JP6949836B2 - Laminated glass interlayer film and laminated glass - Google Patents

Description

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

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

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

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

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

JP-A-2007-070200 US2013 / 0236711A1

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

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

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

Further, it is desired that the laminated glass using the interlayer film has high bending rigidity and high light resistance. In particular, in laminated glass using a thin glass plate, the interlayer film is easily affected by ultraviolet light, so that light resistance tends to be a problem.

Further, in a laminated glass using an interlayer film, it is also required that the glass is less likely to scatter when the laminated glass is broken. In laminated glass using a thin glass plate, the glass plate tends to break easily, so it is important to improve the anti-scattering property when the glass plate breaks.

With a conventional interlayer film, it is difficult to improve all three of high bending rigidity, high light resistance, and high anti-scattering property, not one or two.

An object of the present invention is for a laminated glass that can increase the flexural rigidity of the laminated glass at 20 ° C., enhance the light resistance of the laminated glass, and further enhance the anti-scattering property when the laminated glass is broken. It is to provide an interlayer. Another object of the present invention is to provide a laminated glass using the above-mentioned interlayer film for laminated glass.

According to a broad aspect of the present invention, the polyvinyl acetal resin, the acrylic polymer, and the acrylic monomer are contained, and the content of the acrylic monomer is 0.1 with respect to 100 parts by weight of the acrylic polymer. An interlayer film for laminated glass (hereinafter, may be referred to as an interlayer film) having a weight of 2 parts by weight or more and 1 part by weight or less is provided.

In a specific aspect of the interlayer film according to the present invention, the interlayer film has a phase-separated structure, and in the phase-separated structure, the acrylic polymer is an island portion, and the glass transition temperature of a component derived from the acrylic polymer is determined. It is 30 ° C. or more lower than the glass transition temperature of the component derived from the polyvinyl acetal resin.

In a specific aspect of the interlayer film according to the present invention, the shear storage elastic modulus is 3 MPa or more and 2000 MPa or less in the temperature region of 80% or more of the temperature region of 10 ° C. or higher and 30 ° C. or lower.

In certain aspects of the interlayer film according to the present invention, the acrylic polymer has a crosslinked structure, or the polyvinyl acetal resin and the acrylic polymer are crosslinked.

In a specific aspect of the interlayer film according to the present invention, in the phase-separated structure, the average diameter of the islands is 10 nm or more and 1 μm or less.

In certain aspects of the interlayer film according to the present invention, the interlayer film comprises a plasticizer.

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

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

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

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

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

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

The interlayer film for laminated glass according to the present invention contains a polyvinyl acetal resin, an acrylic polymer, and an acrylic monomer. In the interlayer film for laminated glass according to the present invention, the content of the acrylic monomer is 0.1 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the acrylic polymer. Since the laminated glass interlayer film according to the present invention has the above-mentioned configuration, the bending rigidity of the laminated glass using the laminated glass interlayer film according to the present invention at 20 ° C. can be increased, and the laminated glass can be increased. It is possible to enhance the light resistance of the laminated glass and further enhance the anti-scattering property when the laminated glass is broken.

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

Hereinafter, the present invention will be described in detail.

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

The interlayer film according to the present invention contains a polyvinyl acetal resin, an acrylic polymer, and an acrylic monomer. In the interlayer film according to the present invention, the content of the acrylic monomer is 0.1 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the acrylic polymer.

Since the interlayer film according to the present invention has the above-mentioned structure, the bending rigidity of the laminated glass using the interlayer film according to the present invention at 20 ° C. can be increased. Further, in order to obtain a laminated glass, the interlayer film is often arranged between the first glass plate and the second glass plate. Even if the thickness of the first glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. Further, even if the thickness of both the first glass plate and the second glass plate is thin, the bending rigidity of the laminated glass can be sufficiently increased by using the interlayer film according to the present invention. If both the first glass plate and the second glass plate are thick, the bending rigidity of the laminated glass becomes even higher.

Further, since the interlayer film according to the present invention has the above-mentioned structure, the light resistance of the laminated glass according to the present invention can be enhanced. Even if the laminated glass is exposed to ultraviolet light, the laminated glass is unlikely to discolor. Further, the thickness of the glass plate is thin, and even if a large amount of ultraviolet light reaches the interlayer film through the glass plate, the laminated glass is unlikely to be discolored.

Further, since the interlayer film according to the present invention has the above-mentioned structure, it is possible to improve the anti-scattering property when the laminated glass according to the present invention is broken. Even if the glass plate breaks, it becomes difficult for the broken glass pieces to come off from the interlayer film.

In the present invention, all three of high bending rigidity, high light resistance, and high anti-scattering property can be improved instead of one or two.

