JP2017186229A - Glass laminate for vehicle - Google Patents

Glass laminate for vehicle Download PDF

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Publication number
JP2017186229A
JP2017186229A JP2017048922A JP2017048922A JP2017186229A JP 2017186229 A JP2017186229 A JP 2017186229A JP 2017048922 A JP2017048922 A JP 2017048922A JP 2017048922 A JP2017048922 A JP 2017048922A JP 2017186229 A JP2017186229 A JP 2017186229A
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Prior art keywords
glass
laminated glass
barrier layer
pair
block copolymer
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JP2017048922A
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Japanese (ja)
Inventor
宮坂　誠一
Seiichi Miyasaka
誠一 宮坂
時彦 青木
Tokihiko Aoki
時彦 青木
裕平 儀間
Yuhei Yoshima
裕平 儀間
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AGC Inc
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Asahi Glass Co Ltd
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Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to EP17000508.6A priority Critical patent/EP3225393A1/en
Priority to CN201710191259.2A priority patent/CN107263964A/en
Priority to US15/471,403 priority patent/US10532636B2/en
Publication of JP2017186229A publication Critical patent/JP2017186229A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10293—Edge features, e.g. inserts or holes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
    • B32B17/10467—Variable transmission
    • B32B17/10495—Variable transmission optoelectronic, i.e. optical valve
    • B32B17/10532—Suspended particle layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings

Abstract

PROBLEM TO BE SOLVED: To provide a glass laminate for vehicles, which is excellent in the property of switching transmittance for a long term, by suppressing deterioration over time of a suspended particle device film, in particular, deterioration due to intrusion of moisture at an end portion, in the glass laminate including the suspended particle device film.SOLUTION: A glass laminate for vehicles includes: a pair of glass plates placed opposite to each other; a pair of intermediate adhesive layers in contact with opposing surfaces of the pair of glass plates respectively; a suspended particle device film arranged in a predetermined region in a region between the pair of intermediate adhesive layers corresponding to a region of peripheral edge portions of a main surface of the glass plate except at least a part of band-shaped regions; and a barrier layer arranged in the band-shaped regions between the pair of intermediate adhesive layers and having both of predetermined adhesiveness and predetermined moisture permeability.SELECTED DRAWING: Figure 2

Description

本発明は、合わせガラスに関し、懸濁粒子デバイスフィルムを備える車両用合わせガラスに関する。   The present invention relates to a laminated glass, and relates to a laminated glass for vehicles provided with a suspended particle device film.

車両向けの窓ガラスとして、電源スイッチのオン／オフで電気的に透過率を切り替えられるガラス（スマートガラス）が知られている。このようなスマートガラスに用いられる機能性材料として懸濁粒子デバイス（Suspended Particle Device（ＳＰＤ）、以下「ＳＰＤ」ということがある。）フィルムがある。   As window glass for vehicles, glass (smart glass) whose transmittance can be electrically switched by turning on / off a power switch is known. As a functional material used for such smart glass, there is a suspended particle device (SPD) (hereinafter sometimes referred to as “SPD”) film.

スマートガラスは、例えば、ＳＰＤフィルムを、ガラス板を中間接着層で貼り合わせた合わせガラス中に封入することで作製される。その際、ＳＰＤの端部を保護する目的で、ＳＰＤフィルムはガラス板や中間接着層のサイズより小さく切断され、その端部が中間接着層で覆われるようにして合わせガラスに封入される。具体的には、ＳＰＤフィルムの周辺部に額縁状の中間接着層を配置し、これを２枚の中間接着層で挟持したものをさらに１対のガラス板で挟み込む構成が一般的である。   Smart glass is produced, for example, by enclosing an SPD film in a laminated glass in which a glass plate is bonded with an intermediate adhesive layer. At that time, for the purpose of protecting the end portion of the SPD, the SPD film is cut smaller than the size of the glass plate or the intermediate adhesive layer, and the end portion is covered with the intermediate adhesive layer and sealed in the laminated glass. Specifically, a configuration in which a frame-shaped intermediate adhesive layer is disposed in the periphery of the SPD film and sandwiched between two intermediate adhesive layers is further sandwiched between a pair of glass plates.

しかしながら、ＳＰＤフィルムは上記のようにして合わせガラス中に封入したとしても、合わせガラスの端面から侵入した熱や水分が中間接着層を介してその端部に到達し、あるいは中間接着層に含まれる可塑剤の影響により、端部が劣化し、結果として端部では電源スイッチのオン／オフに対応した透過率の切り替えができなくなるという問題があった。   However, even if the SPD film is encapsulated in the laminated glass as described above, heat or moisture that has entered from the end face of the laminated glass reaches the end via the intermediate adhesive layer, or is included in the intermediate adhesive layer. Due to the influence of the plasticizer, the end portion deteriorates, and as a result, there is a problem that the end portion cannot change the transmittance corresponding to the on / off of the power switch.

このような合わせガラスに封入されたＳＰＤフィルムの端部の劣化を防ぐための手段として、いくつかの技術が示されている。例えば、特許文献１には、中間接着層からの可塑剤の侵入を防ぐために、エチレン−酢酸ビニル共重合体樹脂等の可塑剤フリーの材料からなる中間接着層を使用する技術が記載されている。また、特許文献２には、額縁状の中間接着層より侵入する水分を抑えるため、合わせガラス作製前に額縁状の中間接着層を含む中間接着層の構成材料を乾燥させ、含水量を低くする技術が記載されている。   Several techniques have been shown as means for preventing the deterioration of the end portion of the SPD film sealed in the laminated glass. For example, Patent Document 1 describes a technique that uses an intermediate adhesive layer made of a plasticizer-free material such as ethylene-vinyl acetate copolymer resin in order to prevent the plasticizer from entering from the intermediate adhesive layer. . Further, in Patent Document 2, in order to suppress moisture entering from the frame-shaped intermediate adhesive layer, the constituent material of the intermediate adhesive layer including the frame-shaped intermediate adhesive layer is dried before the laminated glass is produced, thereby reducing the water content. The technology is described.

特表２００９−５３４２８３号公報JP 2009-534283 A 特表２０１３−５０５１８８号公報Special table 2013-505188 gazette

しかしながら、これらの技術を用いても、額縁状の中間接着層の幅が狭くなる、例えば１０ｍｍ以下になると、合わせガラスの端面からの水分の侵入に対しては十分な耐性がなく、劣化が見られてしまう。よって、これらの技術を用いても、自動車のように一年中屋外環境で使用される場合には十分な耐久性を持つとは言い難いものであった。   However, even if these techniques are used, if the width of the frame-shaped intermediate adhesive layer becomes narrower, for example, 10 mm or less, it does not have sufficient resistance to moisture intrusion from the end face of the laminated glass, and deterioration is observed. It will be. Therefore, even if these technologies are used, it is difficult to say that they have sufficient durability when used in an outdoor environment all year round like an automobile.

そこで、発明者らが鋭意検討した結果、合わせガラスにおける中間接着層の接着性と透湿性が所定の数値の場合、ＳＰＤフィルムが水分によって劣化することを抑制出来ることを見出した。   Therefore, as a result of intensive studies by the inventors, it was found that the SPD film can be prevented from being deteriorated by moisture when the adhesiveness and moisture permeability of the intermediate adhesive layer in the laminated glass are predetermined numerical values.

本発明は、ＳＰＤフィルムを備える車両用合わせガラスにおいて、ＳＰＤフィルムの経時的な劣化、特に端部における水分の侵入による劣化を抑制することで、長期に亘って透過率の切り替え特性が良好な合わせガラスを提供することを目的とする。   The present invention relates to a laminated glass for vehicles provided with an SPD film, which suppresses deterioration over time of the SPD film, particularly deterioration due to moisture intrusion at the end portion, so that the switching property of the transmittance is good over a long period of time. The object is to provide glass.

本発明の車両用合わせガラスは、互いに対向する１対のガラス板と、前記１対のガラス板の対向面にそれぞれ接する１対の中間接着層と、前記１対の中間接着層の間の、前記ガラス板の主面における周縁部の少なくとも一部の帯状領域を除く領域に対応する領域内の所定領域に配置される懸濁粒子デバイスフィルムと、前記１対の中間接着層の間に前記帯状領域に配置され、以下に示す所定の接着性（Ａ）と以下に示す所定の透湿性（Ｂ）とを共に有するバリア層と、を備える。
接着性（Ａ）：ＪＩＳ Ｋ ６８６４−２：１９９９に準拠し、接着温度１１０℃、試験片の幅２５ｍｍ、試験速度が毎分３００ｍｍ、引き剥がし角度が１８０度の条件下で測定したガラス板に対する接着力が、４０Ｎ／２５ｍｍ以上。
透湿性（Ｂ）：ＪＩＳ Ｚ ０２０８：１９７６に準じて測定した温度４０℃、湿度９０％ＲＨにおける透湿度が５０ｇ／ｍ２・ｄａｙ以下。 The laminated glass for a vehicle according to the present invention includes a pair of glass plates facing each other, a pair of intermediate adhesive layers in contact with the opposing surfaces of the pair of glass plates, and the pair of intermediate adhesive layers. Between the suspended particle device film disposed in a predetermined region in a region corresponding to a region excluding at least a part of the belt-like region of the peripheral portion on the main surface of the glass plate, and the belt-like shape between the pair of intermediate adhesive layers And a barrier layer that is disposed in the region and has both predetermined adhesiveness (A) shown below and predetermined moisture permeability (B) shown below.
Adhesiveness (A): According to JIS K 6864-2: 1999, with respect to a glass plate measured under conditions of an adhesion temperature of 110 ° C., a test piece width of 25 mm, a test speed of 300 mm per minute, and a peel angle of 180 degrees Adhesive strength is 40N / 25mm or more.
Moisture permeability (B): Moisture permeability at a temperature of 40 ° C. and a humidity of 90% RH measured according to JIS Z 0208: 1976 is 50 g / m 2 · day or less.

