TW201841859A - Intermediate film for laminated glass, and laminated glass - Google Patents

Abstract

Provided is an intermediate film for laminated glass which is capable of enhancing the bending stiffness of laminated glass at 20 DEG C, while being also capable of enhancing the sound insulation properties and penetration resistance of the laminated glass. An intermediate film for laminated glass according to the present invention contains a polyvinyl acetal resin, a second resin other than the polyvinyl acetal resin, and a plasticizer. This intermediate film for laminated glass is configured such that: the content of the plasticizer relative to 100 parts by weight of the polyvinyl acetal resin is 3 parts by weight or more but less than 20 parts by weight; this intermediate film has a phase separation structure; the second resin forms island portions in the phase separation structure; the average diameter of the island portions in the phase separation structure is from 10 nm to 1 [mu]m (inclusive); and the glass transition temperature is within the range of from -40 DEG C to 0 DEG C (inclusive).

Description

Interlayer film for laminated glass and laminated glass

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

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

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

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

The following Patent Document 2 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 disposed between glass plates having a thickness of 4.0 mm or less. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-070200 [Patent Document 2] US2013 / 0236711A1

[Problems to be solved by the invention]

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

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

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

In addition to laminated glass using an intermediate film, in addition to high flexural rigidity, sound insulation and penetration resistance are also expected to be high.

It is difficult for the previous interlayer film to make not one or two but three of them good among higher flexural rigidity, higher sound insulation, and higher penetration resistance.

The object of the present invention is to provide an interlayer film for laminated glass which can improve the flexural rigidity of laminated glass at 20 ° C, and can improve the sound insulation and penetration resistance of laminated glass. Another object of the present invention is to provide a laminated glass using the above-mentioned interlayer film for laminated glass. [Technical means to solve the problem]

According to a wide aspect of the present invention, there is provided an interlayer film (hereinafter, sometimes referred to as an interlayer film) for laminated glass, which contains a polyvinyl acetal resin, a second resin other than the polyvinyl acetal resin, and a plastic. And the content of the plasticizer is 3 parts by weight or more and less than 20 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin, and the interlayer film for laminated glass has a phase separation structure. In the separation structure, the second resin is an island portion, and in the phase separation structure, an average diameter of the island portion is 10 nm or more and 1 μm or less. The glass transition temperature of the interlayer film for laminated glass exists at − Above 40 ° C and below 0 ° C.

In a specific aspect of the intermediate film of the present invention, the shear storage modulus is 3 MPa or more and 2000 MPa or less in a temperature range of 80% or more in a temperature range of 10 ° C or more and 30 ° C or less.

In a specific aspect of the interlayer film of the present invention, the content of the second resin is 20% by weight or more in 100% by weight of the total of the polyvinyl acetal resin and the second resin.

In a specific aspect of the intermediate film of the present invention, the second resin has a crosslinked structure, or the polyvinyl acetal resin is crosslinked with the second resin.

In a specific aspect of the interlayer film of the present invention, the interlayer film is a single-layer interlayer film.

In a specific aspect of the interlayer film of the present invention, the maximum value of tan δ in a temperature range of -40 ° C to 0 ° C is 0.15 or more.

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

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

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

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

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

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

The interlayer film for laminated glass of the present invention contains a polyvinyl acetal resin, a second resin other than the polyvinyl acetal resin, and a plasticizer. In the interlayer film for laminated glass of the present invention, the content of the plasticizer is 3 parts by weight or more and less than 20 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. The interlayer film for laminated glass of the present invention has a phase separation structure. In the interlayer film for laminated glass of the present invention, in the phase separation structure, the second resin is an island portion, and in the phase separation structure, an average diameter of the island portion is 10 nm or more and 1 μm or less. The glass transition temperature of the interlayer film for laminated glass exists at -40 ° C or higher and 0 ° C or lower. Since the interlayer film for laminated glass of the present invention has the above-mentioned structure, the flexural rigidity of the laminated glass using the interlayer film for laminated glass of the present invention at 20 ° C can be improved, and the sound insulation of the laminated glass can be improved. And penetration resistance.

Hereinafter, the present invention will be described in detail.

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

The intermediate film of the present invention contains a polyvinyl acetal resin, a second resin other than the polyvinyl acetal resin, and a plasticizer. In the interlayer film of the present invention, the content of the plasticizer is 3 parts by weight or more and less than 20 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. A resin other than a polyvinyl acetal resin is distinguished from a polyvinyl acetal resin and is referred to as a second resin.

The intermediate film of the present invention has a phase separation structure. In the interlayer film of the present invention, in the phase separation structure, the second resin is an island portion (area). In the interlayer film of the present invention, the average diameter of the island portions is 10 nm or more and 1 μm or less.

Furthermore, the glass transition temperature of the intermediate film of the present invention exists at -40 ° C or higher and 0 ° C or lower.