Since the interlayer film contains a polyvinyl acetal resin and an acrylic polymer, the sound insulation is effectively improved. Further, since the interlayer film contains 100 parts by weight of the acrylic polymer and the acrylic monomer in a specific content, that is, 0.1 part by weight or more and 1 part by weight or less, high bending rigidity and high light resistance are obtained. All with high anti-scattering properties can be improved. From the viewpoint of further improving flexural rigidity, light resistance and shatterproofness, the content of the acrylic monomer is preferably 0.2 parts by weight or more, preferably 0.2 parts by weight or more, based on 100 parts by weight of the acrylic polymer. It is 0.8 parts by weight or less. When the content of the acrylic monomer is at least the above lower limit, the light resistance is excellent. It is considered that this is because the acrylic monomer effectively captures the radicals generated by the irradiation with ultraviolet rays and the like to suppress the deterioration of the resin. Further, when the content of the acrylic monomer is not more than the above upper limit, bleeding out of the acrylic monomer to the glass-adhesive surface can be suppressed, and the anti-scattering property is excellent. When the interlayer film does not contain the acrylic polymer, the acrylic monomer tends to bleed out, so that the shatterproof property may not be exhibited.

From the viewpoint of further enhancing flexural rigidity and penetration resistance, the interlayer film preferably has a phase-separated structure. From the viewpoint of further enhancing flexural rigidity and penetration resistance, it is preferable that the acrylic polymer is an island portion in the phase-separated structure. It is considered that one of the factors that the above-mentioned effect is exhibited by these preferable configurations is that the energy distribution proceeds smoothly due to the existence of the phase separation interface.

The island is preferably a domain. It is preferable that the polyvinyl acetal resin surrounds the domain, and it is preferable that the polyvinyl acetal resin is a matrix. The phase-separated structure is preferably a sea-island structure. When a second resin other than the polyvinyl acetal resin is used, it is preferable that the polyvinyl acetal resin and the second resin are contained in different phases. In the case of a sea-island structure, it is preferable that the polyvinyl acetal resin is the sea portion and the second resin is the island portion. By adopting the above-mentioned phase-separated structure, flexural rigidity and anti-scattering property can be effectively exhibited.

From the viewpoint of further enhancing flexural rigidity and penetration resistance, the average diameter of the islands in the phase-separated structure is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, and particularly preferably 30 nm or more. It is preferably 13 μm or less, more preferably 10 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less. The diameter of each island indicates the maximum diameter, and the average diameter of the islands is obtained by averaging the diameters (maximum diameters) of a plurality of islands.

From the viewpoint of further enhancing the anti-scattering property, in the interlayer film, the glass transition temperature of the component derived from the acrylic polymer is 30 ° C. or more lower than the glass transition temperature of the component derived from the polyvinyl acetal resin. preferable. That is, the glass transition temperature of the acrylic polymer is lower than the glass transition temperature of the polyvinyl acetal resin, and the absolute value of the difference between the glass transition temperature of the acrylic polymer and the glass transition temperature of the polyvinyl acetal resin is It is preferably 30 ° C. or higher. From the viewpoint of further enhancing the anti-scattering property, the glass transition temperature of the component derived from the acrylic polymer is more preferably 35 ° C. or more lower than the glass transition temperature of the component derived from the polyvinyl acetal resin.

When the interlayer film contains an additive such as a plasticizer described later, the glass transition temperature of the component derived from the polyvinyl acetal resin is the glass transition temperature of the polyvinyl acetal resin composition containing the polyvinyl acetal resin and the additive. Means.

When the interlayer film contains an additive such as a plasticizer described later, the glass transition temperature of the component derived from the second resin is the glass transition temperature of the second resin composition containing the second resin and the additive. It means the glass transition temperature.

As a method for measuring the glass transition temperature, immediately after storing the interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, the viscoelasticity measuring device “DVA” manufactured by IT Measurement Control Co., Ltd. A method of measuring viscoelasticity using "-200" can be mentioned. The interlayer film is cut out with a length of 8 mm and a width of 5 mm, and the temperature is raised from -50 ° C to 150 ° C at a heating rate of 3 ° C./min in shear mode, and under the conditions of frequency 1 Hz and strain 0.08%. It is preferable to measure the glass transition temperature.

From the viewpoint of further increasing the flexural rigidity, the shear storage elastic modulus of the interlayer film at 30 ° C. is preferably 3 MPa or more, more preferably 10 MPa or more, preferably 2000 MPa or less, and more preferably 1000 MPa or less.

From the viewpoint of further increasing the flexural rigidity, the shear storage elastic modulus of the interlayer film is 3 MPa or more and 2000 MPa or less in the temperature range of 80% or more (preferably 82% or more) in the temperature range of 10 ° C. or higher and 30 ° C. or lower. It is preferable to have.

When the interlayer film is a multilayer interlayer film, the shear storage elastic modulus means a shear storage equivalent elastic modulus. The shear storage equivalent elastic modulus indicates the shear storage elastic modulus when the multilayer body is regarded as a single layer. When it does not slip between layers, for example, the shear storage equivalent elastic modulus can be measured by measuring the shear storage elastic modulus by a general dynamic viscoelasticity measuring method while keeping the layer structure constituting the interlayer film. can.

The shear storage elastic modulus and the shear storage equivalent elastic modulus are obtained as follows.

