WO2021002032A1

WO2021002032A1 - Interlayer film for laminated glass, and laminated glass

Info

Publication number: WO2021002032A1
Application number: PCT/JP2019/045500
Authority: WO
Inventors: 由貴石川; 晋治河田; 達矢岩本
Original assignee: 積水化学工業株式会社
Priority date: 2019-07-02
Filing date: 2019-11-20
Publication date: 2021-01-07
Also published as: JPWO2021002032A1; JP7372840B2; TW202102364A

Abstract

Provided is an interlayer film for laminated glass, the interlayer film being able to suppress separation between layers of the interlayer film, despite the layers which contain mutually different resins being stacked, and also being able to increase the transparency of the laminated glass.　The interlayer film for laminated glass according to the present invention is for laminated glass having a structure composed of at least two layers. The interlayer film comprises: a first layer including a resin; and a second layer disposed on a first surface of the first layer and including a resin. The first layer and the second layer contain different resins. The glass transition temperature of the fist layer is lower than the glass transition temperature of the second layer. The acid value of the first layer is 3 to 500 mg KOH/g. The haze of laminated glass X obtained by sandwiching the interlayer film between two sheets of clear glass is 0.5% or less.

Description

Laminated glass interlayer film and laminated glass

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

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

As an example of the interlayer film for laminated glass, the following Patent Document 1 contains a modified polyvinyl acetate and a plasticizer, and the modified polyvinyl acetate has a vinyl acetate structural unit and a fatty acid vinyl ester structural unit. An interlayer film for laminated glass is disclosed. Further, Patent Document 1 includes a first layer and a second layer laminated on the first surface of the first layer, and the first layer is the modified polyvinyl acetate. A laminated glass interlayer film containing the above plasticizer and having a second layer containing a polyvinyl acetal resin is disclosed.

WO2014 / 0695993A1

In order to improve the sound insulation of laminated glass, a multilayer interlayer film having a structure of two or more layers may be used. Further, in the multilayer interlayer film, different resins may be used for different layers. However, in an interlayer film in which layers containing different resins are laminated, peeling (delamination) is likely to occur at the interface between these layers.

The interlayer film described in Patent Document 1 can improve the sound insulation of the laminated glass to some extent. However, in the interlayer film described in Patent Document 1, delamination may occur when a multilayer interlayer film is used. Further, in the interlayer film described in Patent Document 1, the interlayer film becomes cloudy and the transparency of the laminated glass is lowered depending on the ratio of the vinyl acetate structural unit and the fatty acid vinyl ester structural unit of the modified polyvinyl acetate. Sometimes.

An object of the present invention is to provide an interlayer film for laminated glass, which can suppress delamination of the interlayer film even though layers containing different resins are laminated and can enhance the transparency of the laminated glass. Is to provide. Another object of the present invention is to provide a laminated glass using the above-mentioned interlayer film for laminated glass.

According to a broad aspect of the present invention, it is an interlayer film for laminated glass having a structure of two or more layers, which is laminated on a first layer containing a resin and a first surface of the first layer. A second layer containing a resin is provided, the first layer and the second layer contain different resins, and the glass transition temperature of the first layer is the glass transition temperature of the second layer. When the acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH / g or less, and an interlayer film is sandwiched between two clear glasses to obtain a laminated glass X, the laminated glass X of the laminated glass X is obtained. An interlayer film for laminated glass having a haze of 0.5% or less (in this specification, "interlayer film for laminated glass" may be abbreviated as "intermediate film") is provided.

In a specific aspect of the interlayer film according to the present invention, the first layer contains a resin having an acid value of 5 mgKOH / g or more and 500 mgKOH / g or less.

In certain aspects of the interlayer film according to the present invention, the first layer contains a resin having a carboxyl group.

In a specific aspect of the interlayer film according to the present invention, the content of the carboxyl group is 4% by weight or more and 15% by weight or less in 100% by weight of the resin having a carboxyl group.

In a specific aspect of the interlayer film according to the present invention, the resin having a carboxyl group is a (meth) acrylic polymer having a carboxyl group.

In certain aspects of the interlayer film according to the present invention, the first layer contains a plasticizer.

In a particular aspect of the interlayer film according to the present invention, the interlayer film has a structure of three or more layers and is laminated on a second surface of the first layer opposite to the first surface. It also has a third layer.

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

According to a broad aspect of the present invention, the first laminated glass member, the second laminated glass member, and a laminated glass interlayer film having a structure of two or more layers are provided, and the first laminated glass member and the above. The laminated glass interlayer film is arranged between the second laminated glass member, and the interlayer film is laminated on the first layer containing a resin and the first surface of the first layer. In the interlayer film, the first layer and the second layer contain different resins, and the glass transition temperature of the first layer is such that the first layer and the second layer contain different resins. Provided is a laminated glass having an acid value of 3 mgKOH / g or more and 500 mgKOH / g or less and a haze of 0.5% or less, which is lower than the glass transition temperature of the second layer.

In a specific aspect of the laminated glass according to the present invention, the first layer contains a resin having an acid value of 5 mgKOH / g or more and 500 mgKOH / g or less.

In a specific aspect of the laminated glass according to the present invention, the first layer contains a resin having a carboxyl group.

In a specific aspect of the laminated glass according to the present invention, the content of the carboxyl group is 4% by weight or more and 15% by weight or less in 100% by weight of the resin having a carboxyl group.

In a specific aspect of the laminated glass according to the present invention, the resin having a carboxyl group is a (meth) acrylic polymer having a carboxyl group.

In certain aspects of the laminated glass according to the present invention, the first layer comprises a plasticizer.

In a particular aspect of the laminated glass according to the present invention, the interlayer film has a structure of three or more layers, and the interlayer film is a second layer opposite to the first surface of the first layer. It is provided with a third layer laminated on the surface of the.

The laminated glass interlayer film according to the present invention has a structure of two or more layers. The laminated glass interlayer film according to the present invention includes a first layer containing a resin and a second layer laminated on the first surface of the first layer and containing a resin. In the interlayer film for laminated glass according to the present invention, the first layer and the second layer contain different resins. In the laminated glass interlayer film according to the present invention, the glass transition temperature of the first layer is lower than the glass transition temperature of the second layer, and the acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH /. It is less than or equal to g. In the laminated glass interlayer film according to the present invention, when the interlayer film is sandwiched between two clear glasses to obtain a laminated glass X, the haze of the laminated glass X is 0.5% or less. Since the interlayer film for laminated glass according to the present invention has the above-mentioned structure, delamination of the interlayer film can be suppressed even though layers containing different resins are laminated, and the interlayer film can be laminated. The transparency of the glass can be increased.

The laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and an interlayer film for laminated glass having a structure of two or more layers. In the laminated glass according to the present invention, the interlayer film for laminated glass is arranged between the first laminated glass member and the second laminated glass member. In the laminated glass according to the present invention, the interlayer film includes a first layer containing a resin and a second layer laminated on the first surface of the first layer and containing a resin. In the laminated glass according to the present invention, in the interlayer film, the first layer and the second layer contain different resins, and the glass transition temperature of the first layer is the glass of the second layer. It is lower than the transition temperature, and the acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH / g or less. The laminated glass according to the present invention has a haze of 0.5% or less. Since the laminated glass according to the present invention has the above-mentioned structure, delamination of the interlayer film can be suppressed even though layers containing different resins are laminated, and the laminated glass is transparent. You can improve your sex.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of a laminated glass using the interlayer film for laminated glass shown in FIG.

The details of the present invention will be described below.

(Interlayer film for laminated glass)
The laminated glass interlayer film according to the present invention (hereinafter, may be abbreviated as "intermediate film") has a structure of two or more layers.

The interlayer film according to the present invention includes a first layer containing a resin and a second layer laminated on the first surface of the first layer and containing a resin.

In the interlayer film according to the present invention, the first layer and the second layer contain different resins. The “different resin” means a resin in which the content of different types of structural units is 50 mol% or more when the two resins are compared. Therefore, for example, the polyvinyl acetate resin and the polyvinyl butyral resin are different resins. Further, for example, the acrylic resin and the polyvinyl butyral resin are different resins. On the other hand, for example, polyvinyl butyral resin A (hydroxyl content 30.5 mol%, acetylation degree 1 mol%, acetalization degree (butyralization degree) 68.5 mol%) and polyvinyl butyral resin B (containing hydroxyl groups). The resin is not different from the rate of 24 mol%, the degree of acetylation of 12 mol%, and the degree of acetalization (butyralization degree) of 64 mol%). Since the polyvinyl butyral resin A and the polyvinyl butyral resin B have a content of 50% or more of structural units of the same type, they are regarded as the same resin in the present specification.

