WO2018181746A1

WO2018181746A1 - Interlayer for laminated glass, and laminated glass

Info

Publication number: WO2018181746A1
Application number: PCT/JP2018/013323
Authority: WO
Inventors: 裕司大東; 郁進藤
Original assignee: 積水化学工業株式会社
Priority date: 2017-03-31
Filing date: 2018-03-29
Publication date: 2018-10-04
Also published as: JPWO2018181746A1; TW201841752A; JP7028769B2

Abstract

Provided is an interlayer for laminated glass with which it is possible to increase the flexural stiffness of laminated glass at 23°C, and improve the sound insulation properties and piercing resistance of the laminated glass. This interlayer for laminated glass contains polyvinyl acetal resin and a plasticizer, and the gel fraction determined by formula (X) falls within the range of 10% to 80% by weight, inclusive, the glass transition temperature falls within the range of -30°C to 0°C, inclusive, and the maximum value for tanδ in the temperature region of -30°C to 0°C is at least 0.1. Formula (X): gel fraction (% by weight)=W2/W1×100 (in the formula, W1 is the weight of the interlayer before being immersed in tetrahydrofuran at 23°C, and W2 is the weight of the interlayer which has been immersed in tetrahydrofuran at 23°C and subsequently dried)

Description

Laminated glass interlayer film and laminated glass

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

Laminated glass is superior in safety even if it is damaged by an external impact and the amount of glass fragments scattered is small. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between two glass plates.

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

Furthermore, the following Patent Document 1 also describes a multilayer intermediate film in which the sound insulation layer and other layers are laminated. The other layer laminated on the sound insulation layer is composed of 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of at least one of an alkali metal salt and an alkaline earth metal salt. 1.0 part by weight and a plasticizer that is 30 parts by weight or less are included.

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

JP 2007-070200 A US2013 / 0236711A1

In conventional laminated glass using an interlayer film as described in

Patent Documents

1 and 2, the bending rigidity may be low. For this reason, for example, when laminated glass is used as a window glass for a side door of an automobile, there is no frame for fixing the laminated glass, and due to bending due to the low rigidity of the laminated glass, May interfere with opening and closing.

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

For example, even if the thickness of the glass plate is thin, the laminated glass can be reduced in weight if the bending rigidity of the laminated glass can be increased due to the intermediate film. If the laminated glass is lightweight, the amount of material used for the laminated glass can be reduced, and the environmental load can be reduced. Furthermore, when a laminated glass that is lightweight is used in an automobile, fuel efficiency can be improved, and as a result, environmental load can be reduced.

In addition, laminated glass using an interlayer film is desired to have high sound insulation and penetration resistance in addition to high bending rigidity.

An object of the present invention is to provide an interlayer film for laminated glass that can increase the bending rigidity of the laminated glass at 23 ° C. and can improve the sound insulation and penetration resistance of the laminated glass. Another object of the present invention is to provide a laminated glass using the interlayer film for laminated glass.

According to a wide aspect of the present invention, the composition contains a polyvinyl acetal resin and a plasticizer, has a gel fraction determined by the following formula (X) of 10% by weight to 80% by weight, and a glass transition temperature of −30 ° C. or higher. Provided is an interlayer film for laminated glass (hereinafter sometimes referred to as an interlayer film) present at 0 ° C. or less and having a maximum tan δ of 0.1 or more in a temperature range of −30 ° C. or more and 0 ° C. or less. The

Gel fraction (% by weight) = W2 / W1 × 100 Formula (X)
W1: Weight of the intermediate film before immersing the intermediate film in tetrahydrofuran at 23 ° C W2: Weight of the intermediate film after being taken out after being immersed in tetrahydrofuran at 23 ° C and dried

In a specific aspect of the interlayer film according to the present invention, the content of the polyvinyl acetal resin is 10% by weight or more in 100% by weight of the insoluble component of the interlayer film with respect to tetrahydrofuran at 23 ° C.

In a specific aspect of the intermediate film according to the present invention, the intermediate film includes a second resin other than the polyvinyl acetal resin.

In a specific aspect of the interlayer film according to the present invention, the content of the polyvinyl acetal resin is 25% by weight or more in a total of 100% by weight of the polyvinyl acetal resin and the second resin.

In a specific aspect of the intermediate film according to the present invention, the intermediate film includes an acrylic polymer as the second resin.

In a specific aspect of the interlayer film according to the present invention, the content of the acrylic polymer is 75% by weight or less in a total of 100% by weight of the polyvinyl acetal resin and the second resin.

In a specific aspect of the interlayer film according to the present invention, the polyvinyl acetal resin contained in the interlayer film is a polyvinyl acetoacetal resin, a polyvinyl butyral resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal resin.

In a specific aspect of the intermediate film according to the present invention, the thickness is 3 mm or less.

On the specific situation with the intermediate film which concerns on this invention, an intermediate film uses the 1st glass plate which is 1.6 mm or less in thickness, Between the said 1st glass plate and a 2nd glass plate. Arranged and used to obtain laminated glass.

On the specific situation with the intermediate film which concerns on this invention, an intermediate film is arrange | positioned between a 1st glass plate and a 2nd glass plate, and is used in order to obtain a laminated glass, Said 1st glass The total of the thickness of the plate and the thickness of the second glass plate is 3.5 mm or less.

According to a wide aspect of the present invention, the first laminated glass member, the second laminated glass member, and the interlayer film for laminated glass described above are provided, and the first laminated glass member and the second laminated glass are provided. There is provided a laminated glass in which the interlayer film for laminated glass is disposed between the members.

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

On the specific situation with the laminated glass which concerns on this invention, a said 1st laminated glass member is a 1st glass plate, a said 2nd laminated glass member is a 2nd glass plate, The said 1st glass The total of the thickness of the plate and the thickness of the second glass plate is 3.5 mm or less.

The interlayer film for laminated glass according to the present invention contains a polyvinyl acetal resin and a plasticizer. In the interlayer film for laminated glass according to the present invention, the gel fraction determined by the formula (X) is from 10% by weight to 80% by weight, the glass transition temperature is from −30 ° C. to 0 ° C., and −30 The maximum value of tan δ in the temperature range from 0 ° C. to 0 ° C. is 0.1 or more. Since the interlayer film for laminated glass according to the present invention has the above-described configuration, the bending rigidity at 23 ° C. of the laminated glass using the interlayer film for laminated glass according to the present invention can be increased. The sound insulation and penetration resistance of glass can be improved.

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

Hereinafter, the present invention will be described in detail.

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

The interlayer film for laminated glass according to the present invention contains a polyvinyl acetal resin and a plasticizer.

Further, in the interlayer film according to the present invention, the gel fraction obtained by the following formula (X) is 10% by weight or more and 80% by weight or less.

Furthermore, in the intermediate film according to the present invention, the glass transition temperature is present between −30 ° C. and 0 ° C. Furthermore, in the intermediate film according to the present invention, the maximum value of tan δ in the temperature range of −30 ° C. or more and 0 ° C. or less is 0.1 or more.

Since the interlayer film according to the present invention has the above-described configuration, the bending rigidity at 23 ° C. of the laminated glass using the interlayer film according to the present invention can be increased. Moreover, in order to obtain a laminated glass, an intermediate film is often disposed between the first glass plate and the second glass plate. Even if the thickness of the first glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. Moreover, even if the thickness of both the first glass plate and the second glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. In addition, when the thickness of both the 1st glass plate and the 2nd glass plate is thick, the bending rigidity of a laminated glass will become still higher.