本発明によれば、ＳＰＤフィルムを備える合わせガラスにおいて、ＳＰＤフィルムの経時的な劣化、特に端部における水分の侵入による劣化を抑制することで、長期に亘って透過率の切り替え特性が良好な車両用合わせガラスを提供できる。   According to the present invention, in a laminated glass provided with an SPD film, a vehicle with good transmittance switching characteristics over a long period of time by suppressing deterioration over time of the SPD film, in particular deterioration due to moisture intrusion at the edge. Laminated glass can be provided.

本発明の合わせガラスの実施形態の一例の正面図である。It is a front view of an example of an embodiment of a laminated glass of the present invention. 図１に示す合わせガラスのＸ−Ｘ線における断面図である。It is sectional drawing in the XX line of the laminated glass shown in FIG. 実施例における評価用サンプルの正面図である。It is a front view of the sample for evaluation in an Example. 実施例における評価用サンプルの端部の断面図である。It is sectional drawing of the edge part of the sample for evaluation in an Example. 実施例１の合わせガラスの正面図である。1 is a front view of a laminated glass of Example 1. FIG. 図５に示す合わせガラスのＹ−Ｙ線における断面図である。It is sectional drawing in the YY line of the laminated glass shown in FIG.

以下に、本発明の実施の形態を説明する。なお、本発明は、これらの実施形態に限定されるものではなく、これらの実施形態を、本発明の趣旨および範囲を逸脱することなく、変更または変形することができる。   Hereinafter, embodiments of the present invention will be described. Note that the present invention is not limited to these embodiments, and these embodiments can be changed or modified without departing from the spirit and scope of the present invention.

本発明の車両用合わせガラスは、互いに対向する１対のガラス板と、前記１対のガラス板の対向面にそれぞれ接する１対の中間接着層とを備え、前記１対の中間接着層の間に、ＳＰＤフィルムと、所定の接着性と透湿性とを共に有するバリア層と、が以下の所定の位置関係で配置された合わせガラスである。ここで、所定の接着性と透湿性は、それぞれ以下の接着性（Ａ）および透湿性（Ｂ）である。   The laminated glass for a vehicle according to the present invention includes a pair of glass plates facing each other and a pair of intermediate adhesive layers in contact with the opposing surfaces of the pair of glass plates, and the gap between the pair of intermediate adhesive layers. In addition, the SPD film and a barrier layer having both predetermined adhesiveness and moisture permeability are laminated glass arranged in the following predetermined positional relationship. Here, the predetermined adhesiveness and moisture permeability are the following adhesiveness (A) and moisture permeability (B), respectively.

接着性（Ａ）：ＪＩＳ Ｋ ６８５４−２：１９９９に準拠し、接着温度１１０℃、試験片幅２５ｍｍ、試験速度毎分３００ｍｍ、引き剥がし角度１８０度の条件下で測定したガラス板に対する接着力が、４０Ｎ／２５ｍｍ以上。
透湿性（Ｂ）：ＪＩＳ Ｚ ０２０８：１９７６に準拠して測定した温度４０℃、湿度９０％ＲＨにおける透湿度が５０ｇ／ｍ２・ｄａｙ以下。 Adhesiveness (A): Based on JIS K 6854-2: 1999, the adhesive strength to a glass plate measured under the conditions of an adhesion temperature of 110 ° C., a test piece width of 25 mm, a test speed of 300 mm per minute, and a peeling angle of 180 degrees. , 40N / 25mm or more.
Moisture permeability (B): The moisture permeability at a temperature of 40 ° C. and a humidity of 90% RH measured according to JIS Z 0208: 1976 is 50 g / m 2 · day or less.

本発明の合わせガラスにおいて、ＳＰＤフィルムは、前記１対の中間接着層の間に配置される。ＳＰＤフィルムが配置される領域は、前記ガラス板の主面における周縁部の少なくとも一部の帯状領域を除く領域に対応する領域内の所定領域である。バリア層は前記帯状領域に対応するように前記１対の中間接着層の間に配置される。   In the laminated glass of the present invention, the SPD film is disposed between the pair of intermediate adhesive layers. The region where the SPD film is disposed is a predetermined region in a region corresponding to a region excluding at least a part of a belt-like region at the peripheral portion on the main surface of the glass plate. A barrier layer is disposed between the pair of intermediate adhesive layers so as to correspond to the belt-like region.

本明細書において、ガラス板の主面の周縁部とは、該主面の外周から中央部に向かって、ある一定の幅を有する領域を意味する。また、本明細書において、ガラス板の主面において中央部から見て外周側を外側、外周からみて中央部側を内側という。   In this specification, the peripheral part of the main surface of a glass plate means the area | region which has a certain fixed width | variety toward the center part from the outer periphery of this main surface. Moreover, in this specification, the outer peripheral side seen from the center part in the main surface of a glass plate is called an outer side, and the central part side is called inner side seeing from the outer periphery.

バリア層が配置される帯状領域は、必要に応じて、前記ガラス板の主面に対応する領域の周縁部の少なくとも一部であってもよく、全部であってもよい。例えば、一定の方向からの水分の侵入が特に懸念されるような用途等においては、その方向に対応する周縁部のみに帯状のバリア層を設ければよい。その場合、ＳＰＤフィルムは、前記ガラス板の主面に対応する領域のバリア層が配置される帯状領域を除く領域のうちの所定の領域に配置される。   The belt-like region in which the barrier layer is disposed may be at least a part of the peripheral edge of the region corresponding to the main surface of the glass plate, or may be the whole as necessary. For example, in applications where there is a particular concern about the intrusion of moisture from a certain direction, a belt-like barrier layer may be provided only at the peripheral edge corresponding to that direction. In that case, the SPD film is disposed in a predetermined region of the region excluding the belt-shaped region in which the barrier layer of the region corresponding to the main surface of the glass plate is disposed.

ＳＰＤフィルムの配置領域は、前記ガラス板の主面に対応する領域のバリア層が配置される帯状領域を除く領域の全体であってもよく、一部であってもよい。ＳＰＤフィルムの配置領域が、前記ガラス板の主面に対応する領域のバリア層が配置される帯状領域を除く領域の一部である場合、残りの領域には、例えば、後述の中間接着層と同様の材料からなる層が設けられる。なお、ＳＰＤフィルムは、ＳＰＤフィルムの外側の端面がバリア層の内側の端面と接するように配置されることが好ましい。ＳＰＤフィルムの配置領域は、前記ガラス板の主面に対応する領域のバリア層が配置される帯状領域を除く領域の全体が好ましい。すなわち、ＳＰＤフィルムとバリア層により、前記ガラス板の主面の形状に相当する平面形状の層が前記１対の中間接着層の間に形成されるのが好ましい。   The entire region of the SPD film may be a part of the region excluding the belt-like region where the barrier layer in the region corresponding to the main surface of the glass plate is disposed, or a part thereof. When the SPD film placement region is a part of the region excluding the belt-like region in which the barrier layer in the region corresponding to the main surface of the glass plate is disposed, the remaining region includes, for example, an intermediate adhesive layer described later. Layers of similar material are provided. The SPD film is preferably arranged so that the outer end surface of the SPD film is in contact with the inner end surface of the barrier layer. The entire region of the SPD film is preferably the region excluding the belt-like region where the barrier layer corresponding to the main surface of the glass plate is disposed. That is, it is preferable that a planar layer corresponding to the shape of the main surface of the glass plate is formed between the pair of intermediate adhesive layers by the SPD film and the barrier layer.

なお、ＳＰＤフィルムをより確実に保護する観点からバリア層は前記ガラス板の主面に対応する領域の周縁部の全体に帯状に配置されることが好ましい。すなわち、バリア層の平面形状は、外周が前記ガラス板の主面の外周と略一致する額縁状であることが好ましい。この場合、ＳＰＤフィルムは、外周がバリア層の内周と略一致するように配置され、ＳＰＤフィルムの外側の端面（以下、「外周面」ともいう。）全体がバリア層の内側の端面（以下、「内周面」ともいう。）全体と接するように配置されることが好ましい。   In addition, it is preferable that a barrier layer is arrange | positioned at strip | belt shape in the whole peripheral part of the area | region corresponding to the main surface of the said glass plate from a viewpoint of protecting SPD film more reliably. That is, the planar shape of the barrier layer is preferably a frame shape in which the outer periphery substantially coincides with the outer periphery of the main surface of the glass plate. In this case, the SPD film is arranged so that the outer periphery substantially coincides with the inner periphery of the barrier layer, and the entire outer end surface (hereinafter also referred to as “outer peripheral surface”) of the SPD film is the end surface (hereinafter referred to as “outer peripheral surface”). , Also referred to as “inner peripheral surface”).