In the interlayer film according to the present invention, the glass transition temperature of the first layer is lower than the glass transition temperature of the second layer, and the acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH / g or less. is there.

In the interlayer film according to the present invention, when the interlayer film is sandwiched between two clear glasses to obtain a laminated glass X, the haze of the laminated glass X is 0.5% or less.

Since the interlayer film for laminated glass according to the present invention has the above-mentioned structure, delamination of the interlayer film can be suppressed even though layers containing different resins are laminated, and the interlayer film can be laminated. The transparency of the glass can be increased. In the laminated glass interlayer film according to the present invention, even though the first layer and the second layer contain different resins, peeling at the interface between the first layer and the second layer can be suppressed. Moreover, the transparency of the laminated glass can be improved.

Further, since the interlayer film for laminated glass according to the present invention has the above-mentioned structure, the sound insulation of the laminated glass can be improved.

The interlayer film has a structure of two or more layers. The interlayer film may have a two-layer structure, a three-layer structure, or a three-layer or more structure.

The interlayer film includes a first layer containing a resin and a second layer containing a resin. A second layer is laminated on the first surface of the first layer. The interlayer film may include a third layer laminated on a second surface of the first layer opposite to the first surface. The third layer preferably contains a resin. When the interlayer film does not include the third layer, the first and second layers may be the surface layer of the interlayer film and may not be the surface layer. When the interlayer film includes a third layer, the second and third layers may be the surface layer of the interlayer film and may not be the surface layer. Another layer may be provided on the surface of the second layer opposite to the first layer. Another layer may be provided on the surface of the third layer opposite to the first layer. The second layer and the third layer are preferably surface layers of an interlayer film.

The glass transition temperature of the first layer is lower than the glass transition temperature of the second layer from the viewpoint of exerting the effect of the present invention and enhancing the sound insulation of the laminated glass.

From the viewpoint of effectively exerting the effect of the present invention and further enhancing the sound insulation of the laminated glass, the absolute value of the difference between the glass transition temperature of the first layer and the glass transition temperature of the second layer. Is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, still more preferably 35 ° C. or higher, preferably 60 ° C. or lower, and more preferably 50 ° C. or lower.

From the viewpoint of effectively exerting the effect of the present invention and further enhancing the sound insulation of the laminated glass, the glass transition temperature of the first layer is lower than the glass transition temperature of the third layer. preferable. In particular, when the first layer and the third layer contain different resins and the glass transition temperature of the first layer is lower than the glass transition temperature of the third layer, the first layer Although the third layer and the third layer contain different resins, peeling at the interface between the first layer and the third layer can be suppressed.

From the viewpoint of effectively exerting the effect of the present invention and further enhancing the sound insulation of the laminated glass, the absolute value of the difference between the glass transition temperature of the first layer and the glass transition temperature of the third layer. Is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, still more preferably 35 ° C. or higher, preferably 60 ° C. or lower, and more preferably 50 ° C. or lower.

From the viewpoint of further enhancing the sound insulation of the laminated glass, the glass transition temperature of the first layer is preferably -20 ° C or higher, more preferably -15 ° C or higher, further preferably -10 ° C or higher, and particularly preferably -7. ° C. or higher, preferably 20 ° C. or lower, more preferably 10 ° C. or lower, still more preferably 5 ° C. or lower, particularly preferably 0 ° C. or lower.

From the viewpoint of further enhancing the sound insulation of the laminated glass, the glass transition temperature of the second layer is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, further preferably 30 ° C. or higher, particularly preferably 34 ° C. or higher. Is 60 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 45 ° C. or lower, and particularly preferably 40 ° C. or lower.

From the viewpoint of further enhancing the sound insulation of the laminated glass, the glass transition temperature of the third layer is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, further preferably 30 ° C. or higher, particularly preferably 34 ° C. or higher. Is 60 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 45 ° C. or lower, and particularly preferably 40 ° C. or lower.

The glass transition temperature is determined by viscoelasticity measurement. Specifically, the viscoelasticity measurement is performed as follows.

Store the test piece in an environment with a room temperature of 23 ± 2 ° C and a humidity of 25 ± 5% for 12 hours. Next, the viscoelasticity is measured using a viscoelasticity measuring device (for example, "ARES-G2" manufactured by TA Instruments). A parallel plate having a diameter of 8 mm is used as a jig, and the measurement is performed under the conditions of a shear mode, a temperature lowering rate of 3 ° C./min from 100 ° C. to −20 ° C., a frequency of 1 Hz, and a strain of 1%.

The tan δ at the peak temperature of tan δ of the first layer is preferably 2.0 or more, more preferably 2.2 or more, further preferably 2.4 or more, particularly preferably 2.5 or more, and preferably 10 or less. , More preferably 8 or less. In this case, the sound insulation of the laminated glass can be further improved.

The tan δ at the peak temperature of the tan δ of the first layer can be measured by viscoelasticity measurement as follows.

Immediately after storing the test piece in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a dynamic viscoelasticity measuring device (for example, “DVA-200” manufactured by IT Measurement Control Co., Ltd.) was used. , Measure viscoelasticity. In the shear mode, the temperature is raised from −50 ° C. to 200 ° C. at a heating rate of 3 ° C./min, and the measurement is performed under the conditions of frequency 1 Hz and strain 1%.

When measuring the glass transition temperature and the tan δ at the peak temperature of the tan δ of the first layer, the viscoelasticity measurement may be performed using the interlayer film itself. In this case, the peak of tan δ derived from the first layer, the second layer, the third layer and the like may be read from the measurement result. Alternatively, the glass transition temperature of the layer to be measured may be measured by peeling off each layer of the interlayer film. Further, in the case of laminated glass, the laminated glass member and the interlayer film may be peeled off after cooling the laminated glass with liquid nitrogen or the like, and viscoelasticity measurement may be performed using the peeled interlayer film.

From the viewpoint of suppressing delamination of the interlayer film, the acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH / g or less. If the acid value of the first layer is less than 3 mgKOH / g or more than 500 mgKOH / g, delamination of the interlayer film is likely to occur. Further, if the acid value of the first layer exceeds 500 mgKOH / g, the laminated glass may become cloudy or equipment such as an extruder may be corroded.

From the viewpoint of more effectively suppressing delamination of the interlayer film, the acid value of the first layer is preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, preferably 200 mgKOH / g or less, more preferably. Is 150 mgKOH / g or less.

The acid value of the first layer is measured according to the potentiometric titration method described in JIS K0070. Specifically, it can be measured as follows.

The sample (first layer) is dissolved in a solvent (for example, methyl ethyl ketone: toluene: methanol = 1: 1: 1 (volume ratio)). The obtained solution was subjected to a potentiometric titrator (for example, "AT-710" manufactured by Kyoto Electronics Co., Ltd., electrode: "H-171, R-173" manufactured by Kyoto Electronics Co., Ltd.) and 0.1 mol / L potassium hydroxide ethanol. Titration is performed using a solution, and the obtained inflection point is used as the end point of the titration, and the acid value is calculated from the following formula.

Acid value (mgKOH / g) = (V1-V0) x N x 56.11 x f / S
S: Mass (g) of sample (first layer)
V0: Titration in blank test (ml)
V1: Titration (ml) in the test when using the sample (first layer)
N: Concentration of titrant (0.1 mol / L)
f: Factor of titrant (f = 1.002)

The sample for acid value measurement (first layer) may be prepared using a composition for forming the first layer, and may be obtained by separating the first layer from a laminated glass or an interlayer film. You may. As a method of obtaining a sample (first layer) for acid value measurement from the laminated glass, after cooling with liquid nitrogen or the like to peel off the laminated glass member and the interlayer film, the first layer in the interlayer film A method of peeling the second layer (and the third layer) and the like can be mentioned. Examples of the method of obtaining the first layer for acid value measurement from the interlayer film include a method of peeling the first layer and the second layer (and the third layer).

Laminated glass X is produced by sandwiching the interlayer film according to the present invention between two clear glasses.

The laminated glass X is manufactured to measure the haze of the laminated glass X.

The thickness of the clear glass used for producing the laminated glass X is preferably 2 mm.

The laminated glass X is preferably produced as follows.

An interlayer film is sandwiched between two pieces of clear glass having a thickness of 2 mm to obtain a laminated body. The obtained laminate was placed in a rubber bag, degassed at a vacuum degree of 2.6 kPa for 20 minutes, then transferred into an oven with the degassed, held at 90 ° C. for 30 minutes, and vacuum pressed. Is pre-crimped. The pre-crimped laminate is crimped in an autoclave at 135 ° C. and a pressure of 1.2 MPa for 20 minutes to obtain a laminated glass X having a size of 25 mm in length and 300 mm in width.