Furthermore, since the intermediate film according to the present invention has the above-described configuration, the sound insulation of the laminated glass using the intermediate film can be improved.

Furthermore, since the intermediate film according to the present invention has the above-described configuration, the penetration resistance of the laminated glass using the intermediate film can be improved. Even if the laminated glass is damaged by an external impact, the amount of glass fragments scattered is reduced.

From the viewpoint of improving penetration resistance, the gel fraction is 10% by weight or more and 80% by weight or less. When the said gel fraction is 10 weight% or more, the improvement effect of penetration resistance becomes high. When the gel fraction is 80% by weight or less, the penetration resistance is considerably increased. From the viewpoint of further improving the penetration resistance, the gel fraction is preferably 30% by weight or more, and preferably 50% by weight or less.

Examples of the method for bringing the gel fraction within the above range include a method of adding a cross-linking agent during the preparation of the intermediate film, a method using a molecule having a crosslinkable group as a resin component, and a solubility in an organic solvent during the preparation of the intermediate film The method of adding a component with low is mentioned.

From the viewpoint of improving sound insulation, the interlayer film has a glass transition temperature of −30 ° C. or higher and 0 ° C. or lower. From the viewpoint of further improving the sound insulation, the interlayer film preferably has a glass transition temperature of −25 ° C. or higher and 0 ° C. or lower, and more preferably −20 ° C. or higher and 0 ° C. or lower. When the glass transition temperature is not less than the above lower limit and not more than the above upper limit, the temperature corresponding to the coincidence frequency can be obtained from the time-temperature conversion rule, and the sound insulation can be effectively improved. Further, since it is possible to cope with a high speed, the energy absorption of high-speed impact is increased, and the penetration resistance is effectively improved.

As a method of measuring the glass transition temperature, a viscoelasticity measuring device “DMA + 1000” manufactured by Metraviv was used immediately after the intermediate film was stored for 12 hours in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5%. And a method of measuring viscoelasticity. The intermediate film was cut out with a length of 50 mm and a width of 20 mm, and the temperature was increased from −50 ° C. to 100 ° C. at a rate of temperature increase of 2 ° C./min in the shear mode, and under the conditions of frequency 1 Hz and strain 0.05% It is preferable to measure the glass transition temperature.

From the viewpoint of improving sound insulation, the maximum value of tan δ in the temperature range of −30 ° C. or more and 0 ° C. or less of the intermediate film is 0.1 or more. The maximum value of tan δ in the temperature range of −30 ° C. to 0 ° C. of the intermediate film is preferably 0.11 or more, preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.6 or less. When the maximum value of tan δ is equal to or greater than the above lower limit, energy loss increases, so that sound insulation, penetration resistance, and bendability are effectively enhanced. When the maximum value of tan δ is less than or equal to the above upper limit, the shear storage modulus is appropriately increased, and the bending rigidity and penetration resistance are effectively increased.

Note that the interlayer film may be applied to bent glass for the purpose of obtaining a curved laminated glass. The bendability mentioned above means the ease of alignment when matching to bent glass.

Tan δ is preferably 0.1 or more in a temperature range of 10% or more of the temperature range of −30 ° C. or more and 0 ° C. or less. In this case, the sound insulation is effectively increased over a wide temperature range. Sound insulation is effectively increased.

From the viewpoint of further improving the bending rigidity and penetration resistance, the intermediate film preferably has a phase separation structure. One of the factors that achieve these effects is considered to be that energy distribution proceeds smoothly by the phase separation structure.

The phase separation structure is preferably a co-continuous structure or a sea-island structure. The phase separation structure may be a co-continuous structure or a sea-island structure. The polyvinyl acetal resin and the second resin are preferably contained in different phases. In the case of a sea-island structure, penetration resistance is improved when the polyvinyl acetal resin is a sea part and the second resin is an island part. In the phase separation structure, the polyvinyl acetal resin and the second resin may form a co-continuous structure. In the case of the bicontinuous structure, the penetration resistance is improved when the polyvinyl acetal resin is continuous (has a continuous structure). In the phase separation structure, the polyvinyl acetal resin may be present in a network form. From the viewpoint of excellent effects of the present invention, the polyvinyl acetal resin and the second resin preferably have a sea-island structure or a bicontinuous structure. That is, in the phase separation structure, it is preferable that the polyvinyl acetal resin and the second resin form a sea-island structure or a bicontinuous structure.

In the sea-island structure, the average diameter of the island part is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, particularly preferably 30 nm or more, preferably 13 μm or less, more preferably 10 μm or less, still more preferably. 2 μm or less. The diameter of one island part indicates the maximum diameter, and the average of the island parts is obtained by averaging the diameters (maximum diameters) of a plurality of islands.

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 the 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 the second surface side of the first layer opposite to the first surface. The

The surface of the second layer opposite to the first layer side is preferably a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated | stacked on the said 2nd layer becomes like this. Preferably it is 1.6 mm or less, More preferably, it is 1.3 mm or less. The second surface opposite to the first surface of the first layer (the surface on the second layer side) may be a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated | stacked on the said 1st layer becomes like this. Preferably it is 1.6 mm or less, More preferably, it is 1.3 mm or less. The surface of the third layer opposite to the first layer side is preferably a surface on which a laminated glass member or a glass plate is laminated. The thickness of the glass plate laminated on the third layer is preferably 1.6 mm or less, more preferably 1.3 mm or less.

The intermediate film is disposed between the first glass plate and the second glass plate and is preferably used for obtaining laminated glass. Since the bending rigidity can be sufficiently increased due to the intermediate film, the total thickness of the first glass plate and the second glass plate is preferably 3.5 mm or less, more preferably 3 mm. It is as follows. The said intermediate film is arrange | positioned between a 1st glass plate and a 2nd glass plate, and is used suitably in order to obtain a laminated glass. Since the bending rigidity can be sufficiently increased due to the intermediate film, the intermediate film is formed using the first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). It arrange | positions between 1 glass plate and 2nd glass plate, and is used suitably in order to obtain a laminated glass. The intermediate film includes a first glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less) and a second glass plate having a thickness of 1.6 mm or less (preferably 1.3 mm or less). It is used between the first glass plate and the second glass plate and is more preferably used to obtain laminated glass. Also in this case, the bending rigidity can be sufficiently increased due to the intermediate film.

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

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

The 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 intermediate film 11 is an intermediate film for laminated glass. The intermediate film 11 includes a first layer 1, a second layer 2, and a third layer 3. On the first surface 1a of the first layer 1, the second layer 2 is disposed and laminated. The third layer 3 is disposed on the second surface 1b opposite to the first surface 1a of the first layer 1 and laminated. The first layer 1 is an intermediate layer. Each of the second layer 2 and the third layer 3 is a protective layer, and is a surface layer in the present embodiment. The first layer 1 is arranged between the second layer 2 and the third layer 3 and is sandwiched between them. Therefore, the intermediate film 11 has a multilayer structure (second layer 2 / first layer 1 / third layer) in which the second layer 2, the first layer 1, and the third layer 3 are laminated in this order. Having layer 3).

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

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

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

The details of the first layer, the second layer, and the third layer constituting the intermediate film according to the present invention, and the first layer, the second layer, and the third layer are as follows. The detail of each component contained is demonstrated.