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

Furthermore, since the interlayer film of the present invention has the above-mentioned structure, the sound insulation properties of the laminated glass using the interlayer film of the present invention can be improved.

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

The present invention can make all three of the higher flexural rigidity, the higher sound insulation, and the higher penetration resistance better than one or two.

Since the said intermediate film contains a polyvinyl acetal resin and a 2nd resin other than a polyvinyl acetal resin, a sound insulation property is effectively improved. Moreover, since the said intermediate film uses a polyvinyl acetal resin and a plasticizer, penetration resistance is effectively improved.

Moreover, since the said intermediate film has a phase separation structure, and in this phase separation structure, since the said 2nd resin is an island part, flexural rigidity and penetration resistance effectively become high. Furthermore, since the average diameter of the said island part is 10 nm or more and 1 μm or less, flexural rigidity and penetration resistance become more effective. In the present invention, as one of the factors that exert the above-mentioned effect, it is considered that the reason is that the interface is effectively increased by the phase separation structure having the radius of the island portion as described above, so that energy distribution and absorption proceed smoothly.

The polyvinyl acetal resin is preferably a surrounding area, and the polyvinyl acetal resin is preferably a matrix. The phase separation structure is preferably a sea-island structure. The polyvinyl acetal resin and the second resin are preferably contained in different phases. In the case of a sea-island structure, it is preferable that the polyvinyl acetal resin is a sea part, and the second resin is an island part. By obtaining the phase separation structure described above, flexural rigidity and penetration resistance can be effectively exhibited.

From the viewpoint of further improving the flexural rigidity and penetration resistance, in the phase separation structure described above, the average diameter of the island portion is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more. Particularly preferred is 30 nm or more. The diameter of each island portion indicates the maximum diameter, and the average of the diameters of the island portions is obtained by averaging the diameters (maximum diameters) of the plurality of island portions.

In order to set the average of the diameter of the island portion within the above range, a method of mechanically kneading a composition for forming an intermediate film under high shear conditions, a method of adding a surfactant to the intermediate film, and A method of using a second resin having a polar functional group such as a hydroxyl group or a carboxyl group.

From the viewpoint of improving the sound insulation property, the glass transition temperature of the intermediate film exists at -40 ° C or higher and 0 ° C or lower. From the viewpoint of further improving sound insulation properties, the glass transition temperature of the intermediate film is preferably present at -35 ° C or higher and -2 ° C or lower. If the glass transition temperature is above the above lower limit and below the above upper limit, the temperature can be set to a temperature corresponding to the correlation frequency according to the time-temperature exchange algorithm, which can effectively improve sound insulation. In addition, since it can respond quickly, the energy absorption of high-speed impact is increased, and the penetration resistance is effectively increased.

As a method for measuring the above-mentioned glass transition temperature, the following method may be mentioned: After the above-mentioned interlayer film is stored in an environment of room temperature 23 ± 2 ° C and humidity 25 ± 5% for 12 hours, the viscoelasticity measurement made by IT Measurement Control Co., Ltd. is immediately used The device "DVA-200" measures viscoelasticity. It is preferable that the intermediate film is cut out with a length of 8 mm and a width of 5 mm, and the temperature is increased from -50 ° C to 150 ° C in a shearing mode at a heating rate of 3 ° C / min, and the frequency is 1 Hz, The glass transition temperature was measured under a strain of 0.08%.

From the viewpoint of improving sound insulation, the maximum value of tan δ in the temperature range of the intermediate film in the temperature range of -40 ° C to 0 ° C is 0.1 or more, more preferably 0.11 or more, and still more preferably 0.15 or more, and more It is 1 or less, more preferably 0.8 or less, and still more preferably 0.6 or less. When the maximum value of tan δ is greater than or equal to the above-mentioned lower limit, energy loss increases, and thus sound insulation, penetration resistance, and bending matching are effectively increased. When the maximum value of tan δ is equal to or less than the above upper limit, the shear storage modulus becomes moderately high, and the flexural rigidity and penetration resistance effectively become high.

Furthermore, the interlayer film may be applied to curved glass for the purpose of obtaining curved laminated glass or the like. The above-mentioned bendability means the ease of matching when matching with curved glass.

From the viewpoint of further improving the flexural rigidity, the shear storage modulus of the above-mentioned interlayer film at 30 ° C is preferably 3 MPa or more, more preferably 10 MPa or more, more preferably 2000 MPa or less, and even more preferably 1000 MPa. the following.

From the viewpoint of further improving the flexural rigidity, the shear storage modulus of the intermediate film is better in a temperature range of 80% or more (preferably 82% or more) in a temperature range of 10 ° C to 30 ° C It is 3 MPa or more and 2000 MPa or less.