本発明の合わせガラスにおいては、ＳＰＤフィルムと、所定の性能、すなわち接着性（Ａ）および透湿性（Ｂ）を有するバリア層を上記のように配置したことで、ＳＰＤフィルムとバリア層の界面付近に気泡が残ることによる外観不良の発生を抑えるとともに、バリア層の透明性を維持しながら、外部からの水分等の侵入を十分に抑制することで、ＳＰＤフィルムの特に端部における劣化を抑制することができる。   In the laminated glass of the present invention, the SPD film and the barrier layer having a predetermined performance, that is, adhesiveness (A) and moisture permeability (B) are arranged as described above, so that the vicinity of the interface between the SPD film and the barrier layer is arranged. In addition, the deterioration of the appearance of the SPD film, particularly at the end portion, is suppressed by sufficiently suppressing the intrusion of moisture and the like from the outside while maintaining the transparency of the barrier layer while suppressing the occurrence of appearance defects due to bubbles remaining on the surface. be able to.

以下、本発明の合わせガラスの実施の形態について図面を参照しながら説明する。図１は本発明の合わせガラスの実施形態の一例における正面図であり、図２は、図１に示す合わせガラスのＸ−Ｘ線における断面図である。   Hereinafter, embodiments of the laminated glass of the present invention will be described with reference to the drawings. FIG. 1 is a front view of an example of an embodiment of a laminated glass of the present invention, and FIG. 2 is a cross-sectional view taken along line XX of the laminated glass shown in FIG.

図１および図２に示す合わせガラス１０は、互いに対向する１対のガラス板１Ａ、１Ｂと、１対のガラス板１Ａ、１Ｂの対向面にそれぞれ接する１対の中間接着層２Ａ、２Ｂと、を備える。合わせガラス１０において、１対のガラス板１Ａ、１Ｂおよび１対の中間接着層２Ａ、２Ｂは略同形、同寸の主面を有する。   A laminated glass 10 shown in FIG. 1 and FIG. 2 includes a pair of glass plates 1A and 1B facing each other, a pair of intermediate adhesive layers 2A and 2B in contact with opposing surfaces of the pair of glass plates 1A and 1B, Is provided. In the laminated glass 10, the pair of glass plates 1A and 1B and the pair of intermediate adhesive layers 2A and 2B have principal surfaces having substantially the same shape and the same dimensions.

合わせガラス１０は、さらに、１対の中間接着層２Ａ、２Ｂの間に、ガラス板１Ａ、１Ｂの主面より面積が小さい主面を有し、該主面の外周がガラス板１Ａ、１Ｂの主面の外周より内側に位置するＳＰＤフィルム３を有し、ＳＰＤフィルム３の外周面に、その内周面が接するように配置された、ガラス板１Ａ、１Ｂの主面の外周と略一致する外周を有する主面形状が額縁状のバリア層４を有する。   The laminated glass 10 further has a main surface having an area smaller than the main surfaces of the glass plates 1A and 1B between the pair of intermediate adhesive layers 2A and 2B, and the outer periphery of the main surface is the glass plate 1A or 1B. It has the SPD film 3 located inside the outer periphery of the main surface, and substantially coincides with the outer periphery of the main surface of the glass plates 1A and 1B arranged so that the inner peripheral surface is in contact with the outer peripheral surface of the SPD film 3. The main surface having an outer periphery has a frame-shaped barrier layer 4.

なお、図１および図２において図示されないが、合わせガラス１０は、ＳＰＤフィルム３が有する透明電極と外部電源を接続するための配線導体を有する。合わせガラス１０は、窓枠等に組み込まれて使用される際に、該配線導体を用いて外部電源に接続されることで、電源スイッチのオン／オフによりＳＰＤフィルム３が変化して電気的に透過率を切り替えられるガラス（スマートガラス）として機能する。   Although not shown in FIGS. 1 and 2, the laminated glass 10 has a wiring conductor for connecting the transparent electrode of the SPD film 3 and an external power source. When the laminated glass 10 is used by being incorporated in a window frame or the like, the SPD film 3 changes electrically by turning on / off the power switch by being connected to an external power source using the wiring conductor. It functions as glass (smart glass) whose transmittance can be switched.

ここで、本明細書において、「略同形、同寸」とは、人の見た目において同じ形状、同じ寸法を有することをいう。他の場合においても、「略」は上記と同様の意味を示す。
以下、合わせガラス１０を構成する各要素について説明する。 Here, in this specification, “substantially the same shape and the same size” means having the same shape and the same size in human appearance. In other cases, “substantially” has the same meaning as described above.
Hereinafter, each element which comprises the laminated glass 10 is demonstrated.

［ガラス板］
本発明の実施形態の合わせガラス１０に用いるガラス板１Ａ、１Ｂの材質としては、透明な無機ガラスや有機ガラス（樹脂）が挙げられる。無機ガラスとしては通常のソーダライムガラス（ソーダライムシリケートガラスともいう）、ホウ珪酸ガラス、無アルカリガラス、石英ガラス等が特に制限なく用いられる。これらのうちでもソーダライムガラスが特に好ましい。成形法についても特に限定されないが、例えば、フロート法等により成形されたフロート板ガラスが好ましい。 [Glass plate]
As a material of glass plate 1A, 1B used for the laminated glass 10 of embodiment of this invention, transparent inorganic glass and organic glass (resin) are mentioned. As the inorganic glass, ordinary soda lime glass (also referred to as soda lime silicate glass), borosilicate glass, alkali-free glass, quartz glass and the like are used without particular limitation. Of these, soda lime glass is particularly preferred. Although it does not specifically limit about a shaping | molding method, For example, the float plate glass shape | molded by the float glass method etc. is preferable.

有機ガラス（樹脂）としては、ポリカーボネート樹脂、ポリスチレン樹脂、芳香族ポリエステル樹脂、アクリル樹脂、ポリエステル樹脂、ポリアリレート樹脂、ハロゲン化ビスフェノールＡとエチレングリコールとの重縮合物、アクリルウレタン樹脂、ハロゲン化アリール基含有アクリル樹脂等が挙げられる。これらのなかでも芳香族系ポリカーボネート樹脂等のポリカーボネート樹脂やポリメチルメタクリレート系アクリル樹脂等のアクリル樹脂が好ましく、ポリカーボネート樹脂がより好ましい。さらに、ポリカーボネート樹脂のなかでも特にビスフェノールＡ系ポリカーボネート樹脂が好ましい。なお、ガラス板は、上記のような樹脂を２種以上含んで構成されてもよい。   As organic glass (resin), polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated aryl group A containing acrylic resin etc. are mentioned. Among these, polycarbonate resins such as aromatic polycarbonate resins and acrylic resins such as polymethyl methacrylate acrylic resins are preferable, and polycarbonate resins are more preferable. Furthermore, bisphenol A-based polycarbonate resin is particularly preferable among polycarbonate resins. In addition, a glass plate may be comprised including 2 or more types of above resins.

上記ガラスとしては、着色成分を添加しない無色透明な材質を用いてもよく、あるいは、本発明の効果を損なわない範囲で着色された着色透明な材質を用いてもよい。さらには、これらのガラスは１種類もしくは２種類以上を組合せて用いてもよく、例えば、２層以上に積層された積層基板であってもよい。合わせガラスの適用箇所にもよるがガラスとしては、無機ガラスが好ましい。   As the glass, a colorless and transparent material to which no coloring component is added may be used, or a colored and transparent material colored within a range not impairing the effects of the present invention may be used. Furthermore, these glasses may be used alone or in combination of two or more, for example, a laminated substrate laminated in two or more layers. Although it depends on the application location of the laminated glass, the glass is preferably inorganic glass.

合わせガラス１０に用いる１対のガラス板１Ａ、１Ｂは、互いに異なった種類の材質から構成されてもよいが、同一であることが好ましい。ガラス板１Ａ、１Ｂの形状は平板でもよく、全面または一部が曲率を有していてもよい。ガラス板１Ａ、１Ｂの厚みは合わせガラス１０の適用箇所により適宜選択できるが、一般的には０．２〜５ｍｍであることが好ましい。さらに、ガラス板１Ａ、１Ｂには、大気に晒される表出面に、撥水機能、親水機能、防曇機能等を付与するコーティングが施されていてもよい。また、ガラス板１Ａ、１Ｂの互いに対向する対向面には、低放射性コーティング、赤外線遮蔽コーティング、導電性コーティング等の機能コーティングが施されていてもよい。   The pair of glass plates 1A and 1B used for the laminated glass 10 may be made of different types of materials, but are preferably the same. The shape of the glass plates 1A and 1B may be a flat plate, or the entire surface or a part thereof may have a curvature. Although the thickness of glass plate 1A, 1B can be suitably selected by the application location of the laminated glass 10, generally it is preferable that it is 0.2-5 mm. Furthermore, the glass plates 1A and 1B may be provided with a coating that imparts a water repellent function, a hydrophilic function, an antifogging function, and the like to the exposed surface exposed to the atmosphere. Moreover, functional coatings, such as a low radiation coating, an infrared shielding coating, and a conductive coating, may be applied to the opposing surfaces of the glass plates 1A and 1B.