The laminated glass X may be produced by peeling the interlayer film of the laminated glass from the laminated glass member.

From the viewpoint of increasing the transparency of the laminated glass, the haze of the laminated glass X is 0.5% or less.

From the viewpoint of further enhancing the transparency of the laminated glass, the haze of the laminated glass X is preferably 0.4% or less, more preferably 0.3% or less.

The haze of the laminated glass X is measured in accordance with JIS K6714.

The interlayer film according to the present invention is arranged between two clear float glasses having a thickness of 2 mm to obtain a laminated glass Y having a size of 300 mm in length and 300 mm in width. When the obtained laminated glass Y was subjected to the following impact resistance test at −20 ° C., the peeling area at the interface between the first layer and the second layer was preferably 50% or less, more preferably 50% or less. Is 40% or less, more preferably 30% or less. When the peeling area is not more than the above upper limit, delamination of the interlayer film can be suppressed even though the layers containing different resins are laminated. The impact resistance test at −20 ° C. is a temperature condition in which delamination is more likely to occur than, for example, an impact resistance test at 20 ° C. or an impact resistance test at 40 ° C.

Impact resistance test at -20 ° C: Laminated glass Y is stored at -20 ± 2 ° C for 4 hours or more. Regarding the laminated glass Y after storage, the mass is 227 ± 2 g and the diameter is 38 mm at the vertical center position and the horizontal center position of the laminated glass Y at −20 ± 2 ° C. in accordance with JIS R3211 or JIS R3212. Drop the steel ball from the height of 9.5m. The peeled area at the interface between the first layer and the second layer of the interlayer film is determined.

The peeled area can be calculated by, for example, the following formula.

Peeling area (%) = 100-[(Area where the first layer and the second layer are adhered after the impact resistance test at -20 ° C) / (Impact resistance test at -20 ° C) Area where the first layer and the second layer are adhered before the implementation of) × 100]

For the area where the first layer and the second layer are adhered, for example, the laminated glass Y is photographed from above with a digital camera or the like, and the bonded portion and the peeled portion are image-analyzed. It can be obtained by calculating the area.

The laminated glass Y is manufactured to carry out an impact resistance test at -20 ° C.

The laminated glass Y is preferably produced as follows.

An interlayer film is sandwiched between two 2 mm thick clear float glasses to obtain a laminate. The obtained laminate was placed in a rubber bag, degassed at a vacuum degree of 2.6 kPa for 20 minutes, then transferred into an oven with the degassed, held at 90 ° C. for 30 minutes, and vacuum pressed. Is pre-crimped. The pre-bonded laminate is crimped in an autoclave at 135 ° C. and a pressure of 1.2 MPa for 20 minutes to obtain a laminated glass Y having a size of 300 mm in length and 300 mm in width.

The laminated glass Y may be produced by peeling the interlayer film of the laminated glass from the laminated glass member.

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

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

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

Other layers are arranged on the surface of the second layer 2 opposite to the first layer 1 and on the surface of the third layer 3 opposite to the first layer 1. You may.

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

(resin)
The interlayer film contains a resin (hereinafter, may be referred to as resin (0)). The first layer contains a resin (hereinafter, may be referred to as a resin (1)). The second layer contains a resin (hereinafter, may be referred to as a resin (2)). The third layer preferably contains a resin (hereinafter, may be referred to as resin (3)). The resin (1) and the resin (2) contain different resins. The resin (1) and the resin (2) may be different resins. The resin (1) and the resin (3) may be the same resin, may contain different resins, or may be different resins. The resin (2) and the resin (3) may be the same resin, may contain different resins, or may be different resins. Since the sound insulation is further improved, it is preferable that the resin (1) and the resin (2) are different from each other, and the resin (1) and the resin (3) are different resins. It is preferable to have. As the resin (0), the resin (1), the resin (2), and the resin (3), only one type may be used, or two or more types may be used in combination.

Examples of the resin (0), the resin (1), the resin (2), and the resin (3) include a cured resin (cured product), a thermoplastic resin, and a modified resin obtained by modifying these resins. Can be mentioned.

Examples of the cured resin include resins obtained by curing a photocurable compound, a moisture-curable compound, and the like. The resin may be a cured product obtained by curing a photocurable compound or a moisture-curable compound. The cured product obtained by curing the photocurable compound or the moisture-curable compound may be a thermoplastic resin.

The photocurable compound or the moisture-curable compound is preferably a curable compound having a (meth) acryloyl group, and more preferably a (meth) acrylic polymer. The resin is preferably a curable compound having a (meth) acryloyl group, and more preferably a (meth) acrylic polymer.

Examples of the thermoplastic resin include polyvinyl acetate, polyester resin, polyvinyl acetal resin, vinyl acetate resin, polystyrene, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, ionomer resin, and polyvinyl alcohol. Examples thereof include resins, polyolefin resins such as aliphatic polyolefins, and (meth) acrylic resins (polymers having a (meth) acryloyl group). The polyoxymethylene (or polyacetal) resin is included in the polyvinyl acetal resin. As the resin, a thermoplastic resin other than these may be used. The thermoplastic resin may be a thermoplastic elastomer.

The thermoplastic resin is a resin that softens when heated and exhibits plasticity, and solidifies when cooled to room temperature (25 ° C.), for example. The thermoplastic elastomer means a resin that softens and exhibits plasticity when heated, and solidifies when cooled to room temperature (25 ° C.) and exhibits rubber elasticity, among other thermoplastic resins.

The thermoplastic resin exemplified above can be a thermoplastic elastomer by adjusting the molecular structure, degree of polymerization, etc. of the resin.

From the viewpoint of further enhancing the sound insulation property, the thermoplastic resin is preferably a polymer having a (meth) acryloyl group, and more preferably a (meth) acrylic polymer.

From the viewpoint of further enhancing the penetration resistance, the thermoplastic resin is preferably a polyvinyl acetal resin, an ionomer resin or an ethylene-vinyl acetate copolymer resin, and more preferably a polyvinyl acetal resin.

<(Meta) acrylic polymer>
The (meth) acrylic polymer is preferably a polymer of a polymerizable composition containing a compound having a (meth) acryloyl group. The above-mentioned polymerizable composition contains a polymerization component. In order to effectively prepare the (meth) acrylic polymer, the polymerizable composition may contain a photoreaction initiator. The polymerizable composition may contain an auxiliary agent for accelerating the reaction together with the photoreaction initiator. Representative examples of the compound having a (meth) acryloyl group include (meth) acrylic acid ester and N-substituted acrylamide having an amide group. The (meth) acrylic polymer is preferably a poly (meth) acrylic acid ester.

The polymerization component is a (meth) acrylic acid ester having a cyclic ether structure, a (meth) acrylic acid ester having an alicyclic structure, a (meth) acrylic acid ester having an aromatic ring, and a (meth) acrylic acid ester having a polar group. , The side chain preferably contains an acyclic (meth) acrylic acid ester having 6 or less carbon atoms, or an N-substituted acrylamide having an amide group. By using these preferable (meth) acrylic acid esters or N-substituted acrylamides having an amide group, the effects of the present invention can be effectively obtained, and both sound insulation and foam suppression performance can be enhanced in a well-balanced manner. Can be done.

Examples of the (meth) acrylic acid ester having a cyclic ether structure include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether. , 5-Hydroxypentyl (meth) acrylate glycidyl, 6-hydroxyhexyl (meth) acrylate glycidyl ether; (3-methyloxetane-3-yl) methyl (meth) acrylate, (3-propyloxetane-3-yl) methyl ( Meta) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, (3-butyloxetane-3-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) ethyl (meth) Acrylate, (3-ethyloxetane-3-yl) propyl (meth) acrylate, (3-ethyloxetane-3-yl) butyl (meth) acrylate, (3-ethyloxetane-3-yl) pentyl (meth) acrylate, (3-Ethyloxetane-3-yl) hexyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, (2,2-dimethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2- Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-isobutyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2- Cyclohexyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, tetrahydrofurfuryl alcohol acrylic acid multimer ester; tetrahydro-2H-pyran-2-yl- (meth) acrylate, 2- {1-[( Tetrahydro-2H-pyran-2-yl) oxy] -2-methylpropyl} (meth) acrylate, cyclic trimethylolpropanformal acrylate, (meth) acryloylmorpholine and the like can be mentioned. From the viewpoint of effectively obtaining the effects of the present invention, the (meth) acrylic acid ester having the cyclic ether structure is preferably tetrahydrofurfuryl (meth) acrylate or cyclic trimethylolpropane formal acrylate.

