, 3 or 4. The carbon number of the acetal group in the polyvinyl acetal resin is preferably 2 or 4. In this case, the production of the polyvinyl acetal resin is efficient.

As the aldehyde, generally, an aldehyde having 1 to 10 carbon atoms can be favorably used. Examples of the aldehyde having a carbon number of 1 to 10 include, for example, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexanal, n-octaldehyde, and n-octaldehyde. Nonanal, n-decanal, p-isopropylbenzaldehyde, and benzaldehyde. Preferred are acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexanal, or n-valeraldehyde. It is more preferably acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde or n-valeraldehyde, and still more preferably acetaldehyde, n-butyraldehyde or n-valeraldehyde. These aldehydes may be used alone or in combination of two or more.

When using the said polyvinyl acetal resin (1) as a part of single-layer intermediate film, it is preferable that the content rate (hydroxyl amount) of the hydroxyl group of the said polyvinyl acetal resin (1) is the following range. The content ratio (hydroxyl content) of the hydroxyl group of the polyvinyl acetal resin (1) is preferably 25 mol% or more, more preferably 28 mol% or more, more preferably 30 mol% or more, and still more preferably 31.5 mol% or more, more preferably 32 mol% or more, and even more preferably 33 mol% or more. The content ratio (hydroxyl content) of the hydroxyl group of the polyvinyl acetal resin (1) is preferably 37 mol% or less, more preferably 36.5 mol% or less, and still more preferably 36 mol% or less. When the content rate of the said hydroxyl group is more than the said minimum, a flexural rigidity will become high more, and the adhesive force of an intermediate film will become high further. Moreover, when the content rate of the said hydroxyl group is below the said upper limit, the flexibility of an intermediate film will become high and handling of an intermediate film will become easy.

The content ratio (hydroxyl content) of the hydroxyl group 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, and more preferably It is 28 mol% or less, more preferably 27 mol% or less, still more preferably 25 mol% or less, and even more preferably 24 mol% or less. When using the said polyvinyl acetal resin (1) as a part of a multilayer intermediate film, it is especially preferable to satisfy the lower limit and upper limit of the content rate of this hydroxyl group. If the content rate of the said hydroxyl group is more than the said lower limit, the mechanical strength of an intermediate film will become higher. In particular, if the hydroxyl group content of the polyvinyl acetal resin (1) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and if it is 28 mol% or less, the laminated glass The sound insulation is further improved. Moreover, when the content rate of the said hydroxyl group is below the said upper limit, the flexibility of an intermediate film will become high and handling of an intermediate film will become easy. In particular, the laminated glass using the intermediate film having a hydroxyl group content of 28 mol% or less of the polyvinyl acetal resin (1) described above tends to have a low flexural rigidity, and can be remarkably improved by the constitution of the present invention. Rigid stiffness.

The content ratios of the hydroxyl groups of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) are preferably 25 mol% or more, more preferably 28 mol% or more, and more preferably 30 mol. More than 3 mole%, more preferably more than 31.5 mole%, still more preferably more than 32 mole%, particularly preferably more than 33 mole%. The content of each hydroxyl group 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, and further preferably 36. Moore% or less. When the content rate of the said hydroxyl group is more than the said minimum, a flexural rigidity will become high more, and the adhesive force of an intermediate film will become high further. Moreover, when the content rate of the said hydroxyl group is below the said upper limit, the flexibility of an intermediate film will become high and handling of an intermediate film will become easy.

From the viewpoint of further improving sound insulation, the content ratio of the hydroxyl group of the polyvinyl acetal resin (1) is preferably lower than the content ratio of the hydroxyl group of the polyvinyl acetal resin (2). From the viewpoint of further improving sound insulation, the content ratio of the hydroxyl group of the polyvinyl acetal resin (1) is preferably lower than the content ratio of the hydroxyl group of the polyvinyl acetal resin (3). From the viewpoint of further improving sound insulation, the absolute value of the difference between the content ratio of the hydroxyl group of the polyvinyl acetal resin (1) and the content ratio of the hydroxyl group 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 improving sound insulation, the absolute value of the difference between the content ratio of the hydroxyl group of the polyvinyl acetal resin (1) and the content ratio of the hydroxyl group 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 content ratio of the hydroxyl group of the polyvinyl acetal resin (1) and the content ratio of the hydroxyl group of the polyvinyl acetal resin (2) is preferably 20 mol% or less. The absolute value of the difference between the content rate of the hydroxyl groups of the polyvinyl acetal resin (1) and the content rate of the hydroxyl groups of the polyvinyl acetal resin (3) is preferably 20 mol% or less.

The content ratio of the hydroxyl group of the said polyvinyl acetal resin is the value of the Mohr fraction calculated | required as the percentage expressing the amount of the extended ethyl group which bonded the hydroxyl group by the total amount of the extended ethyl group of a main chain. The above-mentioned hydroxyl-bonded ethylenic group can be measured in accordance with JIS K6728 "Testing method for polyvinyl butyral", for example.

The degree of acetylation (the amount of ethyl acetate) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and still more preferably 7 mol% or more. It is preferably 9 mol% or more, and more preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 24 mol% or less. When the degree of acetylation is equal to or more than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer or other thermoplastic resin becomes high, the sound insulation property and the penetration resistance are further improved, and the performance is continuously stabilized for a long time. When the degree of acetylation is equal to or less than the above upper limit, the moisture resistance of the interlayer film and the laminated glass becomes high. In particular, if the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol% or more and 25 mol% or less, 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, and preferably 10 Molar% or less, more preferably 2 Molar% or less. When the degree of acetylation is greater than or equal to the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. When the degree of acetylation is equal to or less than the above upper limit, the moisture resistance of the interlayer film and the laminated glass becomes high.