Furthermore, in a case where the intermediate film is a multilayer intermediate film, the shear storage modulus means a shear storage equivalent modulus. The above-mentioned shear storage equivalent modulus indicates the shear storage modulus when a multilayer body is regarded as a single layer. When it is not sliding between layers, for example, the shear storage modulus can be directly measured by a general dynamic viscoelasticity measurement method in the form of a layer constituting the interlayer film, thereby determining the above-mentioned shear storage equivalent modulus.

The shear storage modulus and the shear storage equivalent modulus are determined as follows.

As a method for measuring the above-mentioned shear storage modulus and the above-mentioned shear storage equivalent modulus, the following methods can be cited: Immediately after storing the intermediate film in an environment of room temperature 23 ± 2 ° C and humidity 25 ± 5% for 12 hours, immediately The viscoelasticity was measured using a viscoelasticity measuring device "DVA-200" manufactured by IT Measurement Control Corporation. It is preferable that the intermediate film is cut out with a length of 8 mm and a width of 5 mm, and the temperature is increased from -50 ° C to 150 ° C in a shearing mode at a heating rate of 3 ° C / min, and the frequency is 1 Hz, The above-mentioned shear storage modulus and the above-mentioned shear storage equivalent modulus were measured under a strain of 0.08%.

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

G '* = (Σiai) / (Σiai / G'i) Formula (A)

G′i in the above formula (A) represents the shear storage modulus of the i-th layer in the interlayer film, and ai represents the thickness of the i-th layer in the interlayer film. Σi means to calculate the sum of the values of the i layer.

From the viewpoint of further improving the flexural rigidity, the gel fraction obtained by the following formula (X) in the intermediate film is preferably 10% by weight or more. From the viewpoint of further improving the penetration resistance, the gel fraction obtained by the following formula (X) in the intermediate film is preferably 10% by weight or more, and more preferably 80% by weight or less. When the gel fraction is 10% by weight or more, the effect of improving the flexural rigidity and penetration resistance becomes high. By setting the gel fraction to 80% by weight or less, penetration resistance is significantly increased. From the viewpoint of further improving the flexural rigidity and penetration resistance, the gel fraction is more preferably 30% by weight or more. From the viewpoint of further improving 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 intermediate film before immersion of the intermediate film at 23 ° C tetrahydrofuran W2: After immersion of the intermediate film at 23 ° C tetrahydrofuran The weight of the interlayer film after being taken out and dried

The interlayer film may be a single-layer interlayer film or a multi-layer interlayer film. In the case of a single-layer interlayer film, the flexural rigidity is further improved. In the case of a multilayer intermediate film, penetration resistance is further improved.

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

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

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

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

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

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

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

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

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

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

Hereinafter, details of the first layer, the second layer, and the third layer constituting the interlayer film of the present invention, and details of each component contained in the first layer, the second layer, and the third layer are described below. Contents are explained.

(Resin) The interlayer film contains a polyvinyl acetal resin and a second resin other than the polyvinyl acetal resin. The first layer, the second layer, and the third layer preferably each contain a polyvinyl acetal resin. The first layer, the second layer, and the third layer are each preferably a second resin other than a polyvinyl acetal resin. The polyvinyl acetal resin may be used alone or in combination of two or more. The second resin may be used alone or in combination of two or more.

The content of the polyvinyl acetal resin in the total 100% by weight of the polyvinyl acetal resin and the second resin is preferably 20% by weight or more, more preferably 25% by weight or more, and further preferably 30% by weight. % Or more, particularly preferably 35% by weight or more, and preferably less than 100% by weight. When the content of the polyvinyl acetal resin is at least the above lower limit, the flexural rigidity is effectively increased. The content of the polyvinyl acetal resin may be 90% by weight or less, 80% by weight or less, and 75% by weight of the total amount of the polyvinyl acetal resin and the second resin. It can also be 70% by weight or less and 65% by weight or less.

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

The interlayer film contains a second resin other than a polyvinyl acetal resin from the viewpoint of effectively improving the flexural rigidity and sound insulation properties. From the viewpoint of effectively improving the flexural rigidity and sound insulation properties, the first layer, the second layer, and the third layer are each preferably a second resin other than a polyvinyl acetal resin. Examples of the second resin include a thermosetting resin and a thermoplastic resin. The intermediate film preferably contains a thermoplastic resin (a second thermoplastic resin other than a polyvinyl acetal resin) as the second resin. A thermoplastic resin other than a polyvinyl acetal resin may be distinguished from a polyvinyl acetal resin and may be referred to as a second thermoplastic resin. The second resin may be used alone or in combination of two or more. From the viewpoint of effectively improving the flexural rigidity and sound insulation properties, the interlayer film preferably contains a resin that is not compatible with the polyvinyl acetal resin as the second resin. From the viewpoint of effectively improving the flexural rigidity and sound insulation properties, the interlayer film preferably contains a polyolefin resin, an acrylic polymer, a urethane polymer, a silicone polymer, a rubber, or a vinyl acetate. polymer. From the viewpoint of effectively improving the flexural rigidity and sound insulation properties, the interlayer film is more preferably an acrylic polymer containing a balance of properties that can be easily obtained.