(resin)
The interlayer film includes a polyvinyl acetal resin. Each of the first layer, the second layer, and the third layer preferably includes a polyvinyl acetal resin. As for the said polyvinyl acetal resin, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further improving sound insulation, the content of the polyvinyl acetal resin is preferably 10% by weight or more in 100% by weight of the insoluble component of the interlayer film with respect to tetrahydrofuran at 23 ° C.

The insoluble component of the intermediate film with respect to tetrahydrofuran at 23 ° C. is an intermediate film after the intermediate film is taken out after being immersed in tetrahydrofuran at 23 ° C. and dried.

In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the polyvinyl acetal resin is preferably 20% by weight or more, more preferably 25% by weight or more, and further preferably 30% by weight or more. Especially preferably, it is 35 weight% or more, Preferably it is 100 weight% or less. When the content of the polyvinyl acetal resin is not less than the above lower limit, the bending rigidity is effectively increased. In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the polyvinyl acetal resin may be less than 100% by weight, 90% by weight or less, and 80% by weight. May be 75% by weight or less, 70% by weight or less, or 65% by weight or less. When the content of the polyvinyl acetal resin is not more than the above upper limit, the sound insulation is effectively increased.

From the viewpoint of effectively increasing the affinity between the resin component and the plasticizer and effectively increasing the penetration resistance, the polyvinyl acetal resin is a polyvinyl acetoacetal resin, a polyvinyl butyral resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal. A resin is preferred. From the viewpoint of further increasing the bending rigidity at 40 ° C., a polyvinyl acetoacetal resin is preferable. In the present specification, polyvinyl acetal resins include acetoacetalized resins, benzyl acetalized resins, and cumin acetalized resins.

From the viewpoint of effectively increasing the bending rigidity and sound insulation, the intermediate film preferably includes a second resin other than the polyvinyl acetal resin. From the viewpoint of effectively increasing the bending rigidity and the sound insulation, each of the first layer, the second layer, and the third layer preferably contains a second resin other than the polyvinyl acetal resin. Examples of the second resin include thermosetting resins and thermoplastic resins. The intermediate film preferably contains a thermoplastic resin (second thermoplastic resin other than polyvinyl acetal resin) as the second resin. A thermoplastic resin other than the polyvinyl acetal resin may be referred to as a second thermoplastic resin, as distinguished from the polyvinyl acetal resin. As for said 2nd resin, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of effectively increasing the bending rigidity and sound insulation, the intermediate film contains a polyolefin resin, an acrylic polymer, a urethane polymer, a silicone polymer, rubber, or a vinyl acetate polymer as the second resin. It is more preferable that it contains an acrylic polymer.

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

The poly (meth) acrylic acid ester is not particularly limited. Examples of the poly (meth) acrylic acid ester include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate n-propyl, poly (meth) acrylate i-propyl, poly N-butyl (meth) acrylate, i-butyl poly (meth) acrylate, t-butyl poly (meth) acrylate, 2-ethylhexyl poly (meth) acrylate, 2-hydroxyethyl poly (meth) acrylate, Poly (meth) acrylate 2-hydroxypropyl, poly (meth) acrylate 4-hydroxybutyl, poly (meth) acrylate glycidyl, poly (meth) acrylate octyl, poly (meth) acrylate propyl, poly (meth) 2-ethyloctyl acrylate, poly (meth) acrylate nonyl, poly (meth) acrylate isononyl, Li (meth) acrylate decyl, poly (meth) acrylate isodecyl, poly (meth) acrylate lauryl, poly (meth) acrylate isotetradecyl, poly (meth) acrylate cyclohexyl, poly (meth) acrylate isobornyl, And poly (meth) acrylate benzyl. Examples of (meth) acrylic acid having a polar group and (meth) acrylic acid ester include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and Examples include glycidyl (meth) acrylate. In the dynamic viscoelastic spectrum, the polyacrylic acid ester is preferred because the temperature showing the maximum value of the loss tangent can be easily controlled within an appropriate range, and polyacrylic acid ester is preferable. 2-ethylhexyl acrylate or octyl polyacrylate is more preferred. By using these preferable poly (meth) acrylic acid esters, the productivity of the intermediate film and the balance of the characteristics of the intermediate film are further improved. As for the said poly (meth) acrylic acid ester, only 1 type may be used and 2 or more types may be used together.

Of the total 100% by weight of the polyvinyl acetal resin and the second resin, the content of the second resin other than the polyvinyl acetal resin is preferably 20% by weight or more, more preferably 25% by weight or more, and still more preferably 30%. % By weight or more, particularly preferably 35% by weight or more, and preferably 100% by weight or less. When the content of the second resin is equal to or higher than the lower limit, the sound insulation is effectively increased. In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the second resin may be less than 100% by weight, preferably 90% by weight or less, more preferably 80% by weight. % Or less, more preferably 75% by weight or less, particularly preferably 70% by weight or less, and most preferably 65% by weight or less. When the content of the second resin is not more than the upper limit, the bending rigidity is effectively increased.

In a total of 100% by weight of the polyvinyl acetal resin and the second resin, the content of the acrylic polymer is preferably 20% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more, particularly preferably. Is 35% by weight or more, preferably 100% by weight or less. When the content of the acrylic polymer is not less than the above lower limit, the sound insulation is effectively increased. In the total 100% by weight of the polyvinyl acetal resin and the second resin, the content of the acrylic polymer may be less than 100% by weight, preferably 90% by weight or less, more preferably 80% by weight. Hereinafter, it is more preferably 75% by weight or less, particularly preferably 70% by weight or less, and most preferably 65% by weight or less. When the content of the acrylic polymer is not more than the above upper limit, the bending rigidity is effectively increased.

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

The following methods may be mentioned as methods for crosslinking the resin. A method in which crosslinks are formed by introducing functional groups that react with each other into the polymer structure of the resin. A method of crosslinking using a crosslinking agent having two or more functional groups that react with a functional group present in the polymer structure of the resin. A method of crosslinking a polymer by using a radical generator having a hydrogen abstraction ability such as peroxide. A method of crosslinking by electron beam irradiation. Since the shear storage modulus can be easily controlled and the productivity of the intermediate film is increased, a method in which functional groups that react with each other are introduced into the polymer structure of the resin to form a crosslink is preferable.

The first layer (including a single-layer intermediate film) preferably includes 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 the intermediate film is a single-layer intermediate film composed of only the first layer, the intermediate film contains the 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. Since the sound insulation is further enhanced, the polyvinyl acetal resin (1) is preferably different from the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3). The thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be the same or different. As for the said polyvinyl acetal resin (1), the said polyvinyl acetal resin (2), and the said polyvinyl acetal resin (3), only 1 type may respectively be used and 2 or more types may be used together. As for the said thermoplastic resin (1), the said thermoplastic resin (2), and the said thermoplastic resin (3), only 1 type may respectively be used and 2 or more types may be used together.

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

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

The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably It is 5000 or less, more preferably 4000 or less, and still more preferably 3500 or less. When the average degree of polymerization is not less than the above lower limit, the penetration resistance and bending rigidity of the laminated glass are further increased. When the average degree of polymerization is not more than the above upper limit, the intermediate film can be easily molded.