なお、ガラス板１Ａ、１Ｂの対向面が上記機能コーティングを有する場合には、以下の中間接着層２Ａ、２Ｂはガラス板１Ａ、１Ｂの対向面上の該機能コーティングに接する構成となる。   In addition, when the opposing surface of glass plate 1A, 1B has the said functional coating, the following intermediate | middle adhesive layers 2A, 2B become a structure which touches this functional coating on the opposing surface of glass plate 1A, 1B.

［中間接着層］
合わせガラス１０における１対の中間接着層２Ａ、２Ｂは、ガラス板１Ａ、１Ｂの主面と略同形、同寸の主面を有し、厚みが後述のとおりの平膜状の層である。中間接着層２Ａ、２Ｂは、ＳＰＤフィルム３およびバリア層４を挟持しつつ、それぞれガラス板１Ａ、１Ｂの対向面に接するように設けられる。このように中間接着層２Ａ、２Ｂは、該中間接着層２Ａ、２Ｂを介して１対のガラス板１Ａ、１Ｂの間にＳＰＤフィルム３およびバリア層４を挟み込むように接着して合わせガラス１０として一体化する機能を有する。 [Intermediate adhesive layer]
The pair of intermediate adhesive layers 2A, 2B in the laminated glass 10 is a flat film layer having a main surface substantially the same shape and the same size as the main surfaces of the glass plates 1A, 1B and having a thickness as described later. The intermediate adhesive layers 2A and 2B are provided so as to be in contact with the opposing surfaces of the glass plates 1A and 1B while sandwiching the SPD film 3 and the barrier layer 4, respectively. In this way, the intermediate adhesive layers 2A and 2B are bonded to each other so as to sandwich the SPD film 3 and the barrier layer 4 between the pair of glass plates 1A and 1B via the intermediate adhesive layers 2A and 2B. Has the function of integrating.

中間接着層２Ａ、２Ｂの構成材料としては、通常、合わせガラスに用いられる従来公知の中間接着層を構成する材料と同様の材料が特に制限なく使用できる。
中間接着層２Ａ、２Ｂとして、具体的には、以下の熱可塑性樹脂を主成分として含む組成物を、ガラス板１Ａ、１Ｂの主面と略同形、同寸の主面を有するシート状に製膜したものが挙げられる。 As the constituent material of the intermediate adhesive layers 2A and 2B, the same material as that of the conventionally known intermediate adhesive layer used for laminated glass can be used without particular limitation.
Specifically, as the intermediate adhesive layers 2A and 2B, a composition containing the following thermoplastic resin as a main component is manufactured into a sheet shape having a main surface substantially the same shape and the same size as the main surfaces of the glass plates 1A and 1B. Examples include membranes.

熱可塑性樹脂としては、これを主成分とする組成物をシート状に製膜し１対の中間接着層２Ａ、２Ｂとして、ＳＰＤフィルム３およびバリア層４を挟持して１対のガラス板１Ａ、１Ｂの間に挿入、加熱、加圧して合わせガラス１０を成形した際に、一体化できるものであれば特に限定されない。また、合わせガラスとした際にＳＰＤフィルムの電気的な透過率の切り替えが十分に視認できる可視光透過率を有するものが好ましく、ＳＰＤフィルムに電圧を印加した可視光透過性の状態での合わせガラスとして可視光透過率が３０％以上を達成できるものが特に好ましい。   As a thermoplastic resin, a composition comprising the main component as a main component is formed into a sheet, and a pair of intermediate adhesive layers 2A and 2B is sandwiched between the SPD film 3 and the barrier layer 4, and a pair of glass plates 1A, There is no particular limitation as long as it can be integrated when the laminated glass 10 is formed by inserting, heating, and pressing between 1B. Moreover, when it is set as a laminated glass, what has the visible light transmittance | permeability which can fully switch the electrical transmittance of a SPD film is preferable, and the laminated glass in the visible light transmissive state which applied the voltage to the SPD film Particularly preferred are those capable of achieving a visible light transmittance of 30% or more.

熱可塑性樹脂として、具体的には、ポリビニルブチラール樹脂（ＰＶＢ）等のポリビニルアセタール樹脂、ポリ塩化ビニル樹脂、飽和ポリエステル樹脂、ポリウレタン樹脂、エチレン−酢酸ビニル共重合体樹脂（ＥＶＡ）、エチレン−エチルアクリレート共重合体樹脂等の従来から中間接着層用として用いられている熱可塑性樹脂が挙げられる。これらの熱可塑性樹脂は、単独で用いられてもよいし、２種類以上が併用されてもよい。   Specifically, as the thermoplastic resin, polyvinyl acetal resin such as polyvinyl butyral resin (PVB), polyvinyl chloride resin, saturated polyester resin, polyurethane resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate The thermoplastic resin conventionally used for intermediate | middle adhesive layers, such as copolymer resin, is mentioned. These thermoplastic resins may be used alone or in combination of two or more.

合わせガラスの中間接着層用の熱可塑性樹脂は、用途に応じて、透明性、耐候性、強度、接着力、耐貫通性、衝撃エネルギー吸収性、耐湿性、遮熱性および遮音性等の諸性能のバランスを考慮して選択される。このような観点から、上記熱可塑性樹脂のなかでも、ＰＶＢ、ＥＶＡ等が好ましい。   The thermoplastic resin for the intermediate adhesive layer of laminated glass has various performances such as transparency, weather resistance, strength, adhesion, penetration resistance, impact energy absorption, moisture resistance, heat insulation and sound insulation depending on the application. Is selected in consideration of the balance. From such a viewpoint, PVB, EVA and the like are preferable among the thermoplastic resins.

中間接着層については、製造に際しておよび使用時においてＳＰＤフィルムの機能に影響を及ぼさない材料が好ましい。したがって、熱可塑性樹脂には可塑剤を含まない、もしくはＳＰＤフィルムに影響を及ぼさない可塑剤を含むものがよい。   The intermediate adhesive layer is preferably a material that does not affect the function of the SPD film during production and use. Therefore, it is preferable that the thermoplastic resin does not contain a plasticizer or contains a plasticizer that does not affect the SPD film.

中間接着層２Ａ、２Ｂのうち少なくとも一方に所定の接着力と所定の透湿性を有するものを使用することが好ましい。所定の接着力とは、例えば、上記接着性（Ａ）（ＪＩＳ Ｋ ６８５４−２：１９９９に準拠し、接着温度１１０℃、試験片幅２５ｍｍ、試験速度が毎分３００ｍｍ、引き剥がし角度が１８０度の条件下で測定したガラス板に対する接着力が、４０Ｎ／２５ｍｍ以上）である。接着力は、接着性（Ａ）と同様にして測定される接着力として６０Ｎ／２５ｍｍ以上であることがより好ましく、８０Ｎ／２５ｍｍ以上であることがさらに好ましい。   It is preferable to use at least one of the intermediate adhesive layers 2A and 2B having a predetermined adhesive force and a predetermined moisture permeability. The predetermined adhesive strength is, for example, in accordance with the above-mentioned adhesiveness (A) (JIS K 6854-2: 1999, an adhesion temperature of 110 ° C., a test piece width of 25 mm, a test speed of 300 mm per minute, and a peeling angle of 180 degrees. The adhesive strength with respect to the glass plate measured under the above conditions is 40 N / 25 mm or more). The adhesive force is more preferably 60 N / 25 mm or more, and further preferably 80 N / 25 mm or more, as an adhesive force measured in the same manner as the adhesiveness (A).

中間接着層２Ａもしくは２Ｂが所定の接着力以上であれば、ＳＰＤフィルムの水分による劣化を抑制できる。この理由としては、中間接着層の接着力が所定の値であると、例えばガラス板と中間接着層との界面から水分が侵入することを抑制できるためと考えられる。中間接着層２Ａ、２Ｂの両方が所定の接着力以上であることがより好ましい。   When the intermediate adhesive layer 2A or 2B has a predetermined adhesive strength or more, deterioration of the SPD film due to moisture can be suppressed. The reason for this is considered to be that moisture can be prevented from entering from the interface between the glass plate and the intermediate adhesive layer, for example, when the adhesive force of the intermediate adhesive layer is a predetermined value. It is more preferable that both of the intermediate adhesive layers 2A and 2B have a predetermined adhesive strength or more.