As a method for measuring the shear storage elastic modulus and the shear storage equivalent elastic modulus, immediately after storing the interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, manufactured by IT Measurement Control Co., Ltd. A method of measuring viscoelasticity using the viscoelasticity measuring device "DVA-200" of the above can be mentioned. The interlayer film is cut out with a length of 8 mm and a width of 5 mm, and measured under the conditions of raising the temperature from -50 ° C to 150 ° C at a heating rate of 3 ° C / min in shear mode, and under the conditions of frequency 1 Hz and strain 0.08%. It is preferable to do so.

Further, the shear storage equivalent elastic modulus G'* is obtained by the following formula (A).

G'* = (Σiai) / (Σiai / G'i) ... Equation (A)

In the above formula (A), G'i indicates the shear storage elastic modulus of the i-th layer in the interlayer film, and ai indicates the thickness of the i-th layer in the intermediate film. Σi means to calculate the sum of the numerical values of the i layer.

From the viewpoint of further enhancing the flexural rigidity, the gel fraction determined by the following formula (X) in the interlayer film is preferably 10% by weight or more. From the viewpoint of further enhancing the penetration resistance, the gel fraction determined by the following formula (X) in the interlayer film is preferably 10% by weight or more, preferably 80% by weight or less. When the gel fraction is 10% by weight or more, the effect of improving bending rigidity and penetration resistance becomes high. When the gel fraction is 80% by weight or less, the penetration resistance is considerably high. From the viewpoint of further enhancing flexural rigidity and penetration resistance, the gel fraction is more preferably 30% by weight or more. From the viewpoint of further enhancing the penetration resistance, the gel fraction is more preferably 50% by weight or less.

Gel fraction (% by weight) = W2 / W1 × 100 ・ ・ ・ Formula (X)
W1: Weight of the interlayer film before immersing the interlayer film in tetrahydrofuran at 23 ° C. W2: Weight of the interlayer film after immersing the interlayer film in tetrahydrofuran at 23 ° C. and then taking it out and drying it.

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

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

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

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

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

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

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

Other layers may be arranged between the second layer 2 and the first layer 1 and between the first layer 1 and the third layer 3, respectively. It is preferable that the second layer 2 and the first layer 1 and the first layer 1 and the third layer 3 are directly laminated, respectively. Examples of 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 a second embodiment of the present invention.

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

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

(Polyvinyl acetal resin, acrylic polymer and acrylic monomer)
The interlayer film contains a polyvinyl acetal resin, an acrylic polymer, and an acrylic monomer. It is preferable that the first layer, the second layer, and the third layer each contain a polyvinyl acetal resin. It is preferable that the first layer, the second layer, and the third layer each contain an acrylic polymer. It is preferable that the first layer, the second layer, and the third layer each contain an acrylic monomer. As the polyvinyl acetal resin, only one kind may be used, or two or more kinds may be used in combination. Only one kind of the above-mentioned acrylic polymer may be used, or two or more kinds may be used in combination. Only one kind of the above-mentioned acrylic monomer may be used, or two or more kinds may be used in combination.

In the total 100% by weight of the polyvinyl acetal resin and the acrylic polymer, the content of the polyvinyl acetal resin is preferably 20% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more, particularly. It is preferably 35% by weight or more, preferably less than 100% by weight. When the content of the polyvinyl acetal resin is at least the above lower limit, the bending rigidity and the anti-scattering property are effectively increased. The content of the polyvinyl acetal resin may be 90% by weight or less, 80% by weight or less, or 75% by weight or less in the total 100% by weight of the polyvinyl acetal resin and the acrylic polymer. It may be 70% by weight or less, or 65% by weight or less.

From the viewpoint of effectively enhancing the affinity between the resin component and the plasticizer and effectively enhancing the penetration resistance, the polyvinyl acetal resin is a polyvinyl acetacetal resin, a polyvinyl butyral resin, a polyvinylbenzyl acetal resin or a polyvinyl cumin acetal. It is preferably a resin. From the viewpoint of further increasing the bending rigidity, the polyvinyl acetal resin is preferably a polyvinyl acetal acetal resin, a polyvinyl benzyl acetal resin, or a polyvinyl cumin acetal resin. As used herein, the polyvinyl acetal resin includes an acetal acetalized resin, a benzyl acetalized resin, and a cumin acetalized resin.

From the viewpoint of effectively increasing flexural rigidity and sound insulation, the interlayer film contains an acrylic polymer. From the viewpoint of effectively increasing the flexural rigidity and sound insulation, it is preferable that the first layer, the second layer and the third layer each contain an acrylic polymer.