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

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

In general, an aldehyde having 1 to 10 carbon atoms is suitably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, Examples include n-nonyl aldehyde, n-decyl aldehyde, cumin aldehyde, and benzaldehyde. Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde are preferred. Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde or n-valeraldehyde is more preferred, and acetaldehyde, n-butyraldehyde or n-valeraldehyde is still more preferred. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

When the polyvinyl acetal resin (1) is used as a part of a single-layer interlayer film, the hydroxyl content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably in the following range. The hydroxyl group content (hydroxyl content) 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 even more preferably 31.5 mol%. More preferably, it is at least 32 mol%, particularly preferably at least 33 mol%. The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably not more than 37 mol%, more preferably not more than 36.5 mol%, still more preferably not more than 36 mol%. When the hydroxyl group content is at least the above lower limit, the bending rigidity is further increased, and the adhesive strength of the interlayer film is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.

The hydroxyl group content (hydroxyl content) of the polyvinyl acetal resin (1) is preferably 17 mol% or more, more preferably 20 mol% or more, still more preferably 22 mol% or more, preferably 28 mol% or less, more preferably. Is 27 mol% or less, more preferably 25 mol% or less, and particularly preferably 24 mol% or less. In particular, when the polyvinyl acetal resin (1) is used as a part of a multilayer interlayer film, it is preferable that the lower limit and the upper limit of the hydroxyl group content are satisfied. When the hydroxyl group content is equal to or higher than the lower limit, the mechanical strength of the interlayer film is further increased. In particular, when 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 when it is 28 mol% or less, the sound insulation of the laminated glass is further enhanced. . Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated. In particular, a laminated glass using an interlayer film having a hydroxyl group content of 28 mol% or less in the polyvinyl acetal resin (1) tends to have a low bending rigidity. Can improve.

The content of each hydroxyl group in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, more preferably 30 mol% or more, and still more preferably. It is 31.5 mol% or more, more preferably 32 mol% or more, and particularly preferably 33 mol% or more. Each content rate of the hydroxyl group of the said polyvinyl acetal resin (2) and the said polyvinyl acetal resin (3) becomes like this. Preferably it is 37 mol% or less, More preferably, it is 36.5 mol% or less, More preferably, it is 36 mol% or less. When the hydroxyl group content is at least the above lower limit, the bending rigidity is further increased, and the adhesive strength of the interlayer film is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.

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

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

The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, still more preferably 9 It is at least mol%, preferably at most 30 mol%, more preferably at most 25 mol%, still more preferably at most 24 mol%. When the degree of acetylation is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer or other thermoplastic resin is increased, the sound insulation and penetration resistance are further improved, and the performance is further improved over a long period of time. Stabilize. When the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass is increased. In particular, when the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol% or more and 25 mol% or less, the penetration resistance is further improved.

Each degree of acetylation of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably. Is 2 mol% or less. When the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased. When the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass is increased.

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

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

The degree of acetalization (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 55 mol% or more, more preferably 60 mol% or more, preferably Is 75 mol% or less, more preferably 71 mol% or less. When the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.

The degree of acetalization is obtained as follows. First, a value obtained by subtracting the amount of ethylene groups bonded with hydroxyl groups and the amount of ethylene groups bonded with acetyl groups from the total amount of ethylene groups in the main chain is obtained. The obtained value is divided by the total amount of ethylene groups in the main chain to obtain the mole fraction. A value indicating the mole fraction as a percentage is the degree of acetalization.

The hydroxyl group content (hydroxyl content), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from results measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. However, measurement by ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl amount), the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated from the results measured by

(Plasticizer)
The intermediate film includes a plasticizer. The first layer (including a single-layer interlayer) preferably includes 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 may be referred to as a plasticizer (3)). By using a plasticizer, and by using a polyvinyl acetal resin and a plasticizer in combination, the penetration resistance is further improved, and the adhesive strength of the layer containing the polyvinyl acetal resin and the plasticizer to the laminated glass member or other layers is moderately high. Become. The plasticizer is not particularly limited. The plasticizer (1), the plasticizer (2), and the plasticizer (3) may be the same or different. As for the said plasticizer (1), the said plasticizer (2), and the said plasticizer (3), only 1 type may respectively be used and 2 or more types may be used together.

Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphate 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 a reaction between glycol and a monobasic organic acid. Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.

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

Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, Triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl Hexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate , Dibutyl maleate, bis (2-butoxyethyl) adipate, dibutyl adipate, diisobutyl adipate, 2,2-butoxyethoxyethyl adipate, glycol benzoate, 1,3-butylene glycol polyester adipate, adipic acid Dihexyl, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisoadipate Sill, Hepuchirunoniru adipic acid, tributyl citrate, acetyl tributyl citrate, diethyl carbonate, dibutyl sebacate, oil-modified sebacic alkyds, and mixtures of phosphoric acid esters and adipic acid esters. Organic ester plasticizers other than these may be used. Other adipic acid esters other than the above-mentioned adipic acid esters may be used.

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

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

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

The plasticizer preferably contains triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH) or triethylene glycol di-2-ethylpropanoate. . The plasticizer preferably includes triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and further includes triethylene glycol di-2-ethylhexanoate. preferable.

In the second layer, the plastic with respect to 100 parts by weight of the thermoplastic resin (2) (when the thermoplastic resin (2) is a polyvinyl acetal resin (2), 100 parts by weight of the polyvinyl acetal resin (2)). Let content of an agent (2) be content (2). In the third layer, the plastic relative to 100 parts by weight of the thermoplastic resin (3) (when the thermoplastic resin (3) is a polyvinyl acetal resin (3), 100 parts by weight of the polyvinyl acetal resin (3)). Let content of an agent (3) be 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, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and still more preferably 32 parts. It is 30 parts by weight or less, particularly preferably 30 parts by weight or less. When the content (2) and the content (3) are equal to or higher than the lower limit, the flexibility of the intermediate film is increased and the handling of the intermediate film is facilitated. When the content (2) and the content (3) are equal to or lower than the upper limit, the bending rigidity is further increased.

In the first layer, the plastic relative to 100 parts by weight of the thermoplastic resin (1) (or 100 parts by weight of the polyvinyl acetal resin (1) when the thermoplastic resin (1) is a polyvinyl acetal resin (1)). Let content of an agent (1) be content (1). The content (1) is preferably 1 part by weight or more, more preferably 2 parts by weight or more, still more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more, preferably 90 parts by weight or less, more preferably 85 parts by weight or less, more preferably 80 parts by weight or less, particularly preferably less than 60 parts by weight, and most preferably less than 50 parts by weight. When the content (1) is not less than the above lower limit, the flexibility of the intermediate film is increased, and the handling of the intermediate film is facilitated. Moreover, the penetration resistance of a laminated glass becomes still higher that the said content (1) is more than the said minimum. When the content (1) is not more than the above upper limit and less than the above upper limit, the penetration resistance of the laminated glass is further enhanced. The content (1) may be 50 parts by weight or more, 55 parts by weight or more, or 60 parts by weight or more. The content (1) may be 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

When the interlayer film has two or more layers, the content (1) is preferably larger than the content (2) in order to enhance the sound insulation of the laminated glass, and the content (1) is It is preferable that there is more than the said content (3). In particular, the laminated glass using the intermediate film having the content (1) of 55 parts by weight or more tends to have low bending rigidity, but the structure of the present invention can remarkably improve the bending rigidity.

From the viewpoint of further improving the sound insulation of the laminated glass, the absolute value of the difference between the content (2) and the content (1), and the difference between the content (3) and the content (1). 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 content (2) and the content (1) and the absolute value of the difference between the content (3) and the content (1) are each preferably 80 parts by weight or less. More preferably, it is 75 weight part or less, More preferably, it is 70 weight part or less.