また、所定の透湿性とは、例えば、上記透湿性（Ｂ）（ＪＩＳ Ｚ０２０８：１９７６）に準じて測定される温度４０℃、湿度９０％ＲＨにおける透湿度が５０ｇ／ｍ２・ｄａｙ以下）である。透湿性は、透湿性（Ｂ）と同様にして測定される透湿性として３０ｇ／ｍ２・ｄａｙ以下であることがより好ましく、１５ｇ／ｍ２・ｄａｙ以下であることがさらに好ましく、１０ｇ／ｍ２・ｄａｙ以下であることがさらに好ましい。中間接着層２Ａもしくは２Ｂが上記所定の接着力と所定の低い透湿性とを共に有することで、ＳＰＤフィルムの水分による劣化を大幅に抑制できる。中間接着層２Ａ、２Ｂの両方が所定の接着力と所定の低い透湿性とを共に有することがより好ましい。 The predetermined moisture permeability is, for example, a moisture permeability of 50 g / m 2 · day or less at a temperature of 40 ° C. and a humidity of 90% RH measured according to the moisture permeability (B) (JIS Z0208: 1976). is there. The moisture permeability is more preferably 30 g / m 2 · day or less, more preferably 15 g / m 2 · day or less as the moisture permeability measured in the same manner as the moisture permeability (B), 10 g / m or less. More preferably, it is 2 · day or less. Since the intermediate adhesive layer 2A or 2B has both the predetermined adhesive force and the predetermined low moisture permeability, deterioration of the SPD film due to moisture can be significantly suppressed. It is more preferable that both of the intermediate adhesive layers 2A and 2B have both a predetermined adhesive force and a predetermined low moisture permeability.

なお、後述する接着性樹脂組成物（Ｉ）を、上記同様にシート状に製膜して中間接着層とすることもできる。接着性樹脂組成物（Ｉ）を用いて得られる中間接着層は、ガラス板との接着性が良く、また透湿性も低いことから特に好ましい。さらに、透明性、耐候性、強度、耐貫通性、衝撃エネルギー吸収性、遮熱性および遮音性等の諸性能のバランスにも優れている。   In addition, the adhesive resin composition (I) mentioned later can also be formed into a sheet shape like the above, and it can also be set as an intermediate | middle adhesive layer. The intermediate adhesive layer obtained by using the adhesive resin composition (I) is particularly preferable because it has good adhesion to a glass plate and low moisture permeability. Furthermore, it is excellent in balance of various properties such as transparency, weather resistance, strength, penetration resistance, impact energy absorption, heat insulation, and sound insulation.

さらに、合わせガラス成形時の加熱温度は中間接着層用の熱可塑性樹脂に合わせて設定されるが、該加熱温度がＳＰＤフィルムの耐熱温度以上であると、合わせガラスとした際にＳＰＤフィルムが十分に機能しないことがある。この点から、合わせガラス成形温度が用いるＳＰＤフィルムの耐熱温度以下となるように、中間接着層用の熱可塑性樹脂を選択することが好ましいが、この点においても接着性樹脂組成物（Ｉ）は比較的低温で可塑化することから好ましい。   Furthermore, the heating temperature at the time of forming the laminated glass is set in accordance with the thermoplastic resin for the intermediate adhesive layer. If the heating temperature is higher than the heat resistant temperature of the SPD film, the SPD film is sufficient when the laminated glass is used. May not work. From this point, it is preferable to select a thermoplastic resin for the intermediate adhesive layer so that the laminated glass molding temperature is equal to or lower than the heat resistant temperature of the SPD film used, but also in this respect, the adhesive resin composition (I) is It is preferable because it is plasticized at a relatively low temperature.

上記のとおり中間接着層２Ａ、２Ｂの作製には上記熱可塑性樹脂を主成分として含有する熱可塑性樹脂含有組成物、好ましくは、接着性樹脂組成物（Ｉ）が用いられる。熱可塑性樹脂含有組成物は、本発明の効果を阻害しない範囲で各種目的に応じて、例えば、赤外線吸収剤、紫外線吸収剤、蛍光剤、接着性調整剤、カップリング剤、界面活性剤、酸化防止剤、熱安定剤、光安定剤、脱水剤、消泡剤、帯電防止剤、難燃剤等の各種添加剤の１種類もしくは２種類以上を含有していてもよい。これらの添加剤は中間接着層２Ａ、２Ｂにおいて、全体に均一に含有される。   As described above, for producing the intermediate adhesive layers 2A and 2B, the thermoplastic resin-containing composition containing the thermoplastic resin as a main component, preferably, the adhesive resin composition (I) is used. The thermoplastic resin-containing composition can be used, for example, as an infrared absorber, an ultraviolet absorber, a fluorescent agent, an adhesion adjuster, a coupling agent, a surfactant, an oxidation agent, and the like within a range that does not impair the effects of the present invention. One kind or two or more kinds of various additives such as an inhibitor, a heat stabilizer, a light stabilizer, a dehydrating agent, an antifoaming agent, an antistatic agent and a flame retardant may be contained. These additives are uniformly contained throughout the intermediate adhesive layers 2A and 2B.

中間接着層２Ａ、２Ｂの膜厚は、特に限定されるものではない。具体的には、合わせガラス用等に通常用いられる中間接着層と同様に、１層あたりの膜厚として、０．０５〜０．８ｍｍであることが好ましく、２層の合計膜厚として０．１〜１．６ｍｍであることが好ましい。中間接着層の１層あたりの膜厚が０．０５ｍｍ未満であったり、２層の合計膜厚が０．１ｍｍ未満であったりすると、強度が不十分となることがあり、また、ガラスミスマッチが大きい場合、剥離が発生しやすくなる。逆に中間接着層の１層あたりの膜厚が０．８ｍｍを超えたり、２層の合計膜厚が１．６ｍｍを超えたりすると、後述する合わせガラス１０作製時の圧着工程や、耐久試験（屋外暴露試験や高温試験）において、これが挟み込まれる１対のガラス板１Ａ、１Ｂのずれが生じる現象、いわゆる板ずれ現象が発生することがある。   The film thickness of the intermediate adhesive layers 2A and 2B is not particularly limited. Specifically, it is preferable that the film thickness per layer is 0.05 to 0.8 mm as in the case of the intermediate adhesive layer usually used for laminated glass or the like. It is preferable that it is 1-1.6 mm. If the film thickness per layer of the intermediate adhesive layer is less than 0.05 mm, or the total film thickness of the two layers is less than 0.1 mm, the strength may be insufficient, and a glass mismatch may occur. When it is large, peeling tends to occur. Conversely, if the film thickness per layer of the intermediate adhesive layer exceeds 0.8 mm, or if the total film thickness of the two layers exceeds 1.6 mm, a pressure bonding step or a durability test (described later) during the production of laminated glass 10 will be described. In an outdoor exposure test or a high-temperature test), a phenomenon in which a pair of glass plates 1A and 1B sandwiched between them occurs, that is, a so-called plate displacement phenomenon may occur.

中間接着層２Ａ、２Ｂはそれぞれ単層構造に限定されない。例えば、特開２０００−２７２９３６号公報等に開示された遮音性能の向上を目的として用いられる、性質の異なる（損失正接の異なる）樹脂膜を積層した多層樹脂膜を中間接着層２Ａ、２Ｂとして使用してもよい。この場合においても、中間接着層２Ａ、２Ｂは同一である必要はなく、互いに独立して、単層構造または多層構造が選択できる。   Each of the intermediate adhesive layers 2A and 2B is not limited to a single layer structure. For example, a multilayer resin film in which resin films having different properties (different loss tangents) are used for the purpose of improving the sound insulation performance disclosed in Japanese Patent Application Laid-Open No. 2000-272936 is used as the intermediate adhesive layers 2A and 2B. May be. Also in this case, the intermediate adhesive layers 2A and 2B do not have to be the same, and a single layer structure or a multilayer structure can be selected independently of each other.

［ＳＰＤフィルム］
ＳＰＤフィルム３は、ガラス板１Ａ、１Ｂの主面に対して小面積かつ略相似形状の主面を有し、該主面の外周がガラス板１Ａ、１Ｂの主面の外周より内側に位置するように中間接着層２Ａ、２Ｂの間に配置されている。合わせガラス１０においては、ＳＰＤフィルム３と、ＳＰＤフィルム３の外周面にその内周面が接するように配置された主面形状が額縁状のバリア層４とを組み合せた部材において、主面がガラス板１Ａ、１Ｂの主面と略同形、同寸となる構成である。 [SPD film]
The SPD film 3 has a main surface having a small area and a substantially similar shape with respect to the main surfaces of the glass plates 1A and 1B, and the outer periphery of the main surface is located inside the outer periphery of the main surfaces of the glass plates 1A and 1B. Thus, it is arranged between the intermediate adhesive layers 2A and 2B. In the laminated glass 10, in the member in which the SPD film 3 and the barrier layer 4 whose main surface shape is arranged so that the inner peripheral surface is in contact with the outer peripheral surface of the SPD film 3 are combined, the main surface is glass. It is the structure which becomes substantially the same shape and the same dimension as the main surface of board 1A, 1B.