The acrylic polymer is preferably a polymer of a polymerizable component containing a (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 methyl poly (meth) acrylate, ethyl poly (meth) acrylate, n-propyl poly (meth) acrylate, i-propyl poly (meth) acrylate, and poly. N-butyl (meth) acrylate, i-butyl poly (meth) acrylate, t-butyl poly (meth) acrylate, 2-ethylhexyl poly (meth) acrylate, 2-hydroxyethyl poly (meth) acrylate, 2-Hydroxypropyl poly (meth) acrylate, 4-hydroxybutyl poly (meth) acrylate, glycidyl poly (meth) acrylate, octyl poly (meth) acrylate, propyl poly (meth) acrylate, poly (meth) 2-ethyloctyl acrylate, nonyl poly (meth) acrylate, isononyl poly (meth) acrylate, decyl poly (meth) acrylate, isodecyl poly (meth) acrylate, lauryl poly (meth) acrylate, poly (meth) ) Isotetradecyl acrylate, cyclohexyl poly (meth) acrylate, isobornyl poly (meth) acrylate, benzyl poly (meth) acrylate and the like. The (meth) acrylic acid having a polar group and the (meth) acrylic acid ester include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and Examples thereof include glycidyl acrylate. Polyacrylic acid ester is preferable because the temperature showing the maximum value of tan δ can be easily controlled within an appropriate range in the dynamic viscoelastic spectrum, and ethyl polyacrylate, n-butyl polyacrylate, and polyacrylic acid are preferable. 2-Ethylhexyl acid acid or octyl polyacrylate is more preferred. The use of these preferred poly (meth) acrylic acid esters further improves the balance between the productivity of the interlayer film and the properties of the interlayer film. Only one kind of the poly (meth) acrylic acid ester may be used, or two or more kinds may be used in combination.

In the total 100% by weight of the polyvinyl acetal resin and the acrylic polymer, 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, and particularly preferably 30% by weight or more. It is 35% by weight or more, preferably less than 100% by weight. When the content of the acrylic polymer is at least the above lower limit, the sound insulation and the anti-scattering property are effectively enhanced. In the total 100% by weight of the polyvinyl acetal resin and the acrylic polymer, the content of the acrylic polymer is preferably 90% by weight or less, more preferably 80% by weight or less, still more preferably 75% by weight or less, particularly. It is 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 anti-scattering property is effectively enhanced.

As the acrylic monomer, the acrylic monomer constituting the acrylic polymer can be used as it is as a non-polymerized monomer.

Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) acrylate. , (Meta) i-butyl acrylate, (meth) t-butyl acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) ) Glycidyl acrylate, (meth) octyl acrylate, propyl (meth) acrylate, 2-ethyl octyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Examples thereof include isodecyl (meth) acrylate, lauryl (meth) acrylate, isotetradecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and benzyl (meth) acrylate. The (meth) acrylic acid having a polar group and the (meth) acrylic acid ester include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and Examples thereof include glycidyl acrylate. Only one kind of the above-mentioned acrylic monomer may be used, or two or more kinds may be used in combination.

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

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

The first layer (including a single-layer interlayer film) preferably contains a thermoplastic resin (hereinafter, may be referred to as a thermoplastic resin (1)). The first layer preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (1)) as the thermoplastic resin (1). When the interlayer film is a single layer having only the first layer, the interlayer film contains a polyvinyl acetal resin (1). The second layer preferably contains a thermoplastic resin (hereinafter, may be referred to as a thermoplastic resin (2)). The second layer preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (2)) as the thermoplastic resin (2). The third layer preferably contains a thermoplastic resin (hereinafter, may be referred to as a thermoplastic resin (3)). The third layer preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (3)) as the thermoplastic resin (3). The polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different. The thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be the same or different. The polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be used alone or in combination of two or more. As the thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3), only one type may be used, or two or more types may be used in combination.

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

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

The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, even more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably 2700 or more. It is 5000 or less, more preferably 4000 or less, still more preferably 3500 or less. When the average degree of polymerization is at least the above lower limit, the penetration resistance and flexural rigidity of the laminated glass are further increased. When the average degree of polymerization is not more than the above upper limit, molding of the interlayer film becomes easy.

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

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

As the aldehyde, generally, an aldehyde having 1 to 10 carbon atoms is preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, n-barrel aldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, and n-octylaldehyde. Examples thereof include n-nonyl aldehyde, n-decyl aldehyde, cumin aldehyde, and benz aldehyde. Acetaldehyde, propionaldehyde, n-butylaldehyde, isobutyraldehyde, n-hexylaldehyde or n-barrel aldehyde are preferable, and acetaldehyde, propion aldehyde, n-butyl aldehyde, isobutyraldehyde or n-barrel aldehyde are more preferable. Acetaldehyde, n-butyraldehyde or n-valeraldehyde are more preferred. Only one kind of the above aldehyde may be used, or two or more kinds may be used in combination.

The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) is preferably in the following range. The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 20 mol% or more, more preferably 22 mol% or more, more preferably 24 mol% or more, still more preferably 26 mol% or more. It is more preferably 28 mol% or more, and particularly preferably 30 mol% or more. The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 37 mol% or less, more preferably 36.5 mol% or less, still more preferably 36 mol% or less. When the content of the hydroxyl groups is at least the above lower limit, the flexural rigidity is further increased, and the adhesive force of the interlayer film is further increased. Further, when the content of the hydroxyl group is not more than the above upper limit, the flexibility of the interlayer film is increased and the handling of the interlayer film becomes easy.

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

The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, still more preferably 9. It is mol% or more, preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 24 mol% or less. When the degree of acetylation is at least the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer or other thermoplastic resin becomes high, and the sound insulation, the anti-scattering property, and the penetration resistance are further improved. When the degree of acetylation is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass becomes high. In particular, when the degree of acetylation of the polyvinyl acetal resin (1) is 0.1 mol% or more and 25 mol% or less, the penetration resistance is further excellent.