(Heat shielding material)
The intermediate film preferably contains a heat shielding material (heat shielding compound). The first layer preferably contains a heat shielding material. The second layer preferably includes a heat shielding material. The third layer preferably contains a heat shielding material. As for the said heat-shielding compound, only 1 type may be used and 2 or more types may be used together.

The heat-insulating substance preferably contains at least one component X of phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds, or contains heat-shielding particles. In this case, both the component X and the heat shielding particles may be included.

Component X:
The intermediate film preferably includes at least one component X among a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound. The first layer preferably contains the component X. The second layer preferably contains the component X. The third layer preferably contains the component X. The component X is a heat shielding material. As for the said component X, only 1 type may be used and 2 or more types may be used together.

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

From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X is preferably at least one selected from the group consisting of phthalocyanine, phthalocyanine derivatives, naphthalocyanine, and naphthalocyanine derivatives. More preferably, it is at least one of phthalocyanine and phthalocyanine derivatives.

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

In 100% by weight of the layer containing the component X (first layer, second layer or third layer), the content of the component X is preferably 0.001% by weight or more, more preferably 0.005. % By weight or more, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more. In 100% by weight of the layer containing the component X (first layer, second layer, or third layer), the content of the component X is preferably 0.2% by weight or less, more preferably 0.1%. % By weight or less, more preferably 0.05% by weight or less, particularly preferably 0.04% by weight or less. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high. For example, the visible light transmittance can be 70% or more.

Thermal barrier particles:
The intermediate film preferably contains heat shielding particles. The first layer (including a single-layer intermediate film) preferably includes the heat shielding particles. The second layer preferably includes the heat shielding particles. The third layer preferably contains the heat shielding particles. The heat shielding particles are heat shielding materials. By using heat shielding particles, infrared rays (heat rays) can be effectively blocked. As for the said heat-shielding particle, only 1 type may be used and 2 or more types may be used together.

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 shielding particles are preferably particles (metal oxide particles) formed of a metal oxide.

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

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

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

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

The average particle diameter of the heat shielding particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.1 μm or less, more preferably 0.05 μm or less. When the average particle size is not less than the above lower limit, the heat ray shielding property is sufficiently increased. When the average particle size is not more than the above upper limit, the dispersibility of the heat shielding particles is increased.

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

In 100% by weight of the layer containing the heat shielding particles (first layer, second layer or third layer), the content of the heat shielding particles is preferably 0.01% by weight or more, more preferably 0%. .1% by weight or more, more preferably 1% by weight or more, and particularly preferably 1.5% by weight or more. In 100% by weight of the layer containing the heat shielding particles (first layer, second layer or third layer), the content of the heat shielding particles is preferably 6% by weight or less, more preferably 5.5%. % By weight or less, more preferably 4% by weight or less, particularly preferably 3.5% by weight or less, and most preferably 3% by weight or less. When the content of the heat shielding particles is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high.

(Metal salt)
The intermediate film preferably contains at least one metal salt (hereinafter sometimes referred to as metal salt M) among alkali metal salts, alkaline earth metal salts, and magnesium salts. The first layer preferably includes the metal salt M. The second layer preferably contains the metal salt M. The third layer preferably contains the metal salt M. Use of the metal salt M makes it easy to control the adhesion between the interlayer film and the laminated glass member or the adhesion between the layers in the interlayer film. As for the said metal salt M, only 1 type may be used and 2 or more types may be used together.

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

Examples of the C 2-16 carboxylic acid magnesium salt and the C 2-16 carboxylic acid potassium salt include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, 2-ethylbutanoic acid. Examples include potassium, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.

The total content of Mg and K in the layer containing the metal salt M (first layer, second layer, or third layer) is preferably 5 ppm or more, more preferably 10 ppm or more, and even more preferably 20 ppm or more. , Preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less. When the total content of Mg and K is not less than the above lower limit and not more than the above upper limit, the adhesion between the interlayer film and the laminated glass member or the adhesion between the layers in the interlayer film can be controlled even better.

(UV shielding agent)
The intermediate film preferably contains an ultraviolet shielding agent. The first layer preferably contains an ultraviolet shielding agent. The second layer preferably contains an ultraviolet shielding agent. The third layer preferably contains an ultraviolet shielding agent. By using the ultraviolet shielding agent, even if the interlayer film and the laminated glass are used for a long period of time, the visible light transmittance is more unlikely to decrease. As for the said ultraviolet shielding agent, only 1 type may be used and 2 or more types may be used together.

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 having a benzotriazole structure (benzotriazole compound), and an ultraviolet shielding agent having a benzophenone structure (benzophenone compound). ), UV screening agent having triazine structure (triazine compound), UV screening agent having malonate ester structure (malonic acid ester compound), UV screening agent having oxalic acid anilide structure (oxalic acid anilide compound) and benzoate structure Examples thereof include an ultraviolet shielding agent (benzoate compound).

Examples of the ultraviolet shielding agent containing a metal atom include platinum particles, particles having platinum particles coated with silica, palladium particles, and particles having palladium particles coated with silica. The ultraviolet shielding agent is preferably not a heat shielding 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 triazine structure, or an ultraviolet shielding agent having a benzoate structure. The ultraviolet shielding agent is more preferably an ultraviolet shielding agent having a benzotriazole structure or an ultraviolet shielding agent having a benzophenone structure, and more 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 may be coat | covered regarding the ultraviolet-ray shielding agent containing the said metal oxide. Examples of the coating material on the surface of the ultraviolet shielding agent containing the metal oxide include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.

Examples of the ultraviolet screening agent having the benzotriazole structure include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (“Tinvin 320” manufactured by BASF), 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (BASF) And “Tinuvin 326” manufactured by BASF, etc.) and the like. Since the performance of absorbing ultraviolet rays is excellent, the ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure containing a halogen atom, and may be an ultraviolet shielding agent having a benzotriazole structure containing a chlorine atom. More preferred.

Examples of the ultraviolet shielding agent having the benzophenone structure include octabenzone (“Chimasorb 81” manufactured by BASF).

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

Examples of the UV screening agent having a malonic ester structure include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene). -Bis (1,2,2,6,6-pentamethyl 4-piperidinyl) malonate and the like.

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

Examples of the ultraviolet shielding agent having the oxalic anilide structure include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-tert-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl)- Oxalic acid diamides having an aryl group substituted on the nitrogen atom such as N ′-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2′-ethoxy-oxyanilide (“SlandorVSU” manufactured by Clariant) Kind.

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

In 100% by weight of the layer containing the ultraviolet screening agent (first layer, second layer or third layer), the content of the ultraviolet screening agent is preferably 0.1% by weight or more, more preferably 0%. .2% by weight or more, more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight or more. In 100% by weight of the layer containing the ultraviolet shielding agent (first layer, second layer or third layer), the content of the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2%. % By weight or less, more preferably 1% by weight or less, particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is not less than the above lower limit and not more than the above upper limit, a decrease in visible light transmittance after a lapse of time can be further suppressed. In particular, in 100% by weight of the layer containing the ultraviolet shielding agent, the content of the ultraviolet shielding agent is 0.2% by weight or more, thereby reducing the visible light transmittance after the passage of the intermediate film and the laminated glass. Remarkably 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. As for the said antioxidant, only 1 type may be used and 2 or more types may be used together.

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

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

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

Examples of the phosphorus antioxidant include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphos. Phyto, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, and 2,2′-methylenebis (4 , 6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus and the like. One or more of these antioxidants are preferably used.