図１、図２に示す合わせガラス１０においてガラス板１Ａ、１Ｂの主面は矩形である。ＳＰＤフィルム３の主面形状は、ガラス板１Ａ、１Ｂの主面形状に対して４辺の周縁部の全部が帯状に、言い換えると額縁状に切り欠かれた形状であって、その切り欠かれた部分を補填するようにバリア層４が設けられている。必要に応じて、ＳＰＤフィルム３の主面形状は、ガラス板１Ａ、１Ｂの主面形状に対して周縁部の一部、例えば、４辺のうちのいずれか１辺の周縁部のみが帯状に切り欠かれた形状であってもよく、いずれかの２辺の周縁部が切り欠かれた形状であってもよく、いずれかの３辺の周縁部が切り欠かれた形状であってもよい。その場合も、バリア層４は、ＳＰＤフィルム３の切り欠かれた形状に応じて、その切り欠かれた部分を補填するように配設されればよい。   In the laminated glass 10 shown in FIGS. 1 and 2, the main surfaces of the glass plates 1A and 1B are rectangular. The main surface shape of the SPD film 3 is a shape in which all of the four peripheral edges are strip-shaped, in other words, a frame-like shape with respect to the main surface shape of the glass plates 1A and 1B. A barrier layer 4 is provided so as to compensate for the portion. If necessary, the main surface shape of the SPD film 3 is a part of the peripheral portion of the main surface shape of the glass plates 1A and 1B, for example, only the peripheral portion of any one of the four sides is strip-shaped. It may have a cut-out shape, may have a shape in which the peripheral portion of any two sides is cut out, or may have a shape in which the peripheral portion of any three sides cut out. . Also in that case, the barrier layer 4 may be disposed so as to compensate for the notched portion according to the notched shape of the SPD film 3.

ＳＰＤフィルム３の切り欠き部の幅、すなわちバリア層４の幅ｗは、用途に応じて適宜選択できる。本発明の合わせガラスにおいては、以下に説明するとおり中間接着層とバリア層が合わせガラスの端面からの水分の侵入を効率よく抑制できる構成であることから、ＳＰＤフィルム３の切り欠き部の幅、すなわちバリア層４の幅ｗにおいて１０ｍｍ以下であってもよい。   The width of the cutout portion of the SPD film 3, that is, the width w of the barrier layer 4 can be appropriately selected according to the application. In the laminated glass of the present invention, as described below, since the intermediate adhesive layer and the barrier layer can efficiently suppress the intrusion of moisture from the end face of the laminated glass, the width of the notched portion of the SPD film 3, That is, the width w of the barrier layer 4 may be 10 mm or less.

ＳＰＤフィルムとしては、電圧の印加により配向可能な懸濁粒子を含有するポリマー層を、透明導電膜を内側にコートした２枚の電気絶縁性フィルムで挟み込むようにして構成された、一般的なＳＰＤフィルムが使用可能である。このような、ＳＰＤフィルムは、電源スイッチをオンにして透明導電膜間に電圧を印加することにより、ポリマー層中の懸濁粒子が配向することで可視光透過率が高く、透明性が高い状態になる。電源スイッチがオフの状態では、ポリマー層中の懸濁粒子が配向することがなく可視光透過率が低く、透明性が低い状態となる。   As an SPD film, a general SPD constructed by sandwiching a polymer layer containing suspended particles that can be oriented by applying a voltage between two electrically insulating films coated with a transparent conductive film on the inside. Film can be used. Such an SPD film has a high visible light transmittance and high transparency due to orientation of suspended particles in the polymer layer by applying a voltage between the transparent conductive films with the power switch turned on. become. When the power switch is off, the suspended particles in the polymer layer are not oriented, and the visible light transmittance is low and the transparency is low.

なお、ＳＰＤフィルムの主面は上記のとおり樹脂等の電気絶縁性フィルムの主面からなり、透明導電膜や懸濁粒子を含有するポリマー層が表出していないが、ＳＰＤフィルムの端面においてはこれらが表出する構成である。よって、この端面をバリア層で保護することで、ＳＰＤフィルムの周縁部における電源スイッチのオン／オフに対応する可視光透過率の切り替えの不具合の発生を効果的に抑制できる。   The main surface of the SPD film is the main surface of an electrically insulating film such as a resin as described above, and the transparent conductive film and the polymer layer containing suspended particles are not exposed. It is the structure which expresses. Therefore, by protecting this end face with the barrier layer, it is possible to effectively suppress the occurrence of the problem of switching the visible light transmittance corresponding to the ON / OFF of the power switch at the peripheral edge of the SPD film.

ＳＰＤフィルムとしては、例えば、ＬＣＦ−１１０３ＤＨＡ（商品名、日立化成社製）、等の市販品を用いることができる。なお、このような市販品は、所定の大きさで供給されるため、使用に際しては合わせガラスの大きさに合わせて所望の大きさに切断して使用する。なお、合わせガラス１０に用いるＳＰＤフィルムの厚みとしては、特に制限されないが、取り扱い性および入手容易性の観点から０．２〜０．４ｍｍが好ましい。   As the SPD film, for example, a commercially available product such as LCF-1103DHA (trade name, manufactured by Hitachi Chemical Co., Ltd.) can be used. In addition, since such a commercial item is supplied with a predetermined | prescribed magnitude | size, when using it, it cut | disconnects and uses to a desired magnitude | size according to the magnitude | size of a laminated glass. The thickness of the SPD film used for the laminated glass 10 is not particularly limited, but is preferably 0.2 to 0.4 mm from the viewpoint of handleability and availability.

［バリア層］
合わせガラス１０において、バリア層４は、所定の接着性（Ａ）と所定の透湿性（Ｂ）とを有し、ＳＰＤフィルム３の端面の全体を保護する目的でＳＰＤフィルム３の外周面にその内周面が接するようにＳＰＤフィルム３を取り囲む形で中間接着層２Ａ、２Ｂの間に配置されている。ここで、所定の接着性（Ａ）と所定の透湿性（Ｂ）については、上記 のとおりである。なお、接着性および透湿性の好ましい範囲については、接着性は、接着性（Ａ）と同様にして測定される接着力として６０Ｎ／２５ｍｍ以上が好ましく、８０Ｎ／２５ｍｍ以上がより好ましい。透湿性は、透湿性（Ｂ）と同様にして測定される透湿性として３０ｇ／ｍ２・ｄａｙ以下が好ましく、１５ｇ／ｍ２・ｄａｙ以下がより好ましく、１０ｇ／ｍ２・ｄａｙ以下であることがさらに好ましい。 [Barrier layer]
In the laminated glass 10, the barrier layer 4 has a predetermined adhesiveness (A) and a predetermined moisture permeability (B), and is disposed on the outer peripheral surface of the SPD film 3 for the purpose of protecting the entire end surface of the SPD film 3. The SPD film 3 is disposed between the intermediate adhesive layers 2A and 2B so as to surround the inner peripheral surface. Here, the predetermined adhesiveness (A) and the predetermined moisture permeability (B) are as described above. In addition, about the preferable range of adhesiveness and moisture permeability, 60 N / 25mm or more is preferable as adhesive force measured similarly to adhesiveness (A), and 80 N / 25mm or more is more preferable. Moisture permeability, 30g / m 2 · day or less are preferred as the moisture permeability is measured in the same manner as moisture permeability (B), more preferably not more than 15g / m 2 · day, or less 10g / m 2 · day Is more preferable.

上記のとおり、バリア層４は、ガラス板１Ａ、１Ｂの主面形状に対してＳＰＤフィルム３の主面が有するに切り欠かれた部分の形状に応じて、その切り欠かれた部分を補填するように配設される。バリア層４の幅ｗは、用途に応じて適宜選択される。合わせガラス１０においては、バリア層４の幅ｗは１０ｍｍ以下であっても、合わせガラス１０の端面からの水分の侵入を十分に抑制してＳＰＤフィルム３の端面を水分から保護する性質（以下、「防湿性」という。）を維持することができる。これにより、本実施形態の合わせガラスを用いれば、ＳＰＤフィルムを備える合わせガラスにおいて、より意匠性が求められる用途への適用が可能となる。   As described above, the barrier layer 4 fills the notched portions according to the shape of the notched portions of the main surface of the SPD film 3 with respect to the main surface shapes of the glass plates 1A and 1B. It is arranged as follows. The width w of the barrier layer 4 is appropriately selected according to the application. In the laminated glass 10, even if the width w of the barrier layer 4 is 10 mm or less, the property of protecting the end surface of the SPD film 3 from moisture by sufficiently suppressing the intrusion of moisture from the end surface of the laminated glass 10 (hereinafter, "Moisture-proof") can be maintained. Thereby, if the laminated glass of this embodiment is used, in the laminated glass provided with a SPD film, the application to the use for which the designability is calculated | required will be attained.

本発明の合わせガラスにおいて、防湿性を維持できるバリア層の幅の下限は、バリア層の厚みや構成材料にもよるが、概ね３ｍｍとすることができる。なお、より高い防湿性が要求される場合には、バリア層の幅の下限は、５ｍｍ程度が好ましい。   In the laminated glass of the present invention, the lower limit of the width of the barrier layer capable of maintaining moisture resistance can be approximately 3 mm, although it depends on the thickness of the barrier layer and the constituent materials. When higher moisture resistance is required, the lower limit of the barrier layer width is preferably about 5 mm.

主面形状が矩形の合わせガラス１０が有する、外周がガラス板１Ａ、１Ｂの主面の外周と略一致する額縁状の主面形状を有するバリア層４において、該矩形の４辺に沿った額縁部分において、幅ｗは上記下限以上であれば、辺ごとに同一であっても、異なってもよく、辺に関係なく部分的に大小があってもよい。   The frame along the four sides of the rectangle in the barrier layer 4 having a frame-shaped main surface shape that the outer surface of the laminated glass 10 whose main surface shape is rectangular has substantially the same as the outer periphery of the main surfaces of the glass plates 1A and 1B. In the portion, as long as the width w is equal to or greater than the lower limit, it may be the same or different for each side, and may be partially large or small regardless of the side.