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

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

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

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

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

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

(Plasticizer)
The interlayer film preferably contains a plasticizer. The first layer (including a single-layer interlayer film) preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (3)). By using a plasticizer and by using a polyvinyl acetal resin and a plasticizer in combination, the penetration resistance is further improved, and the adhesive force 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. Only one type of the above-mentioned plasticizer (1), the above-mentioned plasticizer (2), and the above-mentioned plasticizer (3) may be used, or two or more types may be used in combination.

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

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

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

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

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

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

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

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

In the second layer, the plasticization 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)). The content of the agent (2) is defined as the content (2). In the third layer, the plasticization with respect 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)). The content of the agent (3) is defined as the content (3). The content (2) and the content (3) are preferably 10 parts by weight or more, more preferably 15 parts by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, still more preferably 32 parts by weight, respectively. It is less than a part by weight, particularly preferably 30 parts by weight or less. When the content (2) and the content (3) are at least the above lower limit, the flexibility of the interlayer film is increased and the handling of the interlayer film becomes easy. When the content (2) and the content (3) are equal to or less than the upper limit, the bending rigidity becomes even higher.

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

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

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

The contents of the polyvinyl acetal resin, the acrylic polymer, the acrylic monomer and the plasticizer in the interlayer film can be measured as follows.

The interlayer film is cut into a length of 5 cm and a width of 5 cm, and left in an environment of 23 ± 2 ° C. and a humidity of 25 ± 5% for 12 hours. Next, the interlayer film is dissolved in tetrahydrofuran so as to be 1 wt% to obtain a measurement sample. A polyvinyl acetal resin, an acrylic polymer, an acrylic monomer, and a plasticizer are measured using a gas chromatograph (“JMS K-9” manufactured by JEOL Ltd.) as a measurement sample. The measurement conditions are as follows.

Column: SLBTM-5ms (slightly polar), 0.32mm x 30mm x 0.25μm
Column temperature: 40 ° C, 4 minutes → 10 ° C / min → 300 ° C, 10 minutes Inlet temperature: 300 ° C
Carrier: He 1.0 mL / min Injection volume: 1.0 μL
Split ratio: 1:50
Ionization voltage: 70eV
MS temperature: Ion source: 230 ° C, Interface: 250 ° C

(Heat-shielding substance)
The molded product preferably contains a heat-shielding substance (heat-shielding compound). The first layer preferably contains a heat-shielding substance. The second layer preferably contains a heat-shielding substance. The third layer preferably contains a heat-shielding substance. Only one kind of the heat-shielding substance may be used, or two or more kinds thereof may be used in combination.

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

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

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

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

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

The content of the component X is preferably 0.001% by weight or more, more preferably 0.005, based on 100% by weight of the layer containing the component X (first layer, second layer or third layer). By weight% or more, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more. The content of the component X is preferably 0.2% by weight or less, more preferably 0.1 in 100% by weight of the layer containing the component X (first layer, second layer or third layer). It is 0% by weight or less, more preferably 0.05% by weight or less, and particularly preferably 0.04% by weight or less. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high. For example, the visible light transmittance can be 70% or more.

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

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

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

Specific examples of the heat shield particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles (IZO particles). ), Aluminum-doped zinc oxide particles (AZO particles), niob-doped titanium oxide particles, sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, tallium-doped tungsten oxide particles, rubidium-doped tungsten oxide particles, tin-doped indium oxide particles (ITO particles) , Tin-doped zinc oxide particles, silicon-doped zinc oxide particles and other metal oxide particles, hexaborated lanthanum (LaB ₆ ) particles and the like. Heat-shielding particles other than these may be used. Since the heat ray shielding function is high, metal oxide particles are preferable, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferable, and ITO particles or tungsten oxide particles are particularly preferable. 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 property 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, rubidium-doped tungsten oxide particles, and the like.

Cesium-doped tungsten oxide particles are particularly preferable from the viewpoint of further increasing the heat-shielding property of the interlayer film and the laminated glass. From the viewpoint of further increasing the heat shielding property of the interlayer film and the laminated glass, the cesium-doped tungsten oxide particles are preferably tungsten oxide particles represented by the _{formula: Cs 0.33} WO _3.

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

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

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

(Metal salt)
The interlayer film preferably contains at least one metal salt (hereinafter, may be referred to as metal salt M) among alkali metal salts, alkaline earth metal salts and magnesium salts. The first layer preferably contains the metal salt M. The second layer preferably contains the metal salt M. The third layer preferably contains the metal salt M. By using the metal salt M, it becomes easy to control the adhesiveness between the interlayer film and the laminated glass member or the adhesiveness between each layer in the interlayer film. As the metal salt M, only one kind may be used, or two or more kinds may be used in combination.

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

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

Examples of the magnesium carboxylic acid salt having 2 to 16 carbon atoms and the potassium carboxylic acid salt having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, and 2-ethylbutanoic acid. Examples thereof include potassium, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate.

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

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

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). ), An ultraviolet shielding agent having a triazine structure (triazine compound), an ultraviolet shielding agent having a malonic acid ester structure (malonic acid ester compound), an ultraviolet shielding agent having a oxalic acid anilide structure (a oxalate anilide compound), and a benzoate structure. Examples include an ultraviolet shielding agent (benzoate compound).