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

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

(Other ingredients)
The intermediate film, the first layer, the second layer, and the third layer are respectively a coupling agent containing silicon, aluminum, or titanium, a dispersant, a surfactant, a flame retardant, Additives such as antistatic agents, fillers, pigments, dyes, adhesive strength modifiers, moisture-proofing agents, fluorescent brighteners and infrared absorbers may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.

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

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

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

T is the thickness of the intermediate film. The thickness of the first layer is preferably 0.035T or more, more preferably 0.0625T or more, further preferably 0.1T or more, preferably 0.4T or less, more preferably 0.375T or less, and still more preferably. It is 0.25 T or less, particularly preferably 0.15 T or less. When the thickness of the first layer is 0.4 T or less, the bending rigidity is further improved.

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

The total thickness of the second layer and the third layer is preferably 0.625 T or more, more preferably 0.75 T or more, still more preferably 0.85 T or more, preferably 0.97 T or less, more preferably 0.9375T or less, more preferably 0.9T or less. Further, when the total thickness of the second layer and the third layer is not less than the above lower limit and not more than the above upper limit, the rigidity and sound insulation of the laminated glass are further enhanced.

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

The method for producing the interlayer film according to the present invention is not particularly limited. Examples of the method for producing an interlayer film according to the present invention include a method of extruding a resin composition using an extruder in the case of a single-layer interlayer film. As a method for producing an interlayer film according to the present invention, in the case of a multilayer interlayer film, for example, a method in which each layer is formed using each resin composition for forming each layer and then the obtained layers are stacked. In addition, a method of laminating each layer by coextruding each resin composition for forming each layer using an extruder may be used. Since it is suitable for continuous production, an extrusion method is preferred.

Since the production efficiency of the intermediate film is excellent, it is preferable that the same polyvinyl acetal resin is contained in the second layer and the third layer. Since the production efficiency of the intermediate film is excellent, it is more preferable that the same polyvinyl acetal resin and the same plasticizer are contained in the second layer and the third layer. Since the production efficiency of the intermediate film is excellent, 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. More preferably, the intermediate film has a concavo-convex shape on both surfaces. It does not specifically limit as a method of forming said uneven | corrugated shape, For example, the lip embossing method, the embossing roll method, the calender roll method, a profile extrusion method, etc. are mentioned. The embossing roll method is preferable because it can form a large number of concavo-convex embossments that are quantitatively constant.

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

3 includes a first laminated glass member 21, a second laminated glass member 22, and an intermediate film 11. The intermediate film 11 is disposed between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched.

The 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 11 b opposite to the first surface 11 a of the intermediate film 11. 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.

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

A 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. 11 A of intermediate films are arrange | positioned between the 1st laminated glass member 21 and the 2nd laminated glass member 22, and are inserted | pinched.

The 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 opposite to the first surface 11a of the intermediate film 11A.

Thus, the laminated glass which concerns on this invention is equipped with the 1st laminated glass member, the 2nd laminated glass member, and the intermediate film, and this intermediate film is the intermediate film for laminated glasses which concerns on this invention. It is. In the laminated glass according to 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. Laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like. The laminated glass is a laminate including a glass plate, and preferably at least one glass plate is used. Each of the first laminated glass member and the second laminated glass member is a glass plate or a PET film, and the laminated glass is one of the first laminated glass member and the second laminated glass member. It is preferable to provide a glass plate as at least one.

Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, and wire-containing plate glass. The organic glass is a synthetic resin glass that replaces the inorganic glass. Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

The thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. When the laminated glass member is a glass plate, the thickness of the glass plate is preferably 0.5 mm or more, more preferably 0.7 mm or more, preferably 5 mm or less, more preferably 3 mm or less. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.

The use of the interlayer film according to the present invention makes it possible to maintain the bending rigidity of the laminated glass high even if the laminated glass is thin. 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, still more preferably 1.5 mm or less, still more preferably 1.4 mm or less, and even more preferably 1. 0.3 mm or less, still more preferably 1.0 mm or less, and particularly preferably 0.7 mm or less. In this case, the laminated glass can be reduced in weight, the environmental load can be reduced by reducing the material of the laminated glass, and the environmental load can be reduced by improving the fuel efficiency of the automobile by reducing the weight of the laminated glass. . The total thickness of the first glass plate and 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, particularly preferably 2.8 mm or less. It is. In this case, the laminated glass can be reduced in weight, the environmental load can be reduced by reducing the material of the laminated glass, and the environmental load can be reduced by improving the fuel efficiency of the automobile by reducing the weight of the laminated glass. .

The method for producing the laminated glass is not particularly limited. First, an interlayer film is sandwiched between the first laminated glass member and the second laminated glass member to obtain a laminate. Next, for example, by passing the obtained laminate through a pressing roll or putting it in a rubber bag and sucking under reduced pressure, the first laminated glass member, the second laminated glass member, and the intermediate film The remaining air is deaerated. Thereafter, pre-bonding is performed at about 70 to 110 ° C. to obtain a pre-bonded laminate. Next, the pre-pressed laminate is put in an autoclave or pressed and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained. You may laminate | stack a 1st layer, a 2nd layer, and a 3rd layer at the time of manufacture of the said laminated glass.

The interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The said intermediate film and the said laminated glass can be used besides these uses. The interlayer film and the laminated glass are preferably a vehicle or architectural interlayer film and a laminated glass, and more preferably a vehicle interlayer film and a laminated glass. The intermediate film and the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like. The interlayer film and the laminated glass are suitably used for automobiles. The interlayer film is used for obtaining laminated glass for automobiles.

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

The following materials were prepared.

(Polyvinyl acetal resin)
Polyvinyl acetal resins shown in Tables 1 to 5 below were appropriately used.

Regarding the polyvinyl acetal resin, the degree of acetalization (degree of butyralization), the degree of acetylation, and the hydroxyl group content were measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. In addition, when measured by ASTM D1396-92, the same numerical value as the method based on JIS K6728 “Testing method for polyvinyl butyral” was shown. Further, when the type of acetal is acetoacetal or benzyl acetal, the degree of acetalization is similarly measured for the degree of acetylation and the hydroxyl group content, and the molar fraction is calculated from the obtained measurement results, Subsequently, it calculated by subtracting the acetylation degree and the content rate of a hydroxyl group from 100 mol%.

(Second resin)
The acrylic polymers shown in the following Tables 1 to 5 were appropriately used.

The acrylic polymers shown in the following Tables 1 to 5 are acrylic polymers obtained by polymerizing polymerizable components containing the following compounds in the contents shown in the following Tables 1 to 5.

Ethyl acrylate butyl acrylate 2-hydroxyethyl acrylate benzyl acrylate cyclohexyl acrylate tripropylene glycol diacrylate (crosslinking agent)
Pentaerythritol acrylate (crosslinking agent)
Trimethylolpropane trimethacrylate (crosslinking agent)

Polyethylene ("NUC-0965" manufactured by Nihon Unicar)

(Crosslinking agent)
IPDI (isophorone diisocyanate)
Coronate L (manufactured by Tosoh Corporation)

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

(UV shielding agent)
Tinuvin 326 (2- (2′-hydroxy-3′-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, “Tinuvin 326” manufactured by BASF)

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

(Photopolymerization initiator)
1-hydroxycyclohexyl phenyl ketone (a)
Benzoin isopropyl ether (b)

(Polymerization inhibitor)
Hydroquinone (c)
Hydroquinone monomethyl ether (d)

Example 1
Preparation of a composition for forming an intermediate film (first layer):
100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, 100 parts by weight of an acrylic polymer of the type shown in Table 1 below, 5 parts by weight of a plasticizer (3GO), and an ultraviolet shielding agent (Tinvin 326) 0. 2 parts by weight and 0.2 parts by weight of an antioxidant (BHT) were mixed to obtain a composition for forming an intermediate film.