Examples of the (meth) acrylic acid ester having the alicyclic structure include isobolonyl (meth) acrylate and cyclohexyl (meth) acrylate.

Examples of the (meth) acrylic acid ester having the aromatic ring include benzyl acrylate and phenoxypolyethylene glycol acrylate.

Examples of the (meth) acrylic acid ester having the above polar group include (meth) acrylic acid ester having a hydroxyl group, an amide group, an amino group, an isocyanate group, a carboxyl group and the like as the polar group.

Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Be done.

Examples of the (meth) acrylic acid ester having an isocyanate group include triallyl isocyanurate and its derivatives.

Examples of the (meth) acrylic acid ester having a carboxyl group include acrylic acid, ω-carboxy-polycaprolactone monoacrylate, and 2-acryloyloxyethyl succinic acid.

The (meth) acrylic acid ester may be a polyvalent carboxylic acid ester having a (meth) acryloyl group. Examples of the polyvalent carboxylic acid ester having the (meth) acryloyl group include 2-acryloyloxyethyl succinate and the like.

Examples of the acyclic (meth) acrylic acid ester having 6 or less carbon atoms in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. ..

In order to effectively obtain the effects of the present invention, the content of the acyclic (meth) acrylic acid ester having 8 or more carbon atoms in the side chain in 100% by weight of the above-mentioned polymerization component shall be less than 20% by weight. Is preferable.

Examples of the N-substituted acrylamide having an amide group include N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acryloyl morpholine, N-isopropyl (meth) acrylamide, and N. -Hydroxyethyl (meth) acrylamide and the like can be mentioned.

Examples of the (meth) acrylic acid ester include diethylene glycol monoethyl ether (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxypropylphthalate, and 2-acryloyl, in addition to the above compounds. Oxyethyl-2-hydroxylpropylphthalate, cyclohexyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) crylate , 1,9-Nonandiol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis [ 4- (Acryloxyethoxy) phenyl] propandi (meth) acrylate; trimethylolpropanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) crylate, dipentaerythritol penta (meth) acrylate, di. Examples thereof include pentaerythritol hexa (meth) acrylate, tri (2-acryloyloxyethyl) phosphate, tetramethylol methanetri (meth) acrylate, tetramethylol propanetetra (meth) acrylate and derivatives thereof.

Only one type of each of the above (meth) acrylic acid ester and N-substituted acrylamide having an amide group may be used, or two or more types may be used in combination. The (meth) acrylic polymer may be a homopolymer of the above-mentioned (meth) acrylic acid ester, or may be a copolymer of a polymerization component containing the above-mentioned (meth) acrylic acid ester.

Specific examples of the photoreaction initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6 -Trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro) -3- (1H-Pyrol-1-yl) -phenyl) Titanium, 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-Morphorinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, di Ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1 -[4- (1-Methylvinyl) phenyl] propanone oligomer, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4- Benzoyl-4'-methyl-diphenylsulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl- N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanamineium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4- Dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride, 2,4,6-trimethylbenzoyl- Diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, triphenylmethylium tetrakis (Pentafluorophenyl) borate and the like can be mentioned. Only one kind of the photoreaction initiator may be used, or two or more kinds thereof may be used in combination.

The photoreaction initiator is preferably benzyldimethylketal, 1-hydroxycyclohexylphenylketone, or bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

The content of the photoreaction initiator in 100% by weight of the polymerizable composition is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 10% by weight or less, and more preferably 5. It is less than% by weight. When the content of the photoreaction initiator is at least the above lower limit and at least the above upper limit, the photoreactivity and storage stability are further enhanced.

When the above-mentioned polymerizable composition contains a photocurable compound, it is preferable to use a photocurable device such as an ultraviolet irradiation device in order to polymerize the photocurable compound. Examples of the ultraviolet irradiation device include a box type device and a belt conveyor type device. Examples of the ultraviolet lamp installed in the ultraviolet irradiation device include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a chemical lamp, a metal halide lamp, an excima lamp, and a UV-LED. The ultraviolet lamp is preferably a chemical lamp or a UV-LED.

When the photocurable compound is irradiated with ultraviolet rays, the ultraviolet irradiation amount (integrated irradiation amount) is preferably 500 mJ or more, more preferably 1000 mJ or more, still more preferably 1500 mJ or more, and particularly preferably 2000 mJ or more. The ultraviolet irradiation amount (integrated irradiation amount) is preferably 20000 mJ or less, more preferably 10000 mJ or less, and further preferably 8000 mJ or less. When the ultraviolet irradiation amount (integrated irradiation amount) is at least the above lower limit, unreacted monomers can be reduced. When the ultraviolet irradiation amount (integrated irradiation amount) is not more than the above upper limit, the storage stability of the resin becomes high. The irradiation intensity of the ultraviolet irradiation is preferably 0.1 mW or more, more preferably 0.5 mW or more, still more preferably 1 mW or more, and particularly preferably 2 mW or more.

<Polyvinyl acetate>
Since the effect of the present invention is excellent, the polyvinyl acetate is preferably a polymer of a polymerizable composition containing vinyl acetate and the monomer having a functional group.

Examples of the monomer having the above functional group include 3-methyl-3-butene-1-ol, ethylene glycol monovinyl ether, isopropylacrylamide and the like. Examples of the monomer having a carboxyl group as the functional group include acrylic acid and itaconic acid.

From the viewpoint of effectively enhancing the sound insulation, the weight average molecular weight of polyvinyl acetate is preferably 250,000 or more, more preferably 300,000 or more, still more preferably 400,000 or more, and particularly preferably 500,000 or more. From the viewpoint of improving the interlayer adhesive strength, the weight average molecular weight of polyvinyl acetate is preferably 1.2 million or less, more preferably 900,000 or less.

The above weight average molecular weight indicates the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The method for synthesizing the above-mentioned polyvinyl acetate by polymerizing the above-mentioned polymerizable composition is not particularly limited. Examples of this synthesis method include a solution polymerization method, a suspension polymerization method, and a UV polymerization method.

The method for synthesizing polyvinyl acetate is a solution polymerization method from the viewpoint of effectively enhancing the sound insulation and interlayer adhesion in the interlayer film having enhanced transparency and transparency. Is preferable.

<Polyester resin>
Examples of the polyester resin include polyethylene terephthalate and polyethylene naphthalate.

<Polyvinyl acetal resin>
The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with an aldehyde. The polyvinyl acetal resin is preferably an acetal product of polyvinyl alcohol. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is generally in the range of 70 mol% to 99.9 mol%.

The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, preferably 5000 or less, more preferably 4000 or less, still more preferably. It is 3500 or less, particularly preferably 3000 or less. When the average degree of polymerization is at least the above lower limit, the penetration resistance of the laminated glass is further increased. When the average degree of polymerization is not more than the above upper limit, molding of the interlayer film becomes easy.

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

The carbon number of the acetal group contained in the above polyvinyl acetal resin is not particularly limited. The aldehyde used in producing the polyvinyl acetal resin is not particularly limited. The acetal group in the polyvinyl acetal resin preferably has 3 to 5 carbon atoms, and more preferably 3 or 4 carbon atoms. When the acetal group in the polyvinyl acetal resin has 3 or more carbon atoms, the glass transition temperature of the interlayer film becomes sufficiently low.

The above aldehyde is not particularly limited. Generally, an aldehyde having 1 to 10 carbon atoms is preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutylaldehyde, n-barrelaldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, and n-octylaldehyde. Examples thereof include n-nonylaldehyde, n-decylaldehyde and benzaldehyde. Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde are preferred, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferred, and n-butyraldehyde is even more preferred. Only one kind of the above aldehyde may be used, or two or more kinds may be used in combination.

The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 18 mol% or more, preferably 40 mol% or less, and more preferably 35 mol% or less. When the content of the hydroxyl groups is at least the above lower limit, the adhesive strength of the interlayer film becomes even higher. Further, when the content of the hydroxyl group is not more than the above upper limit, the flexibility of the interlayer film is increased and the handling of the interlayer film becomes easy.

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

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

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

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

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

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

Hereinafter, the details of the suitable resins contained in the first layer, the second layer and the third layer will be described in more detail.

Resin contained in the first layer (resin (1)):
As the resin (1), the resin described above can be used.

The first layer preferably contains a resin having an acid value of 5 mgKOH / g or more and 500 mgKOH / g or less (hereinafter, may be referred to as resin (1A)). The resin (1) preferably contains the resin (1A). The resin (1) may be the resin (1A). In this case, the acid value of the first layer can be easily controlled within the above-mentioned range, and as a result, delamination of the interlayer film can be effectively suppressed. The resin (1) may contain a resin other than the resin (1A).