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

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

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

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

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

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

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

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

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

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

The content of the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0, based on 100% by weight of the layer containing the ultraviolet shielding agent (first layer, second layer or third layer). .2% by weight or more, more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight or more. The content of the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2 in 100% by weight of the layer containing the ultraviolet shielding agent (first layer, second layer or third layer). It is 0% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is not less than the above lower limit and not more than the above upper limit, the decrease in the visible light transmittance after the elapse of the period can be further suppressed. In particular, when the content of the ultraviolet shielding agent is 0.2% by weight or more in 100% by weight of the layer containing the ultraviolet shielding agent, the visible light transmittance of the interlayer film and the laminated glass after a period of time is lowered. It can be significantly suppressed.

(Antioxidant)
The interlayer film preferably contains an antioxidant. The first layer preferably contains an antioxidant. The second layer preferably contains an antioxidant. The third layer preferably contains an antioxidant. Only one kind of the above-mentioned antioxidant may be used, or two or more kinds may be used in combination.

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

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

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

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

Examples of commercially available products of the above-mentioned antioxidants include BASF's "IRGANOX 245", BASF's "IRGAFOS 168", BASF's "IRGAFOS 38", Sumitomo Chemical's "Sumilyzer BHT", and Sakai Chemical Industry's. 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 for a long period of time, a layer (first layer, second layer or third layer) containing 100% by weight of the interlayer film or an antioxidant is used. ) The content of the antioxidant is preferably 0.1% by weight or more in 100% by weight. Further, since the effect of adding the antioxidant is saturated, the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the interlayer film or 100% by weight of the layer containing the antioxidant. ..

(Other ingredients)
The interlayer film, the first layer, the second layer, and the third layer are each, if necessary, a coupling agent containing silicon, aluminum, or titanium, a dispersant, a surfactant, a flame retardant, and the like. It may contain additives such as antistatic agents, fillers, pigments, dyes, adhesive strength modifiers, moisture resistant agents, optical brighteners and infrared absorbers. Only one of these additives may be used, or two or more of these additives may be used in combination.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

By using the interlayer film according to the present invention, the bending rigidity of the laminated glass can be maintained high even if the thickness of the laminated glass is thin. The thickness of the glass plate is preferably 2 mm or less, more preferably 1.8 mm or less, even more preferably 1.6 mm or less, still more preferably 1.5 mm or less, still more preferably 1.4 mm or less, still more preferably 1. It is 0.3 mm or less, more preferably 1.0 mm or less, and particularly preferably 0.7 mm or less. In this case, the weight of the laminated glass can be reduced, the material of the laminated glass can be reduced to reduce the environmental load, and the weight reduction of the laminated glass can improve the fuel efficiency of the automobile and reduce the environmental load. .. The total of the thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, more preferably 3.2 mm or less, still more preferably 3 mm or less, and particularly preferably 2.8 mm or less. Is. In this case, the weight of the laminated glass can be reduced, the material of the laminated glass can be reduced to reduce the environmental load, and the weight reduction of the laminated glass can improve the fuel efficiency of the automobile and reduce the environmental load. ..

The method for producing the laminated glass is not particularly limited. First, a molded body is sandwiched between the first laminated glass member and the second laminated glass member to obtain a laminated body. Next, for example, by passing the obtained laminated body through a pressing roll or putting it in a rubber bag and sucking it under reduced pressure, the first laminated glass member, the second laminated glass member, and the molded body are brought into contact with each other. Degas the air remaining in between. Then, it is pre-bonded at about 70 to 110 ° C. to obtain a pre-bonded laminate. Next, the pre-crimped laminate is placed in an autoclave or pressed, and crimped at a pressure of about 120 to 150 ° C. and 1 to 1.5 MPa. In this way, laminated glass can be obtained. At the time of manufacturing the laminated glass, the first layer, the second layer and the third layer may be laminated.

The interlayer film and the laminated glass can be used for automobiles, railroad vehicles, aircraft, ships, buildings and the like. The interlayer film and the laminated glass can be used for other purposes. The interlayer film and the laminated glass are preferably an interlayer film and a laminated glass for a vehicle or a building, and more preferably an interlayer film and a laminated glass for a vehicle. The interlayer film and the laminated glass can be used for windshields, side glasses, rear glasses, roof glasses and the like of automobiles. The interlayer film and the laminated glass are preferably used for automobiles. The interlayer film is used to obtain laminated glass for automobiles.

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

The following materials were prepared.

(Polyvinyl acetal resin)
The polyvinyl acetal resins shown in Tables 1 and 2 below were used as appropriate.

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

In Tables 1 and 2, when the value of the degree of butyralization (acetalization degree) is described, the polyvinyl butyral resin is used and the value of the acetalization degree (acetalization degree) is described. , Polyvinyl acetal acetal resin is used.

(Acrylic polymer)
The acrylic polymers shown in Tables 1 and 2 below were used as appropriate.

The acrylic polymer shown in Tables 1 and 2 below is an acrylic polymer obtained by polymerizing a polymerizable component containing the following compounds at the contents shown in Tables 1 and 2 below.