Preparation of interlayer film:
The composition for forming the intermediate film was extruded using an extruder to produce an intermediate film having a thickness shown in Table 1 below.

Laminated glass production (for bending stiffness measurement):
The obtained intermediate film was cut into a size of 20 cm long × 2.5 cm wide. As a 1st laminated glass member and a 2nd laminated glass member, the two glass plates (clear float glass, 20 cm long x 2.5 cm wide) of the thickness shown in following Table 1 were prepared. The obtained interlayer film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was put in a rubber bag and deaerated at a vacuum degree of 2660 Pa (20 torr) for 20 minutes. Thereafter, the laminate was vacuum-pressed while being deaerated while being further kept at 90 ° C. for 30 minutes in an autoclave. The laminated body preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave under conditions of 135 ° C. and a pressure of 1.2 MPa (12 kg / cm ² ) to obtain a laminated glass.

Laminated glass production (for sound insulation measurement):
The obtained intermediate film was cut into a size of 30 cm long × 2.5 cm wide. As the first laminated glass member and the second laminated glass member, two glass plates (clear float glass, length 30 cm × width 2.5 cm) having thicknesses shown in Table 1 below were prepared. An interlayer film was sandwiched between two glass plates to obtain a laminate. This laminated body is put in a rubber bag, deaerated at a vacuum degree of 2.6 kPa for 20 minutes, transferred to an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum-pressed. Crimped. The pre-pressed laminate was pressed for 20 minutes in an autoclave at 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass.

Laminated glass production (for penetration resistance test):
The obtained intermediate film was cut into a size of 15 cm long × 15 cm wide. As the first laminated glass member and the second laminated glass member, two glass plates (clear float glass, 15 cm long × 15 cm wide) having thicknesses shown in Table 1 below were prepared. An interlayer film was sandwiched between two glass plates to obtain a laminate. This laminated body is put in a rubber bag, deaerated at a vacuum degree of 2.6 kPa for 20 minutes, transferred to an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum-pressed. Crimped. The pre-pressed laminate was pressed for 20 minutes in an autoclave at 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass.

(Examples 2 to 12 and Comparative Examples 1 to 10, 13)
The composition of the composition for forming the interlayer film was set as shown in Tables 1 to 5 below, and the thicknesses of the interlayer film, the first laminated glass member, and the second laminated glass member were set as in Table 1 below. An interlayer film and a laminated glass were obtained in the same manner as in Example 1 except that the settings were made as shown in FIGS. In Examples 2 to 12 and Comparative Examples 1 to 10 and 13, the same type of ultraviolet shielding agent and antioxidant as in Example 1 were added in the same amount as in Example 1 (based on 100 parts by weight of polyvinyl acetal resin). 0.2 parts by weight).

(Comparative Example 11)
Preparation of a composition for forming an intermediate film (first layer):
100 parts by weight of the polyvinyl acetal resin of the kind shown in Table 5 below, 5 parts by weight of an acrylic polymer of the kind shown in Table 5 below, 5 parts by weight of a plasticizer (3GH), and the kind of kind shown in Table 5 below. A composition for forming an intermediate film was obtained by mixing 0.5 part by weight of a photopolymerization initiator and 0.1 part by weight of a polymerization inhibitor of the type shown in Table 5 below. In Comparative Example 11 and Comparative Example 12 to be described later, no ultraviolet absorber and antioxidant were used.

Preparation of intermediate film before photocuring:
The composition for forming the intermediate film was extruded using an extruder to prepare an intermediate film before photocuring having a thickness shown in Table 5 below.

Laminated glass production (for bending stiffness measurement):
A laminated glass before photocuring was obtained in the same manner as in Example 1. Thereafter, this laminated glass was irradiated with ultraviolet rays of 1700 mJ / cm ³ (measured with ORC UV-302A, wavelength range 320 to 390 nm, peak 350 nm) using an ultrahigh pressure mercury lamp, and the interlayer film was crosslinked and cured. Intermediate film (1) and laminated glass were obtained.

Laminated glass production (for sound insulation measurement):
A laminated glass before photocuring was obtained in the same manner as in Example 1. Thereafter, this laminated glass was irradiated with ultraviolet rays of 1700 mJ / cm ³ (measured with ORC UV-302A, wavelength range 320 to 390 nm, peak 350 nm) using an ultrahigh pressure mercury lamp, and the interlayer film was crosslinked and cured. Of the intermediate film (2) and laminated glass were obtained.

Laminated glass production (for penetration resistance test):
A laminated glass before photocuring was obtained in the same manner as in Example 1. Thereafter, this laminated glass was irradiated with ultraviolet rays of 1700 mJ / cm ³ (measured with ORC UV-302A, wavelength range 320 to 390 nm, peak 350 nm) using an ultrahigh pressure mercury lamp, and the interlayer film was crosslinked and cured. Of the intermediate film (3) and laminated glass were obtained.

(Comparative Example 12)
An intermediate film and a laminated glass were obtained in the same manner as in Comparative Example 11 except that the composition of the composition for forming the intermediate film was set as shown in Table 5 below.

(Evaluation)
(1) Gel fraction An intermediate film (Comparative Examples 11 and 12 are photocured intermediate films) 0.2 g was immersed in 40 g of tetrahydrofuran and immersed in a shaker at 23 ° C. for 24 hours. Then, after centrifuging at 10 ° C. and 10,000 rpm with a centrifuge (manufactured by KUBOTA, high-speed, large-capacity cooled centrifuge 7780), the supernatant was removed. The residue in the container was dried by heating at 110 ° C. for 1 hour. Thereafter, the weight of the residue was measured. The gel fraction was calculated by the above formula (X).
The intermediate films (1) to (3) after photocuring in Comparative Examples 11 and 12 had the same gel fraction.

(2) Content of polyvinyl acetal resin in 100% by weight of insoluble component In the measurement of the gel fraction, the intermediate film (Comparative Examples 11 and 12 is an intermediate film after photocuring) was immersed in tetrahydrofuran at 23 ° C. and dried. Then, the intermediate film (insoluble component of the intermediate film with respect to tetrahydrofuran at 23 ° C.) was prepared as a test piece.

The IR spectrum of the test piece was measured by ATR method using a Fourier transform infrared microscope iN10 manufactured by Thermo Fisher Scientific. TiP-ATR (Ge crystal, incident angle of infrared light 27 degrees) was used as an accessory. The test piece and the crystal were sufficiently adhered. Measurement range 4000 ~ 675 cm ^-1 of the spectrum, the spectral resolution were measured at ^{8 cm -1.} About the aperture, the surface was set to 200 μm × 200 μm, and the cross section was set to 30 μm in the thickness direction × 200 μm in the plane direction.

IR spectra were measured for samples having different blending ratios between the polyvinyl acetal resin and the second resin, and a calibration curve was created between the peak value of 1725 cm ⁻¹ derived from C═O and the weight ratio of the polyvinyl acetal resin.

Based on a peak value of 1725 cm ⁻¹ derived from C═O, the content of the polyvinyl acetal resin was calculated from a calibration curve.