The above-mentioned degree of acetylation is a Mohr fraction value obtained by dividing the amount of ethyl groups bonded with an ethyl group by the percentage by the total amount of ethyl groups bonded to the main chain. The amount of the ethylenic group to which the acetofluorenyl group is bonded can be measured in accordance with JIS K6728 "Testing method for polyvinyl butyral", for example.

The degree of acetalization of the polyvinyl acetal resin (1) (the degree of butyralization in the case of a polyvinyl butyral resin) is preferably 47 mol% or more, and more preferably 60 mol%. Above, still more preferably 68 mol% or more, and more preferably 85 mol% or less, more preferably 80 mol% or less, and 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. If the degree of acetalization is equal to or less than the upper limit described above, the reaction time required for producing the polyvinyl acetal resin becomes short.

The degree of acetalization (in the case of polyvinyl butyral resin, the degree of butyralization) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 55. Molar% or more, more preferably 60 mol% or more, and more preferably 75 mol% or less, and 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. If the degree of acetalization is equal to or less than the upper limit described above, the reaction time required for producing the polyvinyl acetal resin becomes short.

The acetalization degree is determined as follows. First, the value obtained by subtracting the total amount of ethyl groups from the main chain minus the amount of ethyl groups bonded with hydroxyl groups and the amount of ethyl groups bonded with acetamidine groups was determined. The Mohr fraction was calculated by dividing the obtained value by the total ethylenic content of the main chain. The value of the mole fraction expressed as a percentage is the degree of acetalization.

In addition, it is preferable that the content ratio (amount of hydroxyl groups), the degree of acetalization (degree of butyralization), and the degree of acetalization of the above-mentioned hydroxyl groups are based on the method according to JIS K6728 "Testing method for polyvinyl butyral" The measured results are calculated. However, a measurement based on ASTM D1396-92 may be used. In the case where the polyvinyl acetal resin is a polyvinyl butyral resin, the content ratio of the above-mentioned hydroxyl group (hydroxyl amount), the above-mentioned acetalization degree (butyralization degree), and the above-mentioned acetylation degree can be determined by Calculated from the results measured in accordance with JIS K6728 "Test method for polyvinyl butyral".

(Plasticizer) The intermediate film contains a plasticizer. The first layer (including a single-layer intermediate film) preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (3)). By using a plasticizer, and by using a polyvinyl acetal resin and a plasticizer together, penetration resistance is further excellent. A layer containing a polyvinyl acetal resin and a plasticizer is useful for laminated glass members or other layers. Then the force becomes moderately high. The plasticizer is not particularly limited. The plasticizer (1) and the plasticizer (2) may be the same as or different from the plasticizer (3). 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 phosphorous 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 a glycol with a monobasic organic acid. Examples of the diol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, hexanoic acid, 2-ethylbutanoic acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, and capric acid.

Examples of the polybasic organic acid ester include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.

Examples of the organic ester plasticizer include triethylene glycol bis (2-ethylpropionate), triethylene glycol bis (2-ethylbutyrate), and triethylene glycol bis (2-ethyl) Hexanoate), triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate Ester, dioctyl sebacate, dibutylcarbitol adipate, ethylene glycol bis (2-ethylbutyrate), 1,3-propanediol bis (2-ethylbutyrate), 1,4-butanediol bis (2-ethylbutyrate), diethylene glycol bis (2-ethylbutyrate), diethylene glycol bis (2-ethylhexanoate), dipropylene glycol Di (2-ethylbutyrate), triethylene glycol bis (2-ethylvalerate), tetraethylene glycol bis (2-ethylbutyrate), diethylene glycol dicaprylate, Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, dibutyl maleate, bis (2-butoxyethyl) adipate, dibutyl adipate, adipic acid di Isobutyl ester, 2,2-butoxyethoxyethyl adipate, glycol benzoate, 1,3-butanediol adipate polyester, dihexyl adipate, adipic acid di Octyl ester, hexyl adipate, cyclohexyl ester, adipic acid Mixture of heptyl and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl adipate nonyl, tributyl citrate, tributyl acetate Diethyl ester, dibutyl sebacate, oil-modified sebacic acid alkyd resin, and a mixture of phosphoric acid ester and adipate. Other organic ester plasticizers can also be used. Adipates other than the above-mentioned adipates can also be used.

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

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

[Chemical 1]

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

The plasticizer preferably contains triethylene glycol bis (2-ethylhexanoate) (3GO), triethylene glycol bis (2-ethylbutyrate) (3GH), or triethylene glycol bis ( 2-ethylpropionate). The plasticizer preferably contains triethylene glycol bis (2-ethylhexanoate) or triethylene glycol bis (2-ethylbutyrate), and further preferably contains triethylene glycol bis (2-ethylbutyrate). -Ethylhexanoate).

In the second layer, 100 parts by weight of the thermoplastic resin (2) (in the case where the thermoplastic resin (2) is a polyvinyl acetal resin (2), it is a polyvinyl acetal resin (2) The content of the above-mentioned plasticizer (2) (100 parts by weight) is set as the content (2). In the third layer, 100 parts by weight of the thermoplastic resin (3) (in the case where the thermoplastic resin (3) is a polyvinyl acetal resin (3), it is a polyvinyl acetal resin (3) The content of the above-mentioned plasticizer (3) (100 parts by weight) is set as the content (3). The content (2) and the content (3) are each preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and even more preferably 32 parts by weight. It is particularly preferably at most 30 parts by weight. When the said content (2) and said content (3) are more than the said minimum, the softness | flexibility of an intermediate film will become high and handling of an intermediate film will become easy. When the content (2) and the content (3) are equal to or less than the upper limit described above, the flexural rigidity is further increased.