From the viewpoint of more effectively suppressing delamination of the interlayer film, the acid value of the resin (1A) is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

The acid value of the resin (1) is measured according to the potentiometric titration method described in JIS K0070. Specifically, it can be measured as follows.

Dissolve the sample (resin (1)) in a solvent (for example, methyl ethyl ketone: toluene: methanol = 1: 1: 1 (volume ratio)). The obtained solution was subjected to a potentiometric titrator (for example, "AT-710" manufactured by Kyoto Electronics Co., Ltd., electrode: "H-171, R-173" manufactured by Kyoto Electronics Co., Ltd.) and 0.1 mol / L potassium hydroxide ethanol. Titration is performed using a solution, and the obtained inflection point is used as the end point of the titration, and the acid value is calculated from the following formula.

Acid value (mgKOH / g) = (V1-V0) x N x 56.11 x f / S
S: Mass (g) of the sample (resin (1))
V0: Titration in blank test (ml)
V1: Titration (ml) in a test using a sample (resin (1))
N: Concentration of titrant (0.1 mol / L)
f: Factor of titrant (f = 1.002)

As the sample for acid value measurement (resin (1)), the resin (1) itself may be used, or the resin (1) may be separated from the first layer. Examples of the method for separating the resin (1) from the first layer include the following methods. The first layer is dissolved in a good solvent (eg, methyl ethyl ketone, tetrahydrofuran, etc.). After reprecipitation of the obtained solution with a poor solvent (for example, ethanol, methanol, etc.), the obtained high-volume component is further subjected to liquid chromatography or the like to obtain a high-molecular-weight component (resin) and a low-molecular-weight component of the first layer. (Plasticizer, etc.) is separated to obtain a high molecular weight component which is a sample (resin (1)).

The content of the resin (1A) in 100% by weight of the first layer is preferably 30% by weight or more, more preferably 50% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less. More preferably, it is 75% by weight or less. When the content of the resin (1A) is at least the above lower limit and at least the above upper limit, the acid value of the first layer can be easily controlled within the above range, and as a result, delamination of the interlayer film is further improved. It can be suppressed more effectively.

The content of the resin (1A) in 100% by weight of the resin contained in the first layer (in 100% by weight of the resin (1)) is preferably 50% by weight or more, more preferably 70% by weight or more. .. When the content of the resin (1A) is at least the above lower limit, the acid value of the first layer can be easily controlled within the above range, and as a result, delamination of the interlayer film is more effectively performed. It can be suppressed.

The first layer preferably contains a resin having a carboxyl group. The resin (1) and the resin (1A) preferably contain a resin having a carboxyl group. In this case, the acid value of the first layer can be easily controlled within the above-mentioned range, and as a result, delamination of the interlayer film can be effectively suppressed. The resin (1) and the resin (1A) may be resins having a carboxyl group. Further, the resin having a carboxyl group may be different from the resin (1A).

The content of the carboxyl group in 100% by weight of the resin having a carboxyl group is preferably 4% by weight or more, more preferably 5% by weight or more, preferably 15% by weight or less, and more preferably 13% by weight or less. When the content of the carboxyl group is not less than the above lower limit and not more than the above upper limit, the acid value of the first layer can be easily controlled within the above range, and as a result, delamination of the interlayer film is further effective. Can be suppressed.

The content of the above carboxyl group can be measured by 1 H-NMR or the like.

From the viewpoint of more effectively suppressing delamination of the interlayer film and further enhancing the transparency and sound insulation of the laminated glass, the resin having a carboxyl group is a (meth) acrylic polymer having a carboxyl group, or It is preferably polyvinyl acetate having a carboxyl group, and more preferably a (meth) acrylic polymer having a carboxyl group. The (meth) acrylic polymer having a carboxyl group can be obtained, for example, by curing a polymerizable composition containing the (meth) acrylic acid ester having a carboxyl group. The polyvinyl acetate having a carboxyl group can be obtained, for example, by using a polymerizable composition containing vinyl acetate and the monomer having a carboxyl group.

The content of the resin having a carboxyl group in 100% by weight of the first layer is preferably 4% by weight or more, more preferably 5% by weight or more, preferably 15% by weight or less, and more preferably 13% by weight or less. Is. When the content of the resin having a carboxyl group is not less than the above lower limit and not more than the above upper limit, the acid value of the first layer can be easily controlled within the above range, and as a result, delamination of the interlayer film is caused. It can be suppressed even more effectively.

The content of the resin having a carboxyl group in 100% by weight of the resin contained in the first layer (in 100% by weight of the resin (1)) is preferably 4% by weight or more, more preferably 5% by weight or more. It is preferably 15% by weight or less, more preferably 13% by weight or less. When the content of the resin having a carboxyl group is not less than the above lower limit and not more than the above upper limit, the acid value of the first layer can be easily controlled within the above range, and as a result, delamination of the interlayer film is caused. It can be suppressed even more effectively.

When the first layer contains two or more kinds of resins, it is preferable that the first layer does not have a phase-separated structure such as a co-continuous structure and a sea-island structure.

The content of the resin (1) in 100% by weight of the first layer is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, still more preferably 60% by weight. As mentioned above, it is particularly preferably 65% by weight or more.

Resin contained in the second and third layers (resin (2), resin (3)):
As the resin (2) and the resin (3), the above-mentioned resin can be used.

From the viewpoint of effectively suppressing delamination of the interlayer film and improving the transparency and sound insulation of the laminated glass, it is preferable that the resin (2) and the resin (3) each contain the thermoplastic resin. , The above thermoplastic resin is more preferable.

From the viewpoint of more effectively suppressing delamination of the interlayer film and further enhancing the transparency and sound insulation of the laminated glass, the resin (2) is preferably the polyvinyl acetal resin, and the resin. (3) is preferably the above-mentioned polyvinyl acetal resin.

From the viewpoint of further increasing the production efficiency of the interlayer film, it is preferable that the resin (2) and the resin (3) are the same resin.

The content of the thermoplastic resin in 100% by weight of the resin contained in the second layer (in 100% by weight of the resin (2)) is preferably 10% by weight or more, more preferably 30% by weight or more, and even more. It is preferably 50% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The main component (50% by weight or more) of the resin (2) is preferably the thermoplastic resin.

The content of the polyvinyl acetal resin in 100% by weight of the thermoplastic resin contained in the second layer is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and further. It is preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The main component (50% by weight or more) of the thermoplastic resin in the second layer is preferably a polyvinyl acetal resin.

The content of the thermoplastic resin in 100% by weight of the resin contained in the third layer (in 100% by weight of the resin (3)) is preferably 10% by weight or more, more preferably 30% by weight or more, and even more. It is preferably 50% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The main component (50% by weight or more) of the resin (3) is preferably the thermoplastic resin.

The content of the polyvinyl acetal resin in 100% by weight of the thermoplastic resin contained in the third layer is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and further. It is preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The main component (50% by weight or more) of the thermoplastic resin in the third layer is preferably a polyvinyl acetal resin.

(Plasticizer)
The interlayer film preferably contains a plasticizer. The first layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (1)). The second layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (2)). The third layer preferably contains a plasticizer (hereinafter, may be referred to as a plasticizer (3)). The use of plasticizers tends to further increase the adhesive strength between the layers. Further, when the polyvinyl acetal resin and the plasticizer are used in combination, the impact resistance and the penetration resistance are further improved, and the adhesive force of the layer containing the polyvinyl acetal resin and the plasticizer to the laminated glass member or another layer is appropriately increased. The plasticizer is not particularly limited. The plasticizer (1), the plasticizer (2), and the plasticizer (3) may be the same or different. As the plasticizer (1), the plasticizer (2), and the plasticizer (3), only one type may be used, or two or more types may be used in combination.

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

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

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

Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, and triethylene glycol dicaprelate. Triethylene Glycol Di-n-Octanoate, Triethylene Glycol Di-n-Heptanoate, Tetraethylene Glycol Di-n-Heptanoate, Dibutyl Sevacate, Dioctyl Azelate, Dibutyl Carbitol Adipate, Ethylene Glycol Di-2-Ethyl Butyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, adipine Examples thereof include a mixture of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl nonyl adipate, dibutyl sebacate, oil-modified sebacic acid alkyd, and a mixture of phosphoric acid ester and adipate ester. Organic ester plasticizers other than these may be used. Adipates other than the above-mentioned adipates may be used.