The content of polyvinyl acetal resin in 100% by weight of insoluble components was determined according to the following criteria.

[Criteria for content of polyvinyl acetal resin in 100% by weight of insoluble component]
A: The content of the polyvinyl acetal resin is 10% by weight or more. B: The content of the polyvinyl acetal resin is less than 10% by weight.

Note that, in the intermediate films (1) to (3) after photocuring in Comparative Examples 11 and 12, the content of the polyvinyl acetal resin in 100% by weight of the insoluble component was the same.

(3) Glass transition temperature Immediately after storing the obtained intermediate film (Comparative Examples 11 and 12 are intermediate films after photocuring) in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, The shear storage modulus was measured using a viscoelasticity measuring device “DMA + 1000” manufactured by the company. An interlayer film is cut out with a length of 50 mm and a width of 20 mm, and the temperature is increased from −50 to 200 ° C. at a temperature increase rate of 2 ° C./min in the shear mode, and the frequency is 0.5 Hz and the strain is 0.05%. It was measured. In the obtained viscoelastic spectrum, when the loss tangent (tan δ) has a peak from −30 ° C. to 0 ° C., the peak temperature is described. In the obtained viscoelastic spectrum, when the loss tangent (tan δ) had no peak from −30 ° C. to 0 ° C., it was described as “None”.
Note that the glass transition temperatures of the intermediate films (1) to (3) after photocuring in Comparative Examples 11 and 12 were the same.

(4) Maximum value of tan δ in the temperature range from −30 ° C. to 0 ° C. The maximum value of tan δ in the temperature range from −30 ° C. to 0 ° C. was evaluated. Specifically, the obtained intermediate film (Comparative Examples 11 and 12 is an intermediate film after photocuring) was stored for 12 hours in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5%. The shear storage modulus was measured using a viscoelasticity measuring device “DMA + 1000”. A condition in which an intermediate film (Comparative Examples 11 and 12 is a photocured intermediate film) is cut into a length of 50 mm and a width of 20 mm, and the temperature is increased from −50 to 200 ° C. at a temperature increase rate of 2 ° C./min in a shear mode. And it measured on the conditions of frequency 0.5Hz and distortion 0.05%. In the obtained viscoelastic spectrum, when the loss tangent (tan δ) has a peak from −30 ° C. to 0 ° C., the peak value (maximum value) is described.

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

[Criteria for bending stiffness]
○: Bending rigidity is 55 N / mm or more ×: Bending rigidity is less than 55 N / mm

(6) Sound insulation The obtained laminated glass was vibrated with a vibration generator for vibration test (“Vibrator G21-005D” manufactured by KENKEN Co., Ltd.). The vibration characteristics obtained therefrom were amplified by a mechanical impedance measuring device (“XG-81” manufactured by Lion Co., Ltd.), and the vibration spectrum was analyzed using an FFT spectrum analyzer (“FFT analyzer HP3582A” manufactured by Yokogawa Hewlett-Packard Co.).

From the ratio between the loss coefficient thus obtained and the resonance frequency of the laminated glass, a graph showing the relationship between the sound frequency (Hz) at 20 ° C. and the sound transmission loss (dB) is created. The minimum sound transmission loss (TL value) near 000 Hz and around 5,000 Hz was obtained. The higher the TL value, the higher the sound insulation. Sound insulation was determined according to the following criteria.

[Criteria for sound insulation]
○○: TL value is 35 dB or more ○: TL value is 30 dB or more and less than 35 dB ×: TL value is less than 30 dB

(7) Penetration resistance The obtained laminated glass was adjusted so that the surface temperature might be 20 degreeC. Next, from a height of 2.0 m, a hard sphere having a mass of 2260 g and a diameter of 82 mm was dropped onto the center portion of the laminated glass for each of the six laminated glasses. For all six laminated glasses, the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. If the number of laminated glasses in which the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was 3 or less, it was rejected. In the case of four sheets, the penetration resistance of six new laminated glasses was evaluated. In the case of 5 sheets, one additional laminated glass was additionally tested, and the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. In the same way, the height is increased by 25 cm, and a hard sphere with a mass of 2260 g and a diameter of 82 mm is dropped on the center of the laminated glass for each of the 6 laminated glasses, and the penetration resistance (maximum height) of the laminated glass is reduced. evaluated. The penetration resistance was determined according to the following criteria.

[Criteria for penetration resistance]
○○: Passed at a height of 4m ○: Not equivalent to ○○ and × standard ×: Failed at any height of 2.0m to 3.5m

Details and results are shown in Tables 1 to 5 below. In Tables 1 to 5 below, the description of the ultraviolet shielding agent and the antioxidant was omitted (only Comparative Example 13 was omitted in Table 5).

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

Claims

Including a polyvinyl acetal resin and a plasticizer,
The gel fraction determined by the following formula (X) is 10 wt% or more and 80 wt% or less,
The glass transition temperature is present between −30 ° C. and 0 ° C.
An interlayer film for laminated glass, wherein the maximum value of tan δ in the temperature range of −30 ° C. to 0 ° C. is 0.1 or more.
Gel fraction (% by weight) = W2 / W1 × 100 Formula (X)
W1: Weight of the intermediate film before immersing the intermediate film in tetrahydrofuran at 23 ° C W2: Weight of the intermediate film after being taken out after being immersed in tetrahydrofuran at 23 ° C and dried
The interlayer film for laminated glass according to claim 1, wherein the content of the polyvinyl acetal resin is 10% by weight or more in 100% by weight of the insoluble component of the interlayer film with respect to tetrahydrofuran at 23 ° C.
The interlayer film for laminated glass according to claim 1 or 2, comprising a second resin other than the polyvinyl acetal resin.
The interlayer film for laminated glass according to claim 3, wherein a content of the polyvinyl acetal resin is 25% by weight or more in a total of 100% by weight of the polyvinyl acetal resin and the second resin.
The interlayer film for laminated glass according to claim 3 or 4, comprising an acrylic polymer as the second resin.
The interlayer film for laminated glass according to claim 5, wherein the content of the acrylic polymer is 75% by weight or less in a total of 100% by weight of the polyvinyl acetal resin and the second resin.
The interlayer film for laminated glass according to any one of claims 1 to 6, wherein the polyvinyl acetal resin contained in the interlayer film is a polyvinyl acetoacetal resin, a polyvinyl butyral resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal resin. .
The interlayer film for laminated glass according to any one of claims 1 to 7, wherein the thickness is 3 mm or less.
The first glass plate having a thickness of 1.6 mm or less is used between the first glass plate and the second glass plate and used to obtain a laminated glass. 9. The interlayer film for laminated glass according to any one of 8 above.
Arranged between the first glass plate and the second glass plate, used to obtain laminated glass,
The interlayer film for laminated glass according to any one of claims 1 to 9, wherein the sum of the thickness of the first glass plate and the thickness of the second glass plate is 3.5 mm or less.
A first laminated glass member;
A second laminated glass member;
An interlayer film for laminated glass according to any one of claims 1 to 10,
Laminated glass in which the interlayer film for laminated glass is disposed between the first laminated glass member and the second laminated glass member.
The first laminated glass member is a first glass plate;
The laminated glass of Claim 11 whose thickness of a said 1st glass plate is 1.6 mm or less.
The first laminated glass member is a first glass plate;
The second laminated glass member is a second glass plate;
The laminated glass of Claim 11 or 12 whose sum total of the thickness of a said 1st glass plate and the thickness of a said 2nd glass plate is 3.5 mm or less.