In the first layer, 100 parts by weight of the thermoplastic resin (1) (in the case where the thermoplastic resin (1) is a polyvinyl acetal resin (1), it is a polyvinyl acetal resin (1) The content of the above-mentioned plasticizer (1) (100 parts by weight) is set 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, and preferably 90 parts by weight or less, more preferably It is 85 parts by weight or less, and more preferably 80 parts by weight or less. When the content (1) is greater than or equal to the above lower limit, the flexibility of the interlayer film becomes high, and handling of the interlayer film becomes easy. When the content (1) is equal to or less than the above 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, and 60 parts by weight or more. The content (1) may be 30 parts by weight or less, 20 parts by weight or less, and 10 parts by weight or less.

When the above-mentioned interlayer film is two or more layers, in order to improve the sound insulation of the laminated glass, the content (1) is preferably more than the content (2), and the content (1) is preferably more than the content ( 3). In particular, the laminated glass using the interlayer film having the content (1) of 55 parts by weight or more tends to have a low flexural rigidity. However, the composition of the present invention can significantly improve the flexural 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 absolute value of the difference between the above-mentioned content (3) and the above-mentioned content (1) are respectively smaller than It is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and still more preferably 20 parts by weight or more. The absolute value of the difference between the above-mentioned content (2) and the above-mentioned content (1) and the absolute value of the difference between the above-mentioned content (3) and the above-mentioned content (1) are preferably 80 parts by weight or less, more preferably 75 parts by weight or less. It is more preferably 70 parts by weight or less.

(Heat-insulating material) The intermediate film preferably contains a heat-insulating material. The first layer preferably contains a heat-insulating substance. The second layer preferably contains a heat-insulating substance. The third layer preferably contains a heat-insulating substance. These heat-insulating substances may be used alone or in combination of two or more.

The heat-shielding substance preferably contains at least one component X of a phthalocyanine compound, a naphthol cyanine compound, and an anthraphthalocyanine compound, or contains heat-shielding particles. In this case, both the component X and the heat-insulating particles may be contained.

Component X: The intermediate film preferably contains at least one component X among a phthalocyanine compound, a naphthol cyanine compound, and an anthraphthalocyanine 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-insulating substance. The component X may be used alone or in combination of two or more.

The component X is not particularly limited. As the component X, conventionally known phthalocyanine compounds, naphthol cyanine compounds, and anthracene phthalocyanine compounds can be used.

From the viewpoint of further improving the heat insulation properties of the interlayer film and the laminated glass, the component X is preferably selected from the group consisting of phthalocyanine, a derivative of phthalocyanine, naphthol cyanine, and a derivative of naphthol cyanine At least one of them is more preferably at least one of phthalocyanine and a derivative of phthalocyanine.

From the viewpoint of effectively improving heat insulation and maintaining 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 also preferably contains a copper atom. The component X is more preferably at least one of a phthalocyanine containing a vanadium atom or a copper atom and a derivative of a phthalocyanine containing a vanadium atom or a copper atom. From the viewpoint of further improving the heat insulation properties of the interlayer film and the laminated glass, the component X is preferably a structural unit having an oxygen atom bonded to a vanadium atom.

In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the component X, the content of the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, and still more preferably 0.01 It is more than 5% by weight, and more preferably 0.02% by weight or more. In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the component X, the content of the component X is preferably 0.2% by weight or less, more preferably 0.1% by weight or less, and still more preferably 0.05. It is preferably at most 0.04% by weight. When content of the said component X is more than the said lower limit and below the said upper limit, heat insulation property will fully become high and a visible light transmittance will become high sufficiently. For example, the visible light transmittance can be made 70% or more.

Heat-insulating particles: The intermediate film preferably contains heat-insulating particles. The first layer (including a single-layer intermediate film) preferably contains the heat-insulating particles. The second layer preferably contains the heat-insulating particles. The third layer preferably contains the heat-insulating particles. The heat-insulating particles are heat-insulating substances. By using heat-insulating particles, infrared rays (hot rays) can be effectively blocked. The heat-insulating particles may be used alone or in combination of two or more.

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

Infrared rays with a wavelength longer than 780 nm longer than visible light have less energy than ultraviolet rays. However, the thermal effect of infrared rays is large, and if infrared rays are absorbed by a substance, they are released as heat. Therefore, infrared rays are generally called hot wires. By using the heat-insulating particles, infrared rays (hot rays) can be effectively blocked. The term "insulation particles" means particles that can absorb infrared rays.

Specific examples of the heat-insulating particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles ( IZO particles), aluminum-doped zinc oxide particles (AZO particles), niobium-doped titanium oxide particles, sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, erbium-doped tungsten oxide particles, erbium-doped tungsten oxide particles, tin-doped indium oxide particles ( ITO particles), metal oxide particles such as tin-doped zinc oxide particles, silicon-doped zinc oxide particles, or lanthanum hexaboride (LaB ₆ ) particles. Insulation particles other than these may be used. As far as the shielding function of the hot wire is higher, metal oxide particles are preferred, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferred, and ITO particles or tungsten oxide particles are particularly preferred. Especially in terms of the high shielding function of the hot wire and easy availability, tin-doped indium oxide particles (ITO particles) are preferred, and tungsten oxide particles are also preferred.