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

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

The content of the second resin other than the polyvinyl acetal resin in 100% by weight of the total of the polyvinyl acetal resin and the second resin is preferably 20% by weight or more, more preferably 25% by weight or more, It is preferably 30% by weight or more, particularly preferably 35% by weight or more, and preferably less than 100% by weight. When content of the said 2nd resin is more than the said lower limit, flexural rigidity, sound insulation, and penetration resistance effectively become high. Of the total 100% by weight of the polyvinyl acetal resin and the second resin, the content of the second resin is preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 75% by weight or less, It is particularly preferably 70% by weight or less, and most preferably 65% by weight or less. When content of the said 2nd resin is below the said upper limit, flexural rigidity, sound insulation, and penetration resistance effectively become high.

The content of the acrylic polymer in the total 100% by weight of the polyvinyl acetal resin and the acrylic polymer is preferably 20% by weight or more, more preferably 25% by weight or more, and further preferably 30% by weight or more. , Particularly preferably 35% by weight or more, and preferably less than 100% by weight. When the content of the acrylic polymer is at least the above lower limit, the flexural rigidity, sound insulation, and penetration resistance are effectively increased. The content of the acrylic polymer in the total 100% by weight of the polyvinyl acetal resin and the second resin is preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 75% by weight or less. , Particularly preferably 70% by weight or less, and most preferably 65% by weight or less. When content of the said acrylic polymer is below the said upper limit, flexural rigidity, sound insulation, and penetration resistance effectively become high.

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

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

When the interlayer film contains a crosslinked product of the polyvinyl acetal resin and the second resin, the glass transition temperature of the polyvinyl acetal resin indicates the polyethylene derived from the crosslinked product. The glass transition temperature of the acetal resin, and the glass transition temperature of the second resin indicate the glass transition temperature of the second resin derived from the crosslinked product.

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

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

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

The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, even more preferably 1500 or more, even more preferably 1600 or more, particularly preferably 2600 or more, and most preferably 2700 or more, and It is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3500 or less. When the average polymerization degree is greater than or equal to the above lower limit, the penetration resistance and flexural rigidity of the laminated glass are further increased. When the average polymerization degree is equal to or less than the above upper limit, the formation of the intermediate film becomes easy.

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

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

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

The content ratio (hydroxyl amount) of the hydroxyl groups of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) is preferably 20 mol% or more, and more It is preferably 22 mol% or more, more preferably 24 mol% or more, and still more preferably 26 mol% or more. The content ratio (hydroxyl content) of the hydroxyl groups of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) is more preferably 28 mol% or more, Especially preferred is more than 30 mol%. The content ratio (hydroxyl content) of the hydroxyl groups of the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) is preferably 37 mol% or less, more preferably It is preferably 36.5 mol% or less, more preferably 36 mol% or less. When the content rate of the said hydroxyl group is more than the said minimum, a flexural rigidity will become high more, and the adhesive force of an intermediate film will become high further. Moreover, when the content rate of the said hydroxyl group is below the said upper limit, the flexibility of an intermediate film will become high and handling of an intermediate film will become easy.

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

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

The degree of acetylation of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, and preferably 10 Molar% or less, more preferably 2 Molar% or less. When the degree of acetylation is greater than or equal to the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. When the degree of acetylation is equal to or less than the above upper limit, the moisture resistance of the interlayer film and the laminated glass becomes high.

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

The degree of acetalization of the polyvinyl acetal resin (1) (the degree of butyralization in the case of a polyvinyl butyral resin) is preferably 47 mol% or more, and more preferably 60 mol%. Above, still more preferably 68 mol% or more, and more preferably 85 mol% or less, more preferably 80 mol% or less, and still more preferably 75 mol% or less. When the degree of acetalization is at least the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. If the degree of acetalization is equal to or less than the upper limit described above, the reaction time required for producing the polyvinyl acetal resin becomes short.

The degree of acetalization (in the case of polyvinyl butyral resin, the degree of butyralization) of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 55. Molar% or more, more preferably 60 mol% or more, and more preferably 75 mol% or less, and more preferably 71 mol% or less. When the degree of acetalization is at least the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer becomes high. If the degree of acetalization is equal to or less than the upper limit described above, the reaction time required for producing the polyvinyl acetal resin becomes short.

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

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

(Plasticizer) The intermediate film preferably contains a plasticizer. The first layer (including a single-layer intermediate film) preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter, sometimes referred to as a plasticizer (3)). By using a plasticizer, and by using a polyvinyl acetal resin and a plasticizer together, penetration resistance is further excellent. A layer containing a polyvinyl acetal resin and a plasticizer is useful for laminated glass members or other layers. Then the force becomes moderately high. The plasticizer is not particularly limited. The plasticizer (1) and the plasticizer (2) may be the same as or different from the plasticizer (3). The plasticizer (1), the plasticizer (2), and the plasticizer (3) may be used alone or in combination of two or more.