また、ＳＰＤフィルム３の端面を十分に保護する観点から、バリア層４の厚みはＳＰＤフィルム３の厚みと略同一であることが好ましい。具体的には、バリア層４の厚みは、ＳＰＤフィルム３の厚みの±０．１ｍｍ以内が好ましく、±０．０７５ｍｍ以内がより好ましい。   Further, from the viewpoint of sufficiently protecting the end surface of the SPD film 3, the thickness of the barrier layer 4 is preferably substantially the same as the thickness of the SPD film 3. Specifically, the thickness of the barrier layer 4 is preferably within ± 0.1 mm of the thickness of the SPD film 3, and more preferably within ± 0.075 mm.

バリア層４は、後述する接着性樹脂組成物（Ｉ）、特許第５６２５７８１号に記載されているような、エチレン−酢酸ビニル共重合体に、有機化層状粘土、シランカップリング剤などを含有させたことを特徴とするエチレン−酢酸ビニル共重合体樹脂組成物、等が好ましい。有機化層状粘土を含有させることにより、通常のエチレン−酢酸ビニル共重合体樹脂組成物に比べて著しく、透湿性を低下させることができる。   The barrier layer 4 contains an organically modified layered clay, a silane coupling agent, etc. in an ethylene-vinyl acetate copolymer as described in the adhesive resin composition (I) described later and Japanese Patent No. 5625781. An ethylene-vinyl acetate copolymer resin composition characterized by the above is preferable. By including the organically modified layered clay, moisture permeability can be significantly reduced as compared with a normal ethylene-vinyl acetate copolymer resin composition.

[接着性樹脂組成物（Ｉ）]
接着性樹脂組成物（Ｉ）は、変性ブロック共重合体水素化物［３］を含有する。変性ブロック共重合体水素化物［３］は、以下に説明する特定のブロック共重合体［１］の炭素−炭素不飽和結合を水素化したブロック共重合体水素化物［２］をアルコキシシリル化することにより得られる。 [Adhesive Resin Composition (I)]
The adhesive resin composition (I) contains a modified block copolymer hydride [3]. The modified block copolymer hydride [3] is an alkoxysilylation of the block copolymer hydride [2] obtained by hydrogenating the carbon-carbon unsaturated bond of the specific block copolymer [1] described below. Can be obtained.

（ブロック共重合体［１］）
ブロック共重合体［１］は、少なくとも２つの重合体ブロック［Ａ］と少なくとも１つの重合体ブロック［Ｂ］を含有する。 (Block copolymer [1])
The block copolymer [1] contains at least two polymer blocks [A] and at least one polymer block [B].

重合体ブロック［Ａ］は、芳香族ビニル化合物由来の構造単位を主成分とする。重合体ブロック［Ａ］中の芳香族ビニル化合物由来の構造単位の含有量は、通常９０質量％以上、好ましくは９５質量％以上、より好ましくは９９質量％以上である。重合体ブロック［Ａ］は、芳香族ビニル化合物由来の構造単位以外の成分として、鎖状共役ジエン由来の構造単位および／またはその他のビニル化合物由来の構造単位を含むことができ、その含有量は通常１０質量％以下、好ましくは５質量％以下、より好ましくは１質量％以下である。重合体ブロック［Ａ］中の芳香族ビニル化合物由来の構造単位が少なすぎると、バリア層の耐熱性が十分でない場合がある。複数の重合体ブロック［Ａ］は、上記の範囲を満足すれば互いに同じであっても、異なっていてもよい。   The polymer block [A] contains a structural unit derived from an aromatic vinyl compound as a main component. The content of the structural unit derived from the aromatic vinyl compound in the polymer block [A] is usually 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more. The polymer block [A] can contain a structural unit derived from a chain conjugated diene and / or a structural unit derived from another vinyl compound as a component other than a structural unit derived from an aromatic vinyl compound, and the content thereof is Usually, it is 10 mass% or less, Preferably it is 5 mass% or less, More preferably, it is 1 mass% or less. When there are too few structural units derived from the aromatic vinyl compound in the polymer block [A], the heat resistance of the barrier layer may not be sufficient. The plurality of polymer blocks [A] may be the same as or different from each other as long as the above range is satisfied.

重合体ブロック［Ｂ］は、鎖状共役ジエン化合物由来の構造単位を主成分とする。重合体ブロック［Ｂ］中の鎖状共役ジエン化合物由来の構造単位の含有量は、通常９０質量％以上、好ましくは９５質量％以上、より好ましくは９９質量％以上である。鎖状共役ジエン化合物由来の構造単位が上記範囲にあると、バリア層は柔軟性、低温での接着性に優れる。重合体ブロック［Ｂ］は、鎖状共役ジエン化合物由来の構造単位以外の成分として、芳香族ビニル化合物由来の構造単位および／またはその他のビニル化合物由来の構造単位を含むことができ、その含有量は、通常１０質量％以下、好ましくは５質量％以下、より好ましくは１質量％以下である。重合体ブロック［Ｂ］中の芳香族ビニル化合物由来の構造単位の含有量が増加すると、バリア層の低温での柔軟性が低下し、得られる合わせガラスの耐衝撃性が低下する恐れがある。重合体ブロック［Ｂ］が複数有る場合には、重合体ブロック［Ｂ］は、上記の範囲を満足すれば互いに同じであっても、異なっていてもよい。   The polymer block [B] contains a structural unit derived from a chain conjugated diene compound as a main component. The content of the structural unit derived from the chain conjugated diene compound in the polymer block [B] is usually 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more. When the structural unit derived from the chain conjugated diene compound is in the above range, the barrier layer is excellent in flexibility and adhesiveness at low temperature. The polymer block [B] can contain a structural unit derived from an aromatic vinyl compound and / or a structural unit derived from another vinyl compound as a component other than the structural unit derived from a chain conjugated diene compound, and the content thereof Is usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less. When the content of the structural unit derived from the aromatic vinyl compound in the polymer block [B] increases, the flexibility of the barrier layer at a low temperature decreases, and the impact resistance of the resulting laminated glass may decrease. When there are a plurality of polymer blocks [B], the polymer blocks [B] may be the same as or different from each other as long as the above range is satisfied.

芳香族ビニル化合物としては、具体的には、スチレン、α−メチルスチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、２，４−ジイソプロピルスチレン、２，４−ジメチルスチレン、４−ｔ−ブチルスチレン、５−ｔ−ブチル−２−メチルスチレン、４−モノクロロスチレン、ジクロロスチレン、４−モノフルオロスチレン、４−フェニルスチレンなどが挙げられ、吸湿性の面で極性基を含有しないものが好ましく、工業的な入手の容易さからスチレンが特に好ましい。   Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4- Examples include t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, and the like that do not contain polar groups in terms of hygroscopicity. Styrene is particularly preferred from the viewpoint of industrial availability.

鎖状共役ジエン系化合物としては、具体的には、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエンなどが挙げられ、吸湿性の面で極性基を含有しないものが好ましく、工業的な入手の容易さから１，３−ブタジエン、イソプレンが特に好ましい。   Specific examples of the chain conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc., and are polar in terms of hygroscopicity. Those containing no group are preferred, and 1,3-butadiene and isoprene are particularly preferred from the viewpoint of industrial availability.

その他のビニル系化合物としては、鎖状ビニル化合物や環状ビニル化合物が挙げられる。その他のビニル系化合物は、ニトリル基、アルコキシカルボニル基、ヒドロキシカルボニル基、またはハロゲン基を有するビニル化合物および／または不飽和の環状酸無水物または不飽和イミド化合物を含んでもよい。その他のビニル系化合物として、具体的には、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ドデセン、１−エイコセン、４−メチル−１−ペンテン、４，６−ジメチル−１−ヘプテンなどの鎖状オレフィン；ビニルシクロヘキサンなどの環状オレフィンなどの、極性基を含有しないものが吸湿性の面で好ましい。これらのなかでも、その他のビニル系化合物としては、鎖状オレフィンがより好ましく、エチレン、プロピレンが特に好ましい。   Examples of other vinyl compounds include chain vinyl compounds and cyclic vinyl compounds. Other vinyl compounds may include a vinyl compound having a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group and / or an unsaturated cyclic acid anhydride or an unsaturated imide compound. Specific examples of other vinyl compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1- A chain olefin such as eicosene, 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; and a cyclic olefin such as vinylcyclohexane, which does not contain a polar group, is preferred in terms of hygroscopicity. Among these, as other vinyl compounds, chain olefins are more preferable, and ethylene and propylene are particularly preferable.