From the viewpoint of further improving the heat insulation properties of the interlayer film and the laminated glass, the tungsten oxide particles are preferably metal-doped tungsten oxide particles. The "tungsten oxide particles" include metal-doped tungsten oxide particles. Specific examples of the metal-doped tungsten oxide particles include sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, erbium-doped tungsten oxide particles, and erbium-doped tungsten oxide particles.

From the viewpoint of further improving the heat insulation properties of the interlayer film and the laminated glass, cesium-doped tungsten oxide particles are particularly preferred. From the viewpoint of further improving the heat insulation properties of the interlayer film and the laminated glass, the cesium-doped tungsten oxide particles are preferably tungsten oxide particles represented by the formula: Cs _0.33 WO ₃ .

The average particle diameter of the heat-insulating particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, and preferably 0.1 μm or less, and more preferably 0.05 μm or less. When the average particle diameter is greater than or equal to the above lower limit, the shielding property of the hot wire is sufficiently increased. When the average particle diameter is equal to or less than the above upper limit, the dispersibility of the heat-insulating particles becomes high.

The "average particle diameter" means a volume average particle diameter. The average particle diameter can be measured using a particle size distribution measuring device ("UPA-EX150" manufactured by Nikkiso Co., Ltd.) and the like.

In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the heat-insulating particles, the content of the heat-insulating particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably It is 1% by weight or more, and particularly preferably 1.5% by weight or more. In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the heat-insulating particles, the content of the heat-insulating particles is preferably 6% by weight or less, more preferably 5.5% by weight or less, and further preferably It is 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-insulating particles is equal to or more than the lower limit and equal to or less than the upper limit, the heat-shielding property is sufficiently increased, and the visible light transmittance is sufficiently increased.

(Metal salt) The intermediate film preferably contains at least one metal salt (hereinafter, sometimes referred to as metal salt M) of 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 above-mentioned metal salt M, it becomes easy to control the adhesiveness between the intermediate film and the laminated glass member or the adhesiveness between the layers in the intermediate film. The metal salt M may be used alone or in combination of two or more.

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

The metal salt M is more preferably an alkali metal salt of an organic acid with 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid with 2 to 16 carbon atoms, or a magnesium salt of an organic acid with 2 to 16 carbon atoms, and more preferably It is a magnesium carboxylate having 2 to 16 carbons or a potassium carboxylate having 2 to 16 carbons.

Examples of the magnesium carboxylate salt having 2 to 16 carbon atoms and the potassium carboxylate salt having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, Potassium 2-ethylbutyrate, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate.

The total content of Mg and K in the layer (the first layer, the second layer, or the third layer) containing the metal salt M is preferably 5 ppm or more, more preferably 10 ppm or more, and still more preferably 20 ppm or more. It is preferably 300 ppm or less, more preferably 250 ppm or less, and still more preferably 200 ppm or less. When the total content of Mg and K is at least the above lower limit and at most the above upper limit, the adhesion between the interlayer film and the laminated glass member or the interlayer adhesion between the interlayer films can be further controlled.

(Ultraviolet shielding agent) It is preferable that the said intermediate film contains an ultraviolet shielding agent. The first layer preferably contains an ultraviolet shielding agent. The second layer preferably contains an ultraviolet shielding agent. The third layer preferably contains an ultraviolet shielding agent. By using an ultraviolet shielding agent, it is difficult to further reduce the visible light transmittance even if the interlayer film and the laminated glass are used for a long time. These ultraviolet shielding agents may be used alone or in combination of two or more.

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

Examples of the ultraviolet shielding agent include an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent (benzotriazole compound) having a benzotriazole structure, and benzophenone. Structured UV shielding agent (benzophenone compound), UV shielding agent with three structures (three compounds), UV shielding agent with malonate structure (malonate compound), Ultraviolet shielding agent (graspidate compound) and ultraviolet shielding agent (benzoate compound) having a benzoate structure.

Examples of the ultraviolet shielding agent containing a metal atom include platinum particles, particles coated with silicon dioxide on the surface of platinum particles, palladium particles, and particles coated with silicon dioxide on the surface of palladium particles. The ultraviolet shielding agent is preferably not a heat-insulating particle.

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 three 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, and cerium oxide. Furthermore, the surface of the above-mentioned ultraviolet shielding agent containing a metal oxide may be coated. Examples of the coating material on the surface of the ultraviolet shielding agent containing a metal oxide include an insulating metal oxide, a hydrolyzable organosilicon compound, and a silicone compound.

Examples of the ultraviolet shielding agent having a benzotriazole structure include, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole ("Tinuvin P" manufactured by BASF), 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole ("Tinuvin 320" manufactured by BASF), 2- (2'-hydroxy-3'-tert-butyl 5-methylphenyl) -5-chlorobenzotriazole ("Tinuvin 326" manufactured by BASF), and 2- (2'-hydroxy-3 ', 5'-dipentylphenyl) benzo Triazole ("Tinuvin 328" manufactured by BASF) and the like. In terms of excellent ultraviolet absorption performance, the above-mentioned ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure containing a halogen atom, and more preferably an ultraviolet shielding agent having a benzotriazole structure containing a chlorine atom. .

Examples of the ultraviolet shielding agent having the benzophenone structure include octanone ("Chimassorb 81" manufactured by BASF) and the like.

Examples of the above-mentioned ultraviolet shielding agent having three structures include "LA-F70" and 2- (4,6-diphenyl-1,3,5-tri-2-yl) -5- manufactured by ADEKA Corporation. [(Hexyl) oxy] -phenol ("Tinuvin 1577FF" manufactured by BASF) and the like.