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

Examples of the monobasic organic acid ester include glycol esters obtained by reacting a glycol with a monobasic organic acid. Examples of the diol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, hexanoic acid, 2-ethylbutanoic acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, and capric acid.

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

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

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

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

[Chemical 1]

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

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

From the viewpoint of effectively improving penetration resistance, the content of the plasticizer in the intermediate film is 3 parts by weight or more and less than 20 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. From the viewpoint of further improving penetration resistance, the content of the plasticizer in the intermediate film is preferably 5 parts by weight or more, and preferably 18 parts by weight, relative to 100 parts by weight of the polyvinyl acetal resin. The following. If the plasticizer is above the lower limit and does not reach the upper limit, flexibility at low temperature can be imparted. Therefore, an intermediate film having excellent shock absorption in a high-speed region equivalent to low temperature can be produced according to a time-temperature exchange algorithm.

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

In the case of a multilayer interlayer film, in the first layer, 100 parts by weight of the thermoplastic resin (1) (when the thermoplastic resin (1) is a polyvinyl acetal resin (1), The content of the plasticizer (1) of the polyvinyl acetal resin (1) (100 parts by weight) was set as the content (1). The content (1) is preferably 1 part by weight or more, more preferably 2 parts by weight or more, still more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more, and preferably 90 parts by weight or less, more preferably It is 85 parts by weight or less, and more preferably 80 parts by weight or less. When the content (1) is greater than or equal to the above lower limit, the flexibility of the interlayer film becomes high, and handling of the interlayer film becomes easy. When the said content (1) is below the said upper limit, the penetration resistance of laminated glass will become still higher. The content (1) may be 50 parts by weight or more, 55 parts by weight or more, and 60 parts by weight or more. The content (1) may be 30 parts by weight or less, 20 parts by weight or less, and 10 parts by weight or less.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the heat-insulating particles, the content of the heat-insulating particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and even more preferably It is 1% by weight or more, and particularly preferably 1.5% by weight or more. In 100% by weight of the layer (the first layer, the second layer, or the third layer) containing the heat-insulating particles, the content of the heat-insulating particles is preferably 6% by weight or less, more preferably 5.5% by weight or less, and further preferably It is 4% by weight or less, particularly preferably 3.5% by weight or less, and most preferably 3% by weight or less. When the content of the heat-insulating particles is equal to or more than the lower limit and equal to or less than the upper limit, the heat-shielding property is sufficiently increased, and the visible light transmittance is sufficiently increased.

(Metal salt) The intermediate film preferably contains at least one metal salt (hereinafter, sometimes referred to as metal salt M) of an alkali metal salt, an alkaline earth metal salt, and a magnesium salt. The first layer preferably contains the metal salt M. The second layer preferably contains the metal salt M. The third layer preferably contains the metal salt M. By using the above-mentioned metal salt M, it becomes easy to control the adhesiveness between the intermediate film and the laminated glass member or the adhesiveness between the layers in the intermediate film. The metal salt M may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

Examples of the ultraviolet shielding agent having the benzophenone structure include octanone ("Chimassorb81" manufactured by BASF) and the like.

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

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

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

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

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

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

(Antioxidant) The intermediate film preferably contains an antioxidant. The first layer preferably contains an antioxidant. The second layer preferably contains an antioxidant. The third layer preferably contains an antioxidant. These antioxidants may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As described above, the laminated glass of the present invention includes the first laminated glass member, the second laminated glass member, and an interlayer film, and the interlayer film is the interlayer film for laminated glass of the present invention. In the laminated glass of the present invention, the interlayer film is disposed between the first laminated glass member and the second laminated glass member.

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

Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. The laminated glass includes not only laminated glass in which an interlayer film is interposed between two glass plates, but also laminated glass in which an interlayer film is interposed between a glass plate and a PET film. The laminated glass is a laminated body including a glass plate, and it is preferable to use at least one glass plate. Preferably, the first laminated glass member and the second laminated glass member are respectively a glass plate or a PET film, and the laminated glass includes a glass plate as the first laminated glass member and the second laminated glass member. At least one of them.

Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include a float plate glass, a heat ray absorption plate glass, a heat ray reflection plate glass, a polishing plate glass, an embossed plate glass, and a spun glass. The organic glass is a synthetic resin glass that replaces the inorganic glass. Examples of the organic glass include a polycarbonate plate and a poly (meth) acrylic resin plate. Examples of the poly (meth) acrylic resin plate include a poly (meth) acrylate plate and the like.