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

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

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

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

In the first layer, the content of the plasticizer (1) with respect to 100 parts by weight of the resin (1) is defined as the content (1). The content (1) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, further preferably 30 parts by weight or more, particularly preferably 35 parts by weight or more, preferably 100 parts by weight or less, and more preferably 80 parts by weight or more. It is less than or equal to parts by weight, more preferably 70 parts by weight or less, and particularly preferably 65 parts by weight or less. When the content (1) is at least the above lower limit, delamination of the interlayer film can be suppressed more effectively, and the sound insulation of the laminated glass can be further improved. When the content (1) is not more than the above upper limit, the penetration resistance of the laminated glass is further increased.

In the second layer, the content of the plasticizer (2) with respect to 100 parts by weight of the resin (2) is defined as the content (2). The content (2) is preferably 20 parts by weight or more, more preferably 25 parts by weight or more, further preferably 30 parts by weight or more, preferably 45 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 37. It is less than a part by weight. When the content (2) is at least the above lower limit, delamination of the interlayer film can be suppressed more effectively, and the sound insulation of the laminated glass can be further improved. When the content (2) is not more than the above upper limit, the penetration resistance of the laminated glass is further increased. When the content (2) is not more than the upper limit, the bending rigidity becomes even higher.

In the third layer, the content of the plasticizer (3) with respect to 100 parts by weight of the resin (3) is defined as the content (3). The content (3) is preferably 20 parts by weight or more, more preferably 25 parts by weight or more, still more preferably 30 parts by weight or more, preferably 45 parts by weight or less, more preferably 40 parts by weight or less, still more preferably 37. It is less than a part by weight. When the content (3) is at least the above lower limit, delamination of the interlayer film can be suppressed more effectively, and the sound insulation of the laminated glass can be further improved. When the content (3) is not more than the above upper limit, the penetration resistance of the laminated glass is further increased. When the content (3) is not more than the upper limit, the bending rigidity becomes even higher.

The above-mentioned content (1) and the above-mentioned content (2) may be the same or different. The content (1) and the content (3) may be the same or different. From the viewpoint of enhancing the sound insulation of the laminated glass, the content (1) and the content (2) are the same, or the content (1) is larger than the content (2). Is preferable, and the content (1) is more preferably higher than the content (2). From the viewpoint of enhancing the sound insulation of the laminated glass, the content (1) and the content (3) are the same, or the content (1) is larger than the content (3). Is preferable, and the content (1) is more preferably higher than the content (3).

From the viewpoint of further improving the sound insulation of the laminated glass, the absolute value of the difference between the content (2) and the content (1), and the difference between the content (3) and the content (1). The absolute value of each is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and further preferably 15 parts by weight or more. The absolute value of the difference between the content (2) and the content (1) and the absolute value of the difference between the content (3) and the content (1) are preferably 80 parts by weight or less, respectively. It is more preferably 75 parts by weight or less, still more preferably 70 parts by weight or less.

(Heat-shielding substance)
The interlayer film may contain a heat-shielding substance. The first layer may contain a heat-shielding substance. The second layer may contain a heat-shielding substance. The third layer may contain a heat-shielding substance. Only one kind of the heat-shielding substance may be used, or two or more kinds thereof may be used in combination.

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

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

Examples of the component X include phthalocyanine, phthalocyanine derivatives, naphthalocyanine, naphthalocyanine derivatives, anthracyanine and anthracyanine derivatives, and the like. The phthalocyanine compound and the phthalocyanine derivative each preferably have a phthalocyanine skeleton. It is preferable that the naphthalocyanine compound and the derivative of the naphthalocyanine each have a naphthalocyanine skeleton. It is preferable that the anthracyanine compound and the derivative of the anthracynin each have an anthracyanine skeleton.

The above component X may contain a vanadium atom or a copper atom. The component X may contain a vanadium atom or may contain a copper atom. The component X may be at least one of a vanadium atom or a copper atom-containing phthalocyanine and a vanadium atom or a copper atom-containing phthalocyanine derivative.

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

Metal oxide particles can be used as the heat shield particles. As the heat shield particles, particles formed of metal oxides (metal oxide particles) can be used.

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

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

(Metal salt)
The interlayer film may contain at least one metal salt (hereinafter, may be referred to as metal salt M) among the alkali metal salt and the alkaline earth metal salt. The alkaline earth metal means six kinds of metals, Be, Mg, Ca, Sr, Ba, and Ra. The first layer may contain the metal salt M. The second layer may contain the metal salt M. The third layer may contain the metal salt M. By using the metal salt M, it becomes easy to control the adhesiveness between the interlayer film and the laminated glass member such as a glass plate or the adhesiveness between each layer in the interlayer film. As the metal salt M, only one kind may be used, or two or more kinds may be used in combination.

The metal salt M may contain at least one metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.

Further, as the metal salt M, an alkali metal salt of an organic acid having 2 to 16 carbon atoms and an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms can be used. The metal salt M may contain a magnesium carboxylic acid salt having 2 to 16 carbon atoms or a potassium carboxylic acid salt having 2 to 16 carbon atoms.

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

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

The above UV shielding agent includes a UV absorbing agent. The ultraviolet shielding agent is preferably an ultraviolet absorber.

When the polymerizable composition containing the compound having a (meth) acryloyl group contains a photocurable compound, the amount of the ultraviolet absorber is smaller than that of the photoinitiator (inhibits polymerization) when the photocurable compound is polymerized. The photocurable compound may be polymerized with a photoinitiator and then an ultraviolet absorber may be contained in a separate step.

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

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

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

Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has, for example, a bandgap energy of 5.0 eV or more.

Examples of the ultraviolet shielding agent having a benzotriazole structure include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole ("TinuvinP" manufactured by BASF), 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole (BASF "Tinuvin320"), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (BASF) "Tinuvin 326" manufactured by BASF) and 2- (2'-hydroxy-3', 5'-di-amylphenyl) benzotriazole ("Tinuvin 328" manufactured by BASF) and the like.

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

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

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

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

Examples of the ultraviolet shielding agent having the oxalic acid anilide structure include N- (2-ethylphenyl) -N'-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide and N- (2-ethylphenyl)-. A oxalic acid having an aryl group substituted on a nitrogen atom such as N'-(2-ethoxy-phenyl) oxalic acid diamide and 2-ethyl-2'-ethoxy-oxalanilide ("Sanduvor VSU" manufactured by Clariant). Examples include diamides.

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

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

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

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

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

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

(Other ingredients)
The interlayer film, the first layer, the second layer, and the third layer are each other than a coupling agent, a dispersant, a surfactant, a flame retardant, an antistatic agent, and a metal salt, if necessary. It may contain additives such as an adhesive strength modifier, a moisture resistant agent, a fluorescent whitening agent, and an infrared absorber. Only one of these additives may be used, or two or more of these additives may be used in combination.

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

Let T be the thickness of the interlayer film. The thickness of the first layer is preferably 0.005 T or more, more preferably 0.01 T or more, still more preferably 0.02 T or more, preferably 0.17 T or less, more preferably 0.15 T or less, and more preferably. It is 0.13T or less, more preferably 0.1T or less, still more preferably 0.08T or less. When the thickness is at least the above lower limit and at least the above upper limit, the sound insulation property is further improved over a wide temperature range.

The thickness of each of the second layer and the third layer is 0.01 T or more, more preferably 0.02 T or more, preferably 0.17 T or less, more preferably 0.15 T or less, and more preferably 0.13 T. Below, it is more preferably 0.1 T or less, still more preferably 0.08 T or less. When the thickness is at least the above lower limit and at least the above upper limit, the sound insulation property is further improved over a wide temperature range.

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

The interlayer film may be rolled into a roll of the interlayer film. The roll body may include a winding core and an interlayer film wound around the outer circumference of the winding core.

The distance between one end and the other end of the interlayer film is preferably 3 m or less, more preferably 2 m or less, particularly preferably 1.5 m or less, preferably 0.5 m or more, more preferably 0.8 m or more, particularly. It is preferably 1 m or more.

The method for producing the interlayer film according to the present invention is not particularly limited. Examples of the method for producing an interlayer film according to the present invention include a method of forming each layer using each resin composition for forming each layer and then laminating the obtained layers, and a method for forming each layer. Examples thereof include a method of laminating each layer by coextruding each resin composition using an extruder. Since it is suitable for continuous production, a manufacturing method of extrusion molding is preferable.

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

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

(Laminated glass)
The laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and the above-mentioned interlayer film for laminated glass. In the laminated glass according to the present invention, the above-mentioned interlayer film for laminated glass is arranged between the first laminated glass member and the second laminated glass member.

The laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and an interlayer film for laminated glass having a structure of two or more layers. In the laminated glass according to the present invention, the interlayer film for laminated glass is arranged between the first laminated glass member and the second laminated glass member. In the laminated glass according to the present invention, the interlayer film includes a first layer containing a resin and a second layer laminated on the first surface of the first layer and containing a resin. In the laminated glass according to the present invention, in the interlayer film, the first layer and the second layer contain different resins, and the glass transition temperature of the first layer is the glass of the second layer. It is preferably lower than the transition temperature and the acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH / g or less. In the laminated glass according to the present invention, the haze is preferably 0.5% or less.

Since the laminated glass according to the present invention has the above-mentioned structure, it is possible to suppress delamination of the interlayer film even though different layers contain different resins, and to improve the transparency of the laminated glass. Can be done.

From the viewpoint of further enhancing the transparency of the laminated glass, the haze of the laminated glass is preferably 0.4% or less, more preferably 0.3% or less.

The haze of the laminated glass is measured in accordance with JIS K6714.

When the following impact resistance test was performed on the laminated glass at −20 ° C., the peeled area at the interface between the first layer and the second layer was preferably 50% or less, more preferably 40%. Below, it is more preferably 30% or less. The impact resistance test at −20 ° C. is a temperature condition in which delamination is more likely to occur than, for example, an impact resistance test at 20 ° C. or an impact resistance test at 40 ° C.

Impact resistance test at -20 ° C: Store the laminated glass at -20 ± 2 ° C for 4 hours or more. Regarding the laminated glass after storage, steel with a mass of 227 ± 2 g and a diameter of 38 mm at the vertical center position and the horizontal center position of the laminated glass at -20 ± 2 ° C in accordance with JIS R3211 or JIS R3212. Drop the ball from a height of 9.5m. The peeled area at the interface between the first layer and the second layer of the interlayer film is determined.

The laminated glass used in the impact resistance test at −20 ° C. is preferably a laminated glass having a size of 300 mm in length and 300 mm in width.

The peeled area can be obtained by, for example, the above formula.

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

The laminated glass 31 shown in FIG. 2 includes a first laminated glass member 21, a second laminated glass member 22, and an interlayer film 11. The interlayer film 11 is arranged between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched therein.

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

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

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

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

The manufacturing method of the above laminated glass is not particularly limited. For example, an interlayer film is sandwiched between the first laminated glass member and the second laminated glass member and passed through a pressing roll, or placed in a rubber bag and sucked under reduced pressure. The air remaining between the laminated glass member, the second laminated glass member, and the interlayer film is degassed. Then, pre-adhesion is performed at about 70 ° C. to 110 ° C. to obtain a laminate. Next, the laminate is placed in an autoclave or pressed, and pressure-bonded at a pressure of about 120 ° C. to 150 ° C. and 1 MPa to 1.5 MPa. In this way, laminated glass can be obtained. At the time of manufacturing the laminated glass, each layer in the interlayer film may be laminated.

The interlayer film and the laminated glass can be used for automobiles, railroad vehicles, aircraft, ships, buildings, etc. The interlayer film and the laminated glass can be used for purposes other than these. The interlayer film and the laminated glass are preferably an interlayer film and a laminated glass for vehicles or buildings, and more preferably an interlayer film and a laminated glass for vehicles. The interlayer film and the laminated glass can be used for windshields, side glasses, rear glasses, roof glasses and the like of automobiles. The interlayer film and the laminated glass are preferably used for automobiles. The interlayer film is suitably used for obtaining laminated glass for automobiles.

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

In the polyvinyl acetal resin used, n-butyraldehyde having 4 carbon atoms is used for acetalization. Regarding the polyvinyl acetal resin, the degree of acetalization (degree of butyralization), the degree of acetylation and the content of hydroxyl groups were measured by a method based on JIS K6728 “Polyvinyl butyral test method”. In addition, when measured by ASTM D1396-92, the same numerical value as the method based on JIS K6728 "Polyvinyl butyral test method" was shown.

The following materials were prepared.

(resin)
Polyvinyl acetal resin (polyvinyl butyral resin (PVB), average degree of polymerization 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree (butyralization degree) 68.5 mol%)

(Meta) Acrylic Polymers (1)-(4), (X1):
The polymerizable composition having the compounding composition shown in Table 1 below is sandwiched between two single-sided release-treated PET sheets (manufactured by Nippers, thickness 50 μm) so that the thickness is 1 mm. Was formed. Spacers were arranged around the two PET sheets. By irradiating the polymerizable composition layer with ultraviolet rays at an irradiation amount of 3000 mJ / cm ² at 3 mW using a chemical lamp, the polymerizable composition was cured by a reaction, and the (meth) acrylic polymers (1) to ( 4) and (X1) were obtained.

Polyvinyl acetate (1):
A glass polymerization container equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. 100 parts by weight of vinyl acetate monomer was placed in this polymerization vessel, and the inside of the polymerization vessel was replaced with nitrogen by heating and stirring at 60 ° C. Next, the compounding composition shown in Table 2 below was added dropwise over 4 hours, and after completion of the addition, the mixture was polymerized for 1 hour to obtain a solution containing polyvinyl acetate (1). The solution was dried in an oven at 110 ° C. for 3 hours to give polyvinyl acetate (1). In polyvinyl acetate (1), the proportion of structural units derived from carboxylic acid was 4% by weight.

Polyvinyl acetate (X1), (X2):
A glass polymerization container equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. In this polymerization vessel, 270 parts by weight of ion-exchanged water and 0.1 part by weight of polyvinyl alcohol (ketenization degree 88%, polymerization degree 300) were placed, and the mixture was heated and stirred to dissolve the polyvinyl alcohol. Next, the temperature in the polymerization vessel was set to 58 ° C., the compounding composition shown in Table 2 below was added, and the mixture was polymerized for 6 hours to obtain particles of polyvinyl acetate (X1) and (X2).

Regarding the obtained (meth) acrylic polymer and polyvinyl acetate, the content of carboxyl groups in 100% by weight of the (meth) acrylic polymer and the content of carboxyl groups in 100% by weight of polyvinyl acetate were set to H-. Obtained by NMR.

(Plasticizer)
Triethylene glycol di-2-ethylhexanoate (3GO)
Dibutyl phthalate (DBA)
(Metal salt M)
Mg mixture (50:50 (weight ratio) mixture of 2-ethylbutyrate magnesium and magnesium acetate)
(UV shield)
Tinuvin326 (2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, BASF's "Tinuvin 326")
(Antioxidant)
BHT (2,6-di-t-butyl-p-cresol)

(Example 1)
Preparation of composition for forming the first layer:
The following ingredients were mixed and thoroughly kneaded with a mixing roll to obtain a composition for forming the first layer.

(Meta) Acrylic Polymer (1) 100 parts by weight Triethylene glycol di-2-ethylhexanoate (3GO) 55 parts by weight

Preparation of compositions for forming the second and third layers:
The following ingredients were mixed and thoroughly kneaded with a mixing roll to obtain a composition for forming the second layer and the third layer.

100 parts by weight of polyvinyl acetal resin (PVB) 31 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) Metal salt M (Mg mixture) in an amount of 70 ppm in the obtained second and third layers.
An amount of UV shielding agent (Tinuvin 326) of 0.2% by weight in the obtained second and third layers.
0.2% by weight of the resulting second and third layers of antioxidant (BHT)

Preparation of interlayer 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 co-extruder to obtain a second layer (thickness). An interlayer film (thickness 800 μm) having a laminated structure of 350 μm) / first layer (thickness 100 μm) / third layer (thickness 350 μm) was produced.

Laminated glass production:
An interlayer film was sandwiched between two clear float glasses having a width of 25 mm, a length of 300 mm and a thickness of 2 mm according to JIS R3202 to obtain a laminate. The obtained laminate was placed in a rubber bag, degassed at a vacuum degree of 2.6 kPa for 20 minutes, then transferred into an oven with the degassed, held at 90 ° C. for 30 minutes, and vacuum pressed. Was pre-crimped. The pre-bonded laminate was pressure-bonded in an autoclave at 135 ° C. and a pressure of 1.2 MPa for 20 minutes to obtain a laminated glass (1). Further, a laminated glass (2) was obtained in the same manner as the laminated glass (1) except that clear float glass having a length of 300 mm, a width of 300 mm and a thickness of 2 mm was used.

The obtained laminated glass (1) corresponds to the above-mentioned laminated glass X, and the obtained laminated glass (2) corresponds to the above-mentioned laminated glass Y.

(Examples 2 to 5 and Comparative Examples 1 to 3)
An interlayer film, a laminated glass (1), and a laminated glass (2) were obtained in the same manner as in Example 1 except that the type of resin, the type and content of the plasticizer were changed as shown in Tables 3 and 4. It was.