Examples of the ultraviolet shielding agent having a malonate structure include dimethyl 2- (p-methoxybenzylidene) malonate and 2,2- (1,4-phenylene dimethylene) ) Tetraethyl dimalonate, 2- (p-methoxybenzylidene) -bis (1,2,2,6,6-pentamethyl 4-piperidinyl) malonate and the like.

Examples of commercially available ultraviolet shielding agents having a malonate structure include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).

Examples of the above-mentioned ultraviolet shielding agent having a chlorfendiamine structure include N- (2-ethylphenyl) -N '-(2-ethoxy-5-third butylphenyl) oxadiamine. N- (2-ethylphenyl) -N '-(2-ethoxy-phenyl) oxadiadiamine, 2-ethyl-2'-ethoxy-oxyaniline (manufactured by Clariant) "Sanduvor VSU") and other oxalodiamines having an aryl group substituted on a nitrogen atom.

Examples of the ultraviolet shielding agent having a benzoate structure include, for example, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester ("Tinuvin" manufactured by BASF Corporation) 120 ") and so on.

In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the ultraviolet shielding agent, the content of the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and further preferably It is 0.3% by weight or more, and particularly preferably 0.5% by weight or more. In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the ultraviolet shielding agent, the content of the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2% by weight or less, and further preferably It is 1% by weight or less, and particularly preferably 0.8% by weight or less. If the content of the ultraviolet shielding agent is above the lower limit and below the upper limit, it is possible to further suppress a decrease in visible light transmittance after a period of time. In particular, by making the content of the above-mentioned ultraviolet shielding agent to be 0.2% by weight or more in 100% by weight of the layer containing the above-mentioned ultraviolet shielding agent, the decrease in visible light transmittance of the interlayer film and laminated glass after a period of time can be significantly suppressed .

(Antioxidant) The intermediate 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. These antioxidants may be used alone or in combination of two or more.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. The phenol-based 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 antioxidant is preferably a phenol-based antioxidant or a phosphorus-based antioxidant.

Examples of the phenol-based antioxidant include 2,6-di-tert-butyl-p-cresol (BHT), butylhydroxyanisole (BHA), and 2,6-di-tert-butyl-4-ethyl Phenol, β- (3,5-di-tert-butyl-4-hydroxyphenyl) stearate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl-6-third-butylphenol), 4,4'-butylene-bis- (3-methyl-6-third-butylphenol), 1,1,3-tri- (2-methyl-hydroxy-5-third butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-butyl-4-hydroxybenzene Propyl) propionate] methane, 1,3,3-tri- (2-methyl-4-hydroxy-5-third butylphenol) butane, 1,3,5-trimethyl-2,4 , 6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene, bis (3,3'-third-butylphenol) butyrate and bis (3-third-butyl) 4-hydroxy-5-methylphenylpropionic acid) ethylene bis (ethylene oxide) and the like. One or more of these antioxidants can be used favorably.

Examples of the phosphorus-based antioxidant include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, and bis (decyl phosphite) Trialkyl ester) pentaerythritol ester, bis (decyl) diphosphite, pentaerythritol diphosphite, tris (2,4-di-third-butylphenyl) phosphite, bis (2,4-di-third-butyl phosphite -6-methylphenyl) ester ethyl ester, and 2,2'-methylenebis (4,6-di-third-butyl-1-phenoxy) (2-ethylhexyloxy) phosphorus, etc. . One or more of these antioxidants can be used favorably.

Examples of commercially available antioxidants include "IRGANOX 245" manufactured by BASF, "IRGAFOS 168" manufactured by BASF, "IRGAFOS 38" manufactured by BASF, and "Sumilizer BHT" manufactured by Sumitomo Chemical Industries, Ltd. "H-BHT" manufactured by Sakai Chemical Industry Co., Ltd., and "IRGANOX 1010" manufactured by BASF Corporation.

In order to maintain the high visible light transmittance of the interlayer film and laminated glass for a long period of time, the anti- The content of the oxidant is preferably 0.1% by weight or more. In addition, since the additive effect of the antioxidant is saturated, the content of the antioxidant in 100% by weight of the intermediate film or 100% by weight of the layer containing the antioxidant is preferably 2% by weight or less.

(Other components) The intermediate film, the first layer, the second layer, and the third layer may each contain a coupling agent containing silicon, aluminum, or titanium, a dispersant, a surfactant, a flame retardant, and an antistatic, as necessary. Additives, fillers, pigments, dyes, adhesion modifiers, moisture resistance agents, fluorescent whitening agents, and infrared absorbers. These additives may be used alone or in combination of two or more.

In order to control the shear storage modulus to a preferable range, the interlayer film, the first layer, the second layer, and the third layer may also contain a filler. Examples of the filler include calcium carbonate particles and silica particles. From the viewpoint of effectively improving the flexural rigidity and effectively suppressing the decrease in transparency, silicon dioxide particles are preferred.

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

(Other details of the interlayer film for laminated glass) The thickness of the interlayer film is not particularly limited. From the viewpoint of practicality and the viewpoint of sufficiently improving the penetration resistance and flexural rigidity of laminated glass, the thickness of the interlayer film is preferably 0.1 mm or more, more preferably 0.25 mm or more, and preferably 3 mm. It is more preferably 1.5 mm or less. When the thickness of the interlayer film is greater than or equal to the above lower limit, the penetration resistance and flexural rigidity of the laminated glass are further increased. When the thickness of the interlayer film is equal to or less than the above upper limit, the transparency of the interlayer film is further improved.