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

By using the interlayer film of the present invention, even if the thickness of the laminated glass is thin, the flexural rigidity of the laminated glass can be maintained high. The thickness of the glass plate is preferably 2 mm or less, more preferably 1.8 mm or less, even more preferably 1.6 mm or less, even more preferably 1.5 mm or less, still more preferably 1.4 mm or less, and still more preferably 1.3 mm or less. It is more preferably 1.0 mm or less, and even more preferably 0.7 mm or less. In this case, the laminated glass can be made lighter, or the material of the laminated glass can be reduced to reduce the environmental load, or the lightweight of the laminated glass can be used to improve the fuel efficiency of the automobile and reduce the environmental load. The total of the thickness of the first glass plate and the thickness of the second glass plate is preferably 3.5 mm or less, more preferably 3.2 mm or less, still more preferably 3 mm or less, and even more preferably 2.8 mm or less. In this case, the laminated glass can be made lighter, or the material of the laminated glass can be reduced to reduce the environmental load, or the lightweight of the laminated glass can be used to improve the fuel efficiency of the automobile and reduce the environmental load.

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

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

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

Prepare the following materials.

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

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

In Tables 1 to 3, when the value of the degree of butyralization (acetalization degree) is described, a polyvinyl butyral resin is used, and the value of the degree of acetalization (degree of acetalization) is used. In the case of a value, a polyvinyl acetal resin is used.

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

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

Ethyl acrylate butyl acrylate benzyl acrylate 2-hydroxyethyl acrylate acrylic acid glycidyl methacrylate (crosslinking agent) tripropylene glycol diacrylate (crosslinking agent)

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

(Ultraviolet shielding agent) Tinuvin 326 (2- (2'-hydroxy-3'-third butyl-5-methylphenyl) -5-chlorobenzotriazole, "Tinuvin 326" manufactured by BASF)

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

(Example 1) Production of a composition for forming a first layer: 100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, and an acrylic polymer of the type shown in Table 1 below 150 parts by weight, 15 parts by weight of a plasticizer (3GO), 0.2 parts by weight of an ultraviolet shielding agent (Tinuvin 326), and 0.2 parts by weight of an antioxidant (BHT) were mixed to obtain a composition for forming a first layer.

Production of a composition for forming the second layer and the third layer: 100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, 18 parts by weight of a plasticizer (3GO), and an ultraviolet shielding agent ( Tinuvin 326) 0.2 parts by weight and antioxidant (BHT) 0.2 parts by weight were mixed to obtain a composition for forming the second layer and the third layer.

Production of intermediate film: The composition for forming the first layer and the composition for forming the second layer and the third layer are co-extruded using a coextruder, thereby producing a layer having the second layer / the first layer / Interlayer with a laminated structure of the third layer. The thickness of each layer is described in Table 1 below.

Production of laminated glass (for measuring flexural rigidity): The obtained intermediate 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 (transparent float glass, 20 cm in height × 2.5 cm in width) having the thickness shown in Table 1 below were prepared. The obtained intermediate film was sandwiched between the two glass plates to obtain a laminated body. The obtained laminated body was put into a rubber bag and degassed for 20 minutes under a vacuum of 2660 Pa (20 torr). Thereafter, while maintaining the degassed state, the laminate was held in an autoclave and further held at 90 ° C. for 30 minutes, and then vacuum-pressurized. The pre-pressed laminated body was press-bonded in an autoclave at 135 ° C and a pressure of 1.2 MPa (12 kg / cm ² ) for 20 minutes to obtain a laminated glass.

Production of laminated glass (for sound insulation measurement): The obtained intermediate film was cut into a size of 30 cm in length × 2.5 cm in width. As the first laminated glass member and the second laminated glass member, two glass plates (transparent float glass, 30 cm in height × 2.5 cm in width) having the thickness shown in Table 1 below were prepared. An interlayer film was sandwiched between two glass plates to obtain a laminated body. The laminated body was put into a rubber bag, and after being degassed under a vacuum of 2.6 kPa for 20 minutes, the degassed state was transferred to an oven, and further held at 90 ° C for 30 minutes. The laminated body is pre-crimped. The pre-pressed laminated body was pressure-bonded in an autoclave at 135 ° C and a pressure of 1.2 MPa for 20 minutes to obtain a laminated glass.

Production of laminated glass (for penetration resistance test): The obtained intermediate film was cut into a size of 15 cm in length × 15 cm in width. As the first laminated glass member and the second laminated glass member, two glass plates (transparent float glass, 15 cm in length × 15 cm in width) having a thickness shown in Table 1 below were prepared. An interlayer film was sandwiched between two glass plates to obtain a laminated body. The laminated body was put into a rubber bag, and after being degassed under a vacuum of 2.6 kPa for 20 minutes, the degassed state was transferred to an oven, and further held at 90 ° C for 30 minutes. The laminated body is pre-crimped. The pre-pressed laminated body was pressure-bonded in an autoclave at 135 ° C and a pressure of 1.2 MPa for 20 minutes to obtain a laminated glass.