(Evaluation)
(1) Acid Value of First Layer The first layer of the obtained interlayer film and the second layer and the third layer were peeled off to obtain a sample (first layer). The sample (first layer) was dissolved in a solvent (methyl ethyl ketone: toluene: methanol = 1: 1: 1 (volume ratio)). According to the potentiometric titration method described in JIS K0070, the obtained solution is subjected to a potentiometric titration device (“AT-710” manufactured by Kyoto Electronics Industry Co., Ltd., electrode: “H-171, R-173” manufactured by Kyoto Electronics Industry Co., Ltd.” ) And 0.1 mol / L potassium hydroxide ethanol solution were used for titration, and the obtained inflection point was used as the end point of the titration. The acid value of the first layer was calculated using the above formula.

(2) Acidity of Resin Contained in First Layer Obtained (meth) acrylic polymers (1) to (4), (X1), polyvinyl acetate (1), (X1), (X2) Each was dissolved in a solvent (methyl ethyl ketone: toluene: methanol = 1: 1: 1 (volume ratio)). According to the potentiometric titration method described in JIS K0070, the obtained solution is subjected to a potentiometric titration device (“AT-710” manufactured by Kyoto Electronics Industry Co., Ltd., electrode: “H-171, R-173” manufactured by Kyoto Electronics Industry Co., Ltd.” ) And 0.1 mol / L potassium hydroxide ethanol solution were used for titration, and the obtained inflection point was used as the end point of the titration. The acid value of each resin was calculated using the above formula.

(3) Glass transition temperature (Tg) of the first layer, the second layer and the third layer
The first layer and the second layer were prepared in the same manner as in the method for producing the interlayer film. A test piece (1) having a thickness of 0.5 mm is prepared by arbitrarily cutting and superimposing the first layer, and the thickness is obtained by arbitrarily cutting and superimposing the second layer. A test piece (2) having a size of 0.5 mm was prepared. The test piece (1) and the test piece (2) were stored for 12 hours in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5%. Next, the viscoelasticity was measured using a viscoelasticity measuring device (“ARES-G2” manufactured by TA Instruments). A parallel plate having a diameter of 8 mm was used as a jig, and the measurement was carried out under the conditions of shearing mode, the temperature was lowered from 100 ° C. to −20 ° C. at a temperature lowering rate of 3 ° C./min, and the frequency was 1 Hz and the strain was 1%. Since the second layer and the third layer have the same composition, the glass transition temperature of the second layer and the glass transition temperature of the third layer are the same.

(4) tan δ at the peak temperature of tan δ in the first layer
The first layer was prepared in the same manner as in the method for producing the interlayer film. A test piece (1) having a thickness of 0.5 mm was prepared by arbitrarily cutting the first layer and superimposing the first layer. Immediately after storing the test piece (1) in an environment of room temperature 23 ± 2 ° C. and humidity 25 ± 5% for 12 hours, a dynamic viscoelasticity measuring device (“DVA-200” manufactured by IT Measurement Control Co., Ltd.) was used. The viscoelasticity was measured. In the shear mode, the measurement was carried out under the condition of raising the temperature from −50 ° C. to 200 ° C. at a heating rate of 3 ° C./min, and the condition of frequency 1 Hz and strain 1%.

(5) Impact resistance test at -20 ° C The laminated glass (2) was stored at -20 ± 2 ° C for 4 hours or more. Regarding the laminated glass (2) after storage, the mass is 227 ± at the vertical center position and the horizontal center position of the laminated glass (2) at −20 ± 2 ° C. in accordance with JIS R3211 or JIS R3212. A 2 g steel ball having a diameter of 38 mm was dropped from a height of 9.5 m. The peeled area at the interface between the first layer and the second layer of the interlayer film was determined using the above formula.

[Criteria for impact resistance test at -20 ° C]
○○: Peeling area is 0% or more and 10% or less ○: Peeling area is more than 10% and 50% or less ×: Peeling area is more than 50%

(6) Laminated glass haze (transparency)
The haze of the obtained laminated glass (1) was measured according to JIS K6714.

(7) Primary loss factor (sound insulation at 20 ° C)
The obtained laminated glass (1) was vibrated by a vibration generator for a damping test (“Shinken G21-005D” manufactured by Shinken Co., Ltd.). The vibration characteristics obtained from this were amplified by a mechanical impedance measuring device (“XG-81” manufactured by Rion Co., Ltd.), and the vibration spectrum was analyzed by an FFT spectrum analyzer (“FFT analyzer SA-01A2” manufactured by Rion Co., Ltd.).

From the above primary loss coefficient, the sound insulation was judged according to the following criteria.

[Criteria for sound insulation]
○ ○: Primary loss coefficient is 0.45 or more ○: Primary loss coefficient is 0.4 or more and less than 0.45 ×: Primary loss coefficient is less than 0.4

Details and results are shown in Tables 1 to 4 below. In the table, the description of the metal salt M, the ultraviolet shielding agent and the antioxidant is omitted.

The details of the components shown in Table 1 are as follows.

IBOA: Isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
CTFA (# 200): Cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat # 200)
Aac: Acrylic acid (manufactured by Nippon Shokubai)
BA: n-Butyl acrylate (manufactured by Nippon Shokubai)
4HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
M5300: ω-carboxy-polycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd.)
CHA: Cyclohexyl acrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat # 155)
HPA: Hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
IRGACURE 184: 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF)

1 ... 1st layer 1a ... 1st surface 1b ... 2nd surface 2 ... 2nd layer 2a ... outer surface 3 ... 3rd layer 3a ... outer surface 11 ... interlayer film 11a ... 1st surface 11b ... Second surface 21 ... First laminated glass member 22 ... Second laminated glass member 31 ... Laminated glass

Claims

An interlayer film for laminated glass having a structure of two or more layers.
The first layer containing the resin and
It is laminated on the first surface of the first layer and includes a second layer containing a resin.
The first layer and the second layer contain different resins and contain different resins.
The glass transition temperature of the first layer is lower than the glass transition temperature of the second layer.
The acid value of the first layer is 3 mgKOH / g or more and 500 mgKOH / g or less.
An interlayer film for laminated glass in which the haze of the laminated glass X is 0.5% or less when the interlayer film is sandwiched between two clear glasses to obtain a laminated glass X.
The interlayer film for laminated glass according to claim 1, wherein the first layer contains a resin having an acid value of 5 mgKOH / g or more and 500 mgKOH / g or less.
The interlayer film for laminated glass according to claim 1 or 2, wherein the first layer contains a resin having a carboxyl group.
The interlayer film for laminated glass according to claim 3, wherein the content of the carboxyl group is 4% by weight or more and 15% by weight or less in 100% by weight of the resin having a carboxyl group.
The interlayer film for laminated glass according to claim 3 or 4, wherein the resin having a carboxyl group is a (meth) acrylic polymer having a carboxyl group.
The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the first layer contains a plasticizer.
Has a structure of 3 or more layers
The interlayer film for laminated glass according to any one of claims 1 to 6, further comprising a third layer laminated on a second surface of the first layer opposite to the first surface.
With the first laminated glass member,
With the second laminated glass member,
The laminated glass interlayer film according to any one of claims 1 to 7 is provided.
A laminated glass in which the laminated glass interlayer film is arranged between the first laminated glass member and the second laminated glass member.
With the first laminated glass member,
With the second laminated glass member,
With an interlayer film for laminated glass having a structure of two or more layers,
The laminated glass interlayer film is arranged between the first laminated glass member and the second laminated glass member.
The interlayer film comprises a first layer containing a resin and a second layer laminated on the first surface of the first layer and containing a resin.
In the interlayer film, the first layer and the second layer contain different resins, and the glass transition temperature of the first layer is lower than the glass transition temperature of the second layer. The acid value of layer 1 is 3 mgKOH / g or more and 500 mgKOH / g or less.
Laminated glass with a haze of 0.5% or less.
The laminated glass according to claim 9, wherein the first layer contains a resin having an acid value of 5 mgKOH / g or more and 500 mgKOH / g or less.
The laminated glass according to claim 9 or 10, wherein the first layer contains a resin having a carboxyl group.
The laminated glass according to claim 11, wherein the content of the carboxyl group is 4% by weight or more and 15% by weight or less in 100% by weight of the resin having a carboxyl group.
The laminated glass according to claim 11 or 12, wherein the resin having a carboxyl group is a (meth) acrylic polymer having a carboxyl group.
The laminated glass according to any one of claims 9 to 13, wherein the first layer contains a plasticizer.
The interlayer film has a structure of three or more layers and has a structure of three or more layers.
The laminated glass according to any one of claims 9 to 14, wherein the interlayer film comprises a third layer laminated on a second surface of the first layer opposite to the first surface. Glass.