The thickness of the intermediate film is set to T. The thickness of the first layer is preferably 0.035T or more, more preferably 0.0625T or more, still more preferably 0.1T or more, and more preferably 0.4T or less, more preferably 0.375T or less, and even more preferably 0.25T or less. , Particularly preferably below 0.15T. When the thickness of the first layer is 0.4 T or less, the flexural rigidity is further improved.

The thickness of each of the second layer and the third layer is preferably 0.3T or more, more preferably 0.3125T or more, still more preferably 0.375T or more, and preferably 0.97T or less, more preferably 0.9375T or less, and further It is preferably 0.9T or less. The thickness of each of the second layer and the third layer may be 0.46875T or less, and may be 0.45T or less. When the thicknesses of the second layer and the third layer are equal to or greater than the lower limit and equal to or lower 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 0.625T or more, more preferably 0.75T or more, still more preferably 0.85T or more, and preferably 0.97T or less, more preferably 0.9375T or less, and It is preferably 0.9T or less. When the total thickness of the second layer and the third layer is equal to or greater than the lower limit and equal to or lower 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 varying thickness. The cross-sectional shape of the intermediate film may be rectangular or wedge-shaped.

The manufacturing method of the intermediate film of this invention is not specifically limited. As a method for producing the interlayer film of the present invention, in the case of a single-layer interlayer film, a method of extruding the resin composition using an extruder can be cited. As a method for manufacturing an intermediate film of the present invention, in the case of a multilayer intermediate film, for example, a method of forming each layer using each resin composition for forming each layer, and then laminating the obtained layers; and A method of laminating each resin composition for forming each layer using an extruder and laminating each layer. The manufacturing method of extrusion molding is preferable because it is suitable for continuous production.

In terms of excellent production efficiency of the intermediate film, it is preferable that the same polyvinyl acetal resin is contained in the second layer and the third layer. In terms of excellent production efficiency of the intermediate film, it is more preferable that the second layer and the third layer contain the same polyvinyl acetal resin and the same plasticizer. In terms of excellent production efficiency of the intermediate film, it is more preferable that the second layer and the third layer are formed of the same resin composition.

The intermediate 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 a concave-convex shape on the surfaces on both sides. The method for forming the uneven shape is not particularly limited, and examples thereof include a die lip embossing method, an embossing roll method, a calender roll method, and a profile extrusion method. The embossing roll method is preferable in that the embossing of a large number of uneven shapes as a constant uneven pattern can be formed quantitatively.

(Laminated Glass) FIG. 3 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG. 1.

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

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

4 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass 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 intermediate film 11A. The interlayer film 11A is arranged and sandwiched between the first laminated glass member 21 and the second laminated glass member 22.

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

As described above, the laminated glass of the present invention includes the first laminated glass member, the second laminated glass member, and an interlayer film, and the interlayer film is the interlayer film for laminated glass of the present invention. In the laminated glass of the present invention, the interlayer film is disposed 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 interposed between two glass plates, but also laminated glass in which an interlayer film is interposed between a glass plate and a PET film. The laminated glass is a laminated body including a glass plate, and it is preferable to use at least one glass plate. Preferably, the first laminated glass member and the second laminated glass member are respectively a glass plate or a PET film, and the laminated glass includes a glass plate as the first laminated glass member and the second laminated glass member. At least one of them.

Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include a float plate glass, a heat ray absorption plate glass, a heat ray reflection plate glass, a polishing plate glass, an embossed plate glass, and a spun 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 poly (meth) acrylate plate and the like.

The thickness of the laminated glass member is preferably 1 mm or more, and 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, and 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, and preferably 0.5 mm or less.

By using the interlayer film of the present invention, even if the thickness of the laminated glass is thin, the flexural rigidity of the laminated glass can be maintained high. The thickness of the glass plate is preferably 2 mm or less, more preferably 1.8 mm or less, even more preferably 1.6 mm or less, even more preferably 1.5 mm or less, still more preferably 1.4 mm or less, and still more preferably 1.3 mm or less. It is more preferably 1.0 mm or less, and even more preferably 0.7 mm or less. In this case, the laminated glass can be made lighter, or the material of the laminated glass can be reduced to reduce the environmental load, or the lightweight of the laminated glass can be used to improve the fuel efficiency of the automobile and 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 even more preferably 2.8 mm or less. In this case, the laminated glass can be made lighter, or the material of the laminated glass can be reduced to reduce the environmental load, or the lightweight of the laminated glass can be used to improve the fuel efficiency of the automobile and reduce the environmental load.

The manufacturing method of the said laminated glass is not specifically limited. First, an interlayer film is interposed between the first laminated glass member and the second laminated glass member to obtain a laminated body. Then, for example, the obtained laminated body is passed through a pressure roller or into a rubber bag to be sucked under reduced pressure, thereby remaining between the first laminated glass member, the second laminated glass member, and the interlayer film. The air is degassed. Thereafter, pre-bonding was performed at about 70 to 110 ° C to obtain a pre-pressed laminated body. Then, the pre-pressed laminated body is put into an autoclave or pressurized, and the press-bonding is performed at a pressure of about 120 to 150 ° C and 1 to 1.5 MPa. Thus, a laminated glass can be obtained. When the laminated glass is manufactured, the first layer, the second layer, and the third layer may be laminated.