Ethyl acrylate butyl acrylate benzyl acrylate 2-hydroxyethyl acrylate Cyclohexyl acrylate 2-ethylhexyl acrylate Isobornyl acrylate Tripropylene glycol diacrylate (crosslinking agent)

(Acrylic monomer)
Benzyl acrylate butyl acrylate

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

(UV shield)
Tinuvin326 (2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, BASF's "Tinuvin 326")

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

(Example 1)
Preparation of composition for forming an interlayer film (first layer):
100 parts by weight of the polyvinyl acetal resin of the type shown in Table 1 below, 120 parts by weight of the acrylic polymer of the type shown in Table 1 below, 0.26 parts by weight of benzyl acrylate, and 0.12 parts by weight of butyl acrylate. , 0.2 part by weight of the ultraviolet shielding agent (Tinuvin 326) and 0.1 part by weight of the antioxidant (BHT) were mixed to obtain a composition for forming an interlayer film.

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

Fabrication of laminated glass (for measurement of flexural rigidity):
The obtained interlayer film was cut into a size of 20 cm in length × 2.5 cm in width. As the first laminated glass member and the second laminated glass member, two glass plates (clear float glass, length 20 cm × width 2.5 cm) having the thickness shown in Table 1 below were prepared. The obtained interlayer film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was placed in a rubber bag and degassed at a vacuum degree of 2660 Pa (20 torr) for 20 minutes. Then, the laminate was vacuum-pressed while being held in an autoclave at 90 ° C. for 30 minutes while being degassed. The laminate pre-bonded in this way was pressure-bonded in an autoclave at 135 ° C. and a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

Preparation of laminated glass (for shatterproof test):
The obtained interlayer film was cut into a size of 30 cm in length × 30 cm in width. As the first laminated glass member and the second laminated glass member, two glass plates (clear float glass, length 30 cm × width 30 cm) having the thickness shown in Table 1 below were prepared. The obtained interlayer film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was placed in a rubber bag and degassed at a vacuum degree of 2660 Pa (20 torr) for 20 minutes. Then, the laminate was vacuum-pressed while being held in an autoclave at 90 ° C. for 30 minutes while being degassed. The laminate pre-bonded in this way was pressure-bonded in an autoclave at 135 ° C. and a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

Preparation of laminated glass (for light resistance test):
The obtained interlayer film was cut into a size of 5 cm in length × 5 cm in width. As the first laminated glass member and the second laminated glass member, two glass plates (clear float glass, length 5 cm × width 5 cm) having the thickness shown in Table 1 below were prepared. The obtained interlayer film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was placed in a rubber bag and degassed at a vacuum degree of 2660 Pa (20 torr) for 20 minutes. Then, the laminate was vacuum-pressed while being held in an autoclave at 90 ° C. for 30 minutes while being degassed. The laminate pre-bonded in this way was pressure-bonded in an autoclave at 135 ° C. and a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

(Examples 2 to 6 and Comparative Examples 1 to 4)
The composition of the composition for forming the interlayer film was set as shown in Tables 1 and 2 below, and the thicknesses of the interlayer film, the first laminated glass member and the second laminated glass member were set 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 set as shown in 2 and 2. Further, in Examples 2 to 6 and Comparative Examples 1 to 4, the same type of ultraviolet shielding agent and antioxidant as in Example 1 was added in the same amount as in Example 1 (0 with respect to 100 parts by weight of the polyvinyl acetal resin). .2 parts by weight and 0.1 parts by weight).

(evaluation)
(1) Viscoelastic Shear storage elastic modulus:
The shear storage elastic modulus was measured at a frequency of 1 Hz. Specifically, immediately after storing the obtained interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, the viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd. The interlayer film was cut out with a length of 8 mm and a width of 5 mm, and measurements were performed in shear mode at a heating rate of 3 ° C./min at a heating rate of -50 ° C to 150 ° C, with a frequency of 1 Hz and a strain of 0.05%. rice field. The shear storage elastic modulus was determined according to the following criteria.

[Criteria for shear storage elastic modulus]
A: Shear storage elastic modulus is 3 MPa or more and 2000 MPa or less in the temperature range of 80% or more of the temperature range of 10 ° C. or more and 30 ° C. or less.

Glass-transition temperature:
Immediately after storing the obtained interlayer film in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, viscoelasticity was measured using a viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd. The elasticity was measured. The interlayer film is cut out with a length of 8 mm and a width of 5 mm, and measured under the conditions of raising the temperature from -50 ° C to 150 ° C at a heating rate of 3 ° C / min in shear mode, and under the conditions of frequency 1 Hz and strain 0.08%. Was done. The glass transition temperature of the polyvinyl acetal resin (glass transition temperature of the component derived from the polyvinyl acetal resin) and the glass transition temperature of the acrylic polymer (glass transition temperature of the component derived from the acrylic polymer) were evaluated.

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

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

Furthermore, when there was a phase-separated structure and there was a matrix, it was confirmed whether the resin component constituting the matrix and the island (domain) was a polyvinyl acetal resin or an acrylic polymer.