(Example 2 and Comparative Example 1) The composition of the composition for forming the first layer and the composition of the composition for forming the second layer and the third layer were set as shown in Table 1 below, and as shown in Table 1 below Except that the thicknesses of the first layer, the second layer, the third layer, the first laminated glass member, and the second laminated glass member were set as shown, an intermediate film and a laminate were obtained in the same manner as in Example 1. glass. In Example 2 and Comparative Example 1, the same amount of ultraviolet shielding agent and the same type of ultraviolet shielding agent as in Example 1 were prepared at the same compounding amount as in Example 1 (0.2 parts by weight based on 100 parts by weight of polyvinyl acetal resin) Antioxidants.

(Example 3) Production of a composition for forming an intermediate film (first layer): 100 parts by weight of a polyvinyl acetal resin of the type shown in Table 2 below, and of the type of a polyvinyl acetal resin shown in Table 2 below 120 parts by weight of an acrylic polymer, 7.5 parts by weight of a plasticizer (3GO), 0.2 parts by weight of an ultraviolet shielding agent (Tinuvin 326), and 0.2 parts by weight of an antioxidant (BHT) were mixed to obtain a composition for forming an intermediate film .

Production of intermediate film: The composition for forming an intermediate film was extruded using an extruder, thereby producing an intermediate film having a thickness shown in Table 2 below.

Production of laminated glass (for measurement of flexural rigidity): Using the obtained intermediate film, a laminated glass was produced in the same manner as in Example 1.

Production of laminated glass (for sound insulation measurement): Using the obtained intermediate film, a laminated glass was produced in the same manner as in Example 1.

Production of laminated glass (for penetration resistance test measurement): Using the obtained intermediate film, a laminated glass was produced in the same manner as in Example 1.

(Examples 4 to 9 and Comparative Examples 2 to 6) The composition of the composition for forming an intermediate film was set as shown in Tables 2 and 3 below, and the intermediate film and the first film were set as shown in Tables 2 and 3 below. Except for the thickness of the laminated glass member and the second laminated glass member, an interlayer film and a laminated glass were obtained in the same manner as in Example 3. In Examples 4 to 9 and Comparative Examples 2 to 6, the same amount of the same compound as in Example 3 (0.2 parts by weight relative to 100 parts by weight of the polyvinyl acetal resin) was blended. UV shielding agent and antioxidant.

(Evaluation) (1) Viscoelastic Shear Storage Modulus: The shear storage modulus was measured at a frequency of 1 Hz (in the case of a multilayer interlayer film, the shear storage equivalent modulus was measured). Specifically, after the obtained intermediate film was stored in an environment of room temperature 23 ± 2 ° C and humidity 25 ± 5% for 12 hours, the viscosity was measured immediately using a viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Corporation. elasticity. Cut out the interlayer film with a length of 8 mm and a width of 5 mm. In the shear mode, increase the temperature from -50 ° C to 150 ° C at a heating rate of 3 ° C / min, and the frequency is 1 Hz and the strain is 0.08%. The measurement was performed under the conditions. In a multilayer interlayer film, when there is no measurement failure due to sliding between layers, the shear storage modulus is determined based on the following criteria. When there is a poor measurement, the viscoelasticity of each layer is measured in the multilayer intermediate film by the above method, and the shear storage modulus is calculated by calculation. The shear storage modulus was determined based on the following criteria.

[Judgment Criteria for Shear Storage Modulus] A: In a temperature range of 80% or more in a temperature range of 10 ° C or more and 30 ° C or less, the shear storage modulus is 3 MPa or more and 2000 MPa or less B: and A The benchmarks do not match

Glass transition temperature: For example, after storing the obtained intermediate film in an environment of room temperature 23 ± 2 ° C and humidity 25 ± 5% for 12 hours, immediately use a viscoelasticity measuring device “DVA-200” manufactured by IT Measurement and Control Corporation. Method for measuring viscoelasticity. Cut out the interlayer film with a length of 8 mm and a width of 5 mm. In the shear mode, increase the temperature from -50 ° C to 150 ° C at a heating rate of 3 ° C / min, and the frequency is 1 Hz and the strain is 0.08%. The measurement was performed under the conditions. The temperature at which the maximum value of tan δ is displayed is set as the glass transition temperature, and the case where the maximum value of tan δ does not exist above -40 ° C and below 0 ° C is set to "none".

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

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

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

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

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

(3) Gel fraction 0.2 g of the intermediate film was immersed in 40 g of tetrahydrofuran, and then immersed by shaking at 23 ° C for 24 hours. Then, after centrifuging at 10 ° C and 10,000 rpm with a centrifugal separator (manufactured by KUBOTA, high-speed large-capacity cooling centrifuge 7780), the supernatant liquid was removed. The residue in the container was heated at 110 ° C for 1 hour and dried. Thereafter, the weight of the residue was measured. The gel fraction was calculated by the above formula (X). The gel fraction was determined based on the following criteria.