The interlayer film and the laminated glass can be used in automobiles, rail vehicles, aircraft, ships and buildings. The above-mentioned interlayer film and the above-mentioned laminated glass can also be used in addition to these applications. The intermediate film and the laminated glass are preferably an intermediate film and laminated glass for a vehicle or a building, and more preferably an intermediate film and laminated glass for a vehicle. The above-mentioned interlayer film and the above-mentioned laminated glass can be used for windshield, side glass, rear glass, sunroof glass, etc. of automobiles. The interlayer film and the laminated glass can be suitably used in automobiles. The above interlayer film can be used to obtain laminated glass for automobiles.

Examples and comparative examples are disclosed below to further explain the present invention. The invention is not limited to these examples.

Prepare the following materials.

(Polyvinyl acetal resin) The polyvinyl acetal resin shown in the following Tables 1-3 is used suitably.

Regarding polyvinyl acetal resin, the degree of acetalization, the degree of acetylation, and the content ratio of hydroxyl groups were measured by a method in accordance with JIS K6728 "Test method for polyvinyl butyral". In addition, when measured by ASTM D1396-92, it also showed the same value as the method based on JIS K6728 "Testing method for polyvinyl butyral". When the type of acetal is acetal, acetal, or p-isopropylbenzaldehyde, the degree of acetalization is similarly determined by measuring the degree of acetalization and the content ratio of hydroxyl groups. From the measurement results, the molar fraction was calculated, and then the molar ratio of acetylation and the hydroxyl group content were calculated from 100 molar%.

(Second resin) The acrylic polymers shown in the following Tables 1 to 3 are appropriately used.

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

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 ("manufactured by Shin Nakamura Chemical Co., Ltd." APG-700 ") ethoxylated bisphenol A diacrylate (" A-BPE-20 "manufactured by Shin Nakamura Chemical Co., Ltd.) ε-caprolactone modified tri- (2-propenyloxyethyl) isocyanurate Acid ester ("A-9300-1CL" manufactured by Shin Nakamura Chemical Co., Ltd.) Tri [2- (propenyloxy) ethyl] phosphate triethoxylate pentaerythritol tetraacrylate ("ATM-35E" manufactured by Shin Nakamura Chemical Co., Ltd. )

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

(Example 1) A polyvinyl acetal resin (average degree of polymerization of 560, acetalization degree of 74.0 mol%, hydroxyl group content of 25.0 mol%, and acetalization degree of 0.9 mol%) was prepared. 100 parts by weight of a polymerizable component (60 parts by weight of ethyl acrylate, 14.4 parts by weight of butyl acrylate, 25 parts by weight of benzyl acrylate, and 0.6 parts by weight of tripropylene glycol diacrylate) were prepared. 100 parts by weight of the above-mentioned polyvinyl acetal resin, 100 parts by weight of the above-mentioned polymerizable component, and 300 parts by weight of ethyl acetate as a polymerization solvent were added to a reaction container having a thermometer, a stirrer, a nitrogen introduction pipe, and a cooling pipe. While stirring, the polyvinyl acetal resin is dissolved. Next, nitrogen was blown into the reaction vessel for 30 minutes to replace the inside of the reaction vessel, and then heated to 80 ° C. while stirring in the reaction vessel. After 30 minutes, 6 parts by weight of ethyl acetate will be used as the polymerization initiator as the polymerization initiator (2-ethylhexanoic acid) third butyl ester (1 hour half-life temperature: 92.1 ° C, 10-hour half-life temperature: 72.1 ° C) 0.5 parts by weight of the polymerization initiator solution obtained by dilution was added dropwise into the reaction container. Then, after further reacting at 80 ° C. for 6 hours, the reaction solution was cooled to obtain a solution containing a modified polyvinyl acetal resin.

To the obtained solution, 3GO as a plasticizer was added in an amount of 5 parts by weight based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer (second resin), and a dilution solvent (mixture of methanol and toluene) The solvent, the weight ratio of methanol to toluene was 1: 2), and a 20% by weight solid solution was obtained. Then, the solution was applied to a PET film subjected to a release treatment so that the thickness after drying became 50 μm 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 overlapped and subjected to thermal compression bonding at 150 ° C. and 20 MPa, thereby obtaining an intermediate film having a thickness of 780 μm.

Production of laminated glass: Prepare two glass plates that have been washed and dried (the first laminated glass member and the second laminated glass member, transparent float glass, and flexural rigidity evaluation: 25 mm in length × 200 mm in width Thickness 1 mm, falling ball evaluation: 300 mm in height × 300 mm in width × 1 mm in thickness). The obtained intermediate film was sandwiched between the two glass plates to obtain a laminated body. The obtained laminated body was put into a rubber bag and degassed for 20 minutes under a vacuum of 2660 Pa (20 torr). Thereafter, while maintaining the degassed state, the laminate was held in an autoclave and further held at 90 ° C. for 30 minutes, and then vacuum-pressurized. The pre-pressed laminated body was press-bonded 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) The composition of the composition for forming an intermediate film was set as shown in Tables 1 to 3 below, except that an intermediate film and an intermediate film were obtained in the same manner as in Example 1. Laminated glass.

(Evaluation) (1) Observation of phase structure The obtained intermediate film was processed with a microtome to prepare a slice having a thickness of 100 nm. The obtained sections were stained with osmium tetroxide and observed with a transmission electron microscope. Determine whether there is a phase separation structure.

[Criteria for determining presence or absence of phase separation structure] ○: Structure with phase separation ×: Structure without phase separation

Furthermore, when there is a phase separation structure and a matrix, it is confirmed that the resin component constituting the matrix and the island portion (region) is a polyvinyl acetal resin or a second resin.