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

Further, when there was a phase-separated structure and there was an island (domain), the diameter (maximum diameter) of the island was observed at 3000 times or 5000 times, and the average value was calculated.

(3) Gel fraction 0.2 g of the interlayer film was immersed in 40 g of tetrahydrofuran and shaken and immersed at 23 ° C. for 24 hours. Then, the supernatant was removed after centrifuging at 10 ° C. and 10000 rpm with a centrifuge (KUBOTA, high-speed, large-capacity cooling centrifuge 7780). The residue in the container was heated at 110 ° C. for 1 hour to dry. The weight of the residue was then weighed. The gel fraction was calculated by the above formula (X). The gel fraction was determined according to the following criteria.

[Criteria for gel fraction]
A: Gel fraction is 10% or more B: Gel fraction is less than 10%

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

[Criteria for flexural rigidity at 20 ° C]
◯: Flexural rigidity is 55 N / mm or more Δ: Flexural rigidity is 45 N / mm or more and less than 55 N / mm ×: Flexural rigidity is less than 45 N / mm

(5) Anti-scattering property A laminated glass 2 hours after the autoclave (ACV) and a laminated glass 1 month after the autoclave (ACV) were prepared.

The laminated glass was adjusted so that the surface temperature was 20 ° C. Then, from a height of 9 m, a hard sphere having a mass of 227 g and a diameter of 38 mm was dropped onto the central portion of the laminated glass, respectively, for each of the six laminated glasses. For all six laminated glasses, the weight of the fallen glass on the side opposite to the surface on which the hard sphere collided was measured, and the average weight was calculated. The anti-scattering property was judged according to the following criteria.

[Criteria for shatterproofness]
○○: The average weight of the dropped glass is less than 0.5 g ○: The average weight of the dropped glass is 0.5 g or more and less than 1 g Δ: The average weight of the dropped glass is 1 g or more and less than 3 g ×: The average weight of the dropped glass Is 3g or more

(6) Light resistance With a light resistance tester (“Super Xenon Weather Meter SX75” manufactured by Suga Test Instruments Co., Ltd.), YI was measured before and after irradiation at a light source of 180 W and a temperature of 63 ° C. for 3000 hours. Using a spectrophotometer (“U-4100” manufactured by Hitachi High-Tech), the YI value (yellowness, yellow index) of the obtained laminated glass was measured according to JIS K7105. The measurement region of the YI value was defined as a region from the end portion to a distance of 5 mm inward in the direction orthogonal to the end portion having the end portion. The absolute value of the difference between the initial YI value and the YI value after irradiation was determined as ΔYI. From the ΔYI value, the light resistance was determined according to the following criteria.

[Criteria for light resistance]
◯: ΔYI is less than 3 Δ: ΔYI is 3 or more and less than 5 ×: ΔYI is 5 or more

Details and results are shown in Tables 1 and 2 below. In Tables 1 and 2 below, the description of the ultraviolet shielding agent and the antioxidant is omitted.

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

Claims (12)

It contains a polyvinyl acetal resin, an acrylic polymer, and an acrylic monomer, and the content of the acrylic monomer is 0.1 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the acrylic polymer. , Polymer for laminated glass. It has a phase-separated structure, and in the phase-separated structure, the acrylic polymer is an island.
The interlayer film for laminated glass according to claim 1, wherein the glass transition temperature of the component derived from the acrylic polymer is 30 ° C. or more lower than the glass transition temperature of the component derived from the polyvinyl acetal resin. The interlayer film for laminated glass according to claim 1 or 2, wherein the shear storage elastic modulus is 3 MPa or more and 2000 MPa or less in the temperature range of 80% or more of the temperature range of 10 ° C. or higher and 30 ° C. or lower. The interlayer film for laminated glass according to any one of claims 1 to 3, wherein the acrylic polymer has a crosslinked structure, or the polyvinyl acetal resin and the acrylic polymer are crosslinked. The interlayer film for laminated glass according to claim 2, wherein in the phase-separated structure, the average diameter of the islands is 10 nm or more and 1 μm or less. The interlayer film for laminated glass according to any one of claims 1 to 5, which contains a plasticizer. The interlayer film for laminated glass according to any one of claims 1 to 6, which has a thickness of 3 mm or less. A first glass plate having a thickness of 1.6 mm or less is used to obtain a laminated glass by being arranged between the first glass plate and the second glass plate. 7. The interlayer film for laminated glass according to any one of 7. It is placed between the first glass plate and the second glass plate and used to obtain laminated glass.
The interlayer film for laminated glass according to any one of claims 1 to 8, wherein the total thickness of the first glass plate and the thickness of the second glass plate is 3.5 mm or less. With the first laminated glass member,
With the second laminated glass member,
The laminated glass interlayer film according to any one of claims 1 to 9 is provided.
A laminated glass in which the laminated glass interlayer film is arranged between the first laminated glass member and the second laminated glass member. The first laminated glass member is a first glass plate.
The laminated glass according to claim 10, wherein the thickness of the first 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 according to claim 10 or 11, wherein the total of the thickness of the first glass plate and the thickness of the second glass plate is 3.5 mm or less.

Images