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

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

[Judgment criteria for flexural rigidity at 20 ° C] ○: Flexural rigidity is 55 N / mm or more ○: Flexural rigidity is 50 N / mm or more and less than 55 N / mm △: Flexural rigidity is 45 N / mm or more and less than 50 N / mm ×: The flexural rigidity is less than 45 N / mm

(5) Sound insulation A vibration was applied to the obtained laminated glass by a vibration generator ("Vibrator G21-005D" manufactured by Zhenken Co., Ltd.) for a damping test. A mechanical impedance measuring device ("XG-81" manufactured by RION Corporation) was used to amplify the vibration characteristics obtained therefrom, and a FFT (Fast Fourier Transform) spectrum analyzer ("FFT Analyzer manufactured by Yokogawa HP Corporation") was used. HP3582A ") to analyze the vibration spectrum.

Based on the ratio of the loss coefficient obtained in the above manner to the resonance frequency of the laminated glass, a graph showing the relationship between the audio frequency (Hz) and the sound transmission loss (dB) at 20 ° C is made. Sound transmission loss (TL value). The higher the TL value, the higher the sound insulation property. The sound insulation was judged by the following criteria.

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

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

[Criterion for judging penetration resistance] ○: Maximum height is 4 m or more ○: Maximum height is 3.75 m ×: Maximum height is 3.5 m or less

The details and results are shown in Tables 1 to 3 below. In addition, in the following Tables 1-3, description of an ultraviolet shielding agent and an antioxidant is abbreviate | omitted.

[Table 1]

[Table 2]

[table 3]

1‧‧‧ Level 1

1a‧‧‧The first surface

1b‧‧‧ 2nd surface

2‧‧‧ Level 2

2a‧‧‧outer surface

3‧‧‧ Level 3

3a‧‧‧ outside surface

11‧‧‧ Interlayer

11A‧‧‧Interlayer (first layer)

11a‧‧‧First surface

11b‧‧‧ 2nd surface

21‧‧‧The first laminated glass member

22‧‧‧ 2nd laminated glass member

31‧‧‧ laminated glass

31A‧‧‧Laminated glass

D1‧‧‧distance

D2‧‧‧distance

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

Claims (12)

An interlayer film for laminated glass comprising a polyvinyl acetal resin, a second resin other than the polyvinyl acetal resin, and a plasticizer, and the plastic is 100 parts by weight of the polyvinyl acetal resin. The content of the chemical agent is 3 parts by weight or more and less than 20 parts by weight. The interlayer film for laminated glass has a phase separation structure. In the phase separation structure, the second resin is an island portion and in the phase separation structure. The average diameter of the islands is 10 nm or more and 1 μm or less, and the glass transition temperature of the interlayer film for laminated glass exists at -40 ° C or higher and 0 ° C or lower. For example, the interlayer film for laminated glass of claim 1 has a shear storage modulus of 3 MPa or more and 2000 MPa or less in a temperature range of 80% or more in a temperature range of 10 ° C or more and 30 ° C or less. For example, the interlayer film for laminated glass according to claim 1 or 2, wherein the content of the second resin is 20% by weight or more in the total 100% by weight of the polyvinyl acetal resin and the second resin. For example, the interlayer film for laminated glass according to claim 1 or 2, wherein the second resin has a crosslinked structure, or the polyvinyl acetal resin is crosslinked with the second resin. If the interlayer film for laminated glass of claim 1 or 2 is a single layer interlayer film for laminated glass. For example, if the interlayer film for laminated glass of claim 1 or 2 has a maximum value of tanδ of 0.15 or higher in a temperature range of -40 ° C or higher and 0 ° C or lower. If the interlayer film for laminated glass of claim 1 or 2 has a thickness of 3 mm or less. For example, the interlayer film for laminated glass according to claim 1 or 2 is used to obtain a laminated glass by using a first glass plate having a thickness of 1.6 mm or less and placing it between the first glass plate and the second glass plate. For example, the interlayer film for laminated glass of claim 1 or 2 is used to obtain laminated glass disposed between the first glass plate and the second glass plate, and the thickness of the first glass plate and the second glass plate are The total thickness is 3.5 mm or less. A laminated glass comprising: a first laminated glass member, a second laminated glass member, and the interlayer film for laminated glass according to any one of claims 1 to 9, and the interlayer film for laminated glass is configured Between the first laminated glass member and the second laminated glass member. For example, the laminated glass of claim 10, wherein the first laminated glass member is a first glass plate, and the thickness of the first glass plate is 1.6 mm or less. For example, the laminated glass of claim 10 or 11, wherein the first laminated glass member is a first glass plate, the second laminated glass member is a second glass plate, and the thickness of the first glass plate is the same as that of the second glass plate. The total thickness of the glass plate is 3.5 mm or less.