[Judging criteria for resin components constituting matrix and island part] A: The component constituting the matrix is a polyvinyl acetal resin and the component constituting the island part is a second resin B: The component constituting the matrix is a second resin and constituting the island part Polyvinyl acetal resin

Furthermore, when there is a phase separation structure and an island portion (area), the diameter (maximum diameter) of the island portion is observed at 3000 times or 5000 times, and the average value is calculated. The average of the diameter of the island was determined based on the following criteria.

[Criteria for determining the average of the diameter of the island] A: The average of the diameter of the island is 10 nm or more and 1 μm or less B: Does not meet the A standard

(2) Flexural rigidity The flexural rigidity was evaluated using the test method schematically shown in FIG. 5. As a measuring device, UTA-500 manufactured by Orientec Co., Ltd. equipped with a 3-point bending test jig was used. As measurement conditions, the measurement temperature was set to 23 ° C (23 ° C ± 3 ° C) or 65 ° C (65 ° C ± 3 ° C), the distance D1 was set to 12 cm, the distance D2 was set to 20 cm, and the displacement speed was 1 mm / min at Deformation was applied to the laminated glass in the direction of F, and the stress when a displacement of 1.5 mm was applied was measured to calculate the flexural rigidity. The flexural rigidity was determined based on the following criteria. The higher the value of the flexural rigidity, the better the flexural rigidity.

[Judging 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 less than 40 N / mm

(3) Penetration resistance The obtained laminated glass was adjusted so that the surface temperature became 20 ° C. Then, for 6 pieces of laminated glass, hard balls with a mass of 2260 g and a diameter of 82 mm were dropped from a height of 2.0 m to the central part of the laminated glass. All 6 pieces of laminated glass were considered to pass if the hard ball did not penetrate within 5 seconds after the hard ball collided. In the case where the laminated glass which has not penetrated the hard ball within 3 seconds after the collision of the hard ball is less than 3 pieces, it is regarded as a failure. In the case of 4 sheets, the penetration resistance of the new 6 sheets of laminated glass was evaluated. In the case of 5 pieces, an additional test is performed on a new piece of laminated glass, and the case where the hard ball does not penetrate within 5 seconds after the hard ball collision is considered to be a pass. Using the same method, each time raising 25 cm, for 6 pieces of laminated glass, hard balls with a mass of 2260 g and a diameter of 82 mm were dropped to the center of the laminated glass, and the penetration resistance (maximum height) of the laminated glass was evaluated. ). The penetration resistance was determined on the basis of the following.

[Determination criteria for penetration resistance] ○: 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.

[Table 1]

[Table 2]

[table 3]

1‧‧‧ Level 1

1a‧‧‧The first surface

1b‧‧‧ 2nd surface

2‧‧‧ Level 2

2a‧‧‧outer surface

3‧‧‧ Level 3

3a‧‧‧ outside surface

11‧‧‧ Interlayer

11A‧‧‧Interlayer (first layer)

11a‧‧‧First surface

11b‧‧‧ 2nd surface

21‧‧‧The first laminated glass member

22‧‧‧ 2nd laminated glass member

31‧‧‧ laminated glass

31A‧‧‧Laminated glass

D1‧‧‧distance

D2‧‧‧distance

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

Claims (11)

An interlayer film for laminated glass comprising a polyvinyl acetal resin, a polymer containing a polymerizable component of a (meth) acrylate compound having two or more (meth) acrylfluorenyl groups, and a plasticizer The content of the polymer is 85 parts by weight or more and 160 parts by weight or less based on 100 parts by weight of the polyvinyl acetal resin, and 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. The content of the plasticizer is 3 parts by weight or more and less than 15 parts by weight, and the interlayer film for laminated glass has a phase separation structure. For example, the interlayer film for laminated glass according to claim 1, wherein the (meth) acrylic acid ester compound having two or more (meth) acrylfluorenyl groups and two having 100 The total amount of the polymerizable compound having a (meth) acrylfluorene group other than the (meth) acrylic acid ester compound of the above (meth) acrylfluorene group is 50% by weight or more, and the polymer is an acrylic polymer. For example, the interlayer film for laminated glass according to claim 1 or 2, wherein the content of the plasticizer is 5 parts by weight or more relative to 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. For example, 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 based on 100 parts by weight of the total of the polyvinyl acetal resin and the polymer. The interlayer film for laminated glass according to claim 1 or 2, wherein the polyvinyl acetal resin and the polymer are crosslinked. If the interlayer film for laminated glass of claim 1 or 2 has a thickness of 3 mm or less. For example, the interlayer film for laminated glass according to claim 1 or 2 is used to obtain a laminated glass by using a first glass plate having a thickness of 1.6 mm or less and placing it between the first glass plate and the second glass plate. For example, the interlayer film for laminated glass of claim 1 or 2 is used to obtain laminated glass disposed between the first glass plate and the second glass plate, and the thickness of the first glass plate and the second glass plate are The total thickness is 3.5 mm or less. A laminated glass comprising: a first laminated glass member, a second laminated glass member, and the interlayer film for laminated glass according to any one of claims 1 to 8, and the interlayer film for laminated glass is configured Between the first laminated glass member and the second laminated glass member. For example, the laminated glass of claim 9, wherein the first laminated glass member is a first glass plate, and the thickness of the first glass plate is 1.6 mm or less. For example, the laminated glass of claim 9 or 10, wherein the first laminated glass member is a first glass plate, the second laminated glass member is a second glass plate, and the thickness of the first glass plate is the same as that of the second glass plate. The total thickness of the glass plate is 3.5 mm or less.