ブロック共重合体［１］中の重合体ブロック［Ａ］の数は、通常５個以下、好ましくは４個以下、より好ましくは３個以下である。重合体ブロック［Ａ］および／または重合体ブロック［Ｂ］が複数存在する場合、重合体ブロック［Ａ］の中で重量平均分子量が最大と最少の重合体ブロックの重量平均分子量をそれぞれＭｗ（Ａ１）およびＭｗ（Ａ２）とし、重合体ブロック［Ｂ］の中で重量平均分子量が最大と最少の重合体ブロックの重量平均分子量をそれぞれＭｗ（Ｂ１）およびＭｗ（Ｂ２）としたとき、該Ｍｗ（Ａ１）とＭｗ（Ａ２）との比（Ｍｗ（Ａ１）／Ｍｗ（Ａ２））、および、該Ｍｗ（Ｂ１）とＭｗ（Ｂ２）との比（Ｍｗ（Ｂ１）／Ｍｗ（Ｂ２））は、それぞれ２．０以下、好ましくは１．５以下、より好ましくは１．２以下である。   The number of polymer blocks [A] in block copolymer [1] is usually 5 or less, preferably 4 or less, more preferably 3 or less. When there are a plurality of polymer blocks [A] and / or polymer blocks [B], the weight average molecular weights of the polymer blocks having the largest and smallest weight average molecular weights in the polymer block [A] are represented by Mw (A1 ) And Mw (A2), and Mw (B1) and Mw (B2) are the weight average molecular weights of the polymer block [B] having the largest and smallest weight average molecular weight, respectively. The ratio between A1) and Mw (A2) (Mw (A1) / Mw (A2)) and the ratio between Mw (B1) and Mw (B2) (Mw (B1) / Mw (B2)) Each is 2.0 or less, preferably 1.5 or less, more preferably 1.2 or less.

ブロック共重合体［１］のブロックの形態は、鎖状型ブロックでもラジアル型ブロックでもよく、鎖状型ブロックであるものが、機械的強度に優れ好ましい。ブロック共重合体［１］の最も好ましい形態は、重合体ブロック［Ｂ］の両端に重合体ブロック［Ａ］が結合したトリブロック共重合体、および、重合体ブロック［Ａ］の両端に重合体ブロック［Ｂ］が結合し、さらに、該両重合体ブロック［Ｂ］の他端にそれぞれ重合体ブロック［Ａ］が結合したペンタブロック共重合体である。   The block form of the block copolymer [1] may be a chain block or a radial block, and a chain block is preferred because of its excellent mechanical strength. The most preferred form of the block copolymer [1] is a triblock copolymer in which the polymer block [A] is bonded to both ends of the polymer block [B], and a polymer on both ends of the polymer block [A]. It is a pentablock copolymer in which the block [B] is bonded and the polymer block [A] is bonded to the other end of the both polymer blocks [B].

ブロック共重合体［１］中の、全重合体ブロック［Ａ］がブロック共重合体［１］に占める質量分率をｗＡとし、全重合体ブロック［Ｂ］がブロック共重合体［１］全体に占める質量分率をｗＢとしたときに、ｗＡとｗＢとの比（ｗＡ：ｗＢ）は、３０：７０〜６０：４０である。ｗＡ：ｗＢは、好ましくは３５：６５〜５５：４５、より好ましくは４０：６０〜５０：５０である。ｗＡが高過ぎる場合は、変性ブロック共重合体水素化物［３］の耐熱性は高くなるが、柔軟性が低くなりやすい。ｗＡが低過ぎる場合は、屈折率が汎用のフロートガラスの屈折率に比べて小さくなり過ぎる。それにより、バリア層とその他の層との界面において全反射が起き易くなり視認性が低下するため好ましくない。   In the block copolymer [1], the mass fraction of the entire polymer block [A] in the block copolymer [1] is wA, and the entire polymer block [B] is the entire block copolymer [1]. The ratio of wA to wB (wA: wB) is 30:70 to 60:40, where wB is the mass fraction occupied by. wA: wB is preferably 35:65 to 55:45, more preferably 40:60 to 50:50. When wA is too high, the heat resistance of the modified block copolymer hydride [3] increases, but the flexibility tends to decrease. When wA is too low, the refractive index is too small compared to the refractive index of general-purpose float glass. As a result, total reflection tends to occur at the interface between the barrier layer and other layers, and visibility is lowered, which is not preferable.

ブロック共重合体［１］の分子量は、テトラヒドロフランを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により測定されるポリスチレン換算の重量平均分子量（Ｍｗ）で、通常３０，０００〜２００，０００、好ましくは４０，０００〜１５０，０００、より好ましくは５０，０００〜１００，０００である。また、ブロック共重合体［１］の分子量分布（Ｍｗ／Ｍｎ）は、好ましくは３以下、より好ましくは２以下、特に好ましくは１．５以下である。   The molecular weight of the block copolymer [1] is a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is usually 30,000 to 200,000, Preferably it is 40,000-150,000, More preferably, it is 50,000-100,000. Further, the molecular weight distribution (Mw / Mn) of the block copolymer [1] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.

ブロック共重合体［１］の製造方法は、例えばリビングアニオン重合などの方法により、芳香族ビニル化合物を主成分として含有するモノマー混合物（ａ）と鎖状共役ジエン系化合物を主成分として含有するモノマー混合物（ｂ）を交互に重合させる方法；芳香族ビニル化合物を主成分として含有するモノマー混合物（ａ）と鎖状共役ジエン系化合物を主成分として含有するモノマー混合物（ｂ）を順に重合させた後、重合体ブロック［Ａ］と重合体ブロック［Ｂ］の末端同士を、カップリング剤によりカップリングさせる方法などがある。   The production method of the block copolymer [1] includes a monomer mixture (a) containing an aromatic vinyl compound as a main component and a monomer containing a chain conjugated diene compound as a main component by, for example, a method such as living anion polymerization. A method of alternately polymerizing the mixture (b); after sequentially polymerizing the monomer mixture (a) containing an aromatic vinyl compound as a main component and the monomer mixture (b) containing a chain conjugated diene compound as a main component And a method of coupling the ends of the polymer block [A] and the polymer block [B] with a coupling agent.

（ブロック共重合体水素化物［２］）
ブロック共重合体水素化物［２］は、上記のブロック共重合体［１］が有する全不飽和結合の９０％以上を水素化したものである。ブロック共重合体［１］が有する全不飽和結合とは、主鎖および側鎖の炭素−炭素不飽和結合、並びに芳香環の炭素−炭素不飽和結合の合計である。上記水素化率は、好ましくは９７％以上、より好ましくは９９％以上である。水素化率が高いほど、バリア層の耐候性、耐熱性が良好である。ブロック共重合体水素化物［２］の水素化率は、１Ｈ−ＮＭＲによる測定において求めることができる。 (Block copolymer hydride [2])
The block copolymer hydride [2] is obtained by hydrogenating 90% or more of the total unsaturated bonds of the block copolymer [1]. The total unsaturated bond which block copolymer [1] has is the sum total of the carbon-carbon unsaturated bond of a main chain and a side chain, and the carbon-carbon unsaturated bond of an aromatic ring. The hydrogenation rate is preferably 97% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the weather resistance and heat resistance of the barrier layer. The hydrogenation rate of the block copolymer hydride [2] can be determined by measurement by 1H-NMR.

不飽和結合の水素化方法や反応形態などは特に限定されず、公知の方法にしたがって行えばよいが、水素化率を高くでき、重合体鎖切断反応の少ない水素化方法が好ましい。このような水素化方法としては、例えば、国際公開ＷＯ２０１１／０９６３８９号、国際公開ＷＯ２０１２／０４３７０８号などに記載された方法を挙げることができる。   There are no particular restrictions on the hydrogenation method or reaction mode of the unsaturated bond, and it may be carried out according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction is preferred. Examples of such a hydrogenation method include methods described in International Publication WO2011 / 096389, International Publication WO2012 / 043708, and the like.

上記の方法で得られるブロック共重合体水素化物［２］は、水素化触媒および／または重合触媒を、ブロック共重合体水素化物［２］を含む反応溶液から除去した後、反応溶液から回収される。回収されたブロック共重合体水素化物［２］の形態は限定されるものではないが、通常はペレット形状にして、その後のアルコキシシリル基の導入反応に供することができる。   The block copolymer hydride [2] obtained by the above method is recovered from the reaction solution after removing the hydrogenation catalyst and / or the polymerization catalyst from the reaction solution containing the block copolymer hydride [2]. The Although the form of the recovered block copolymer hydride [2] is not limited, it can usually be formed into a pellet and used for the subsequent introduction reaction of alkoxysilyl groups.

ブロック共重合体水素化物［２］の分子量は、テトラヒドロフランを溶媒としたＧＰＣにより測定されるポリスチレン換算の重量平均分子量（Ｍｗ）で、通常、３５，０００〜２００，０００、好ましくは４０，０００〜１５０，０００、より好ましくは４５，０００〜１００，０００である。また、ブロック共重合体水素化物［２］の分子量分布（Ｍｗ／Ｍｎ）を、好ましくは３以下、より好ましくは２以下、特に好ましくは１．５以下にする。ＭｗおよびＭｗ／Ｍｎが上記範囲となるようにすると、バリア層の機械強度や耐熱性が向上する。   The molecular weight of the block copolymer hydride [2] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using tetrahydrofuran as a solvent, and is usually 35,000 to 200,000, preferably 40,000 to It is 150,000, More preferably, it is 45,000-100,000. The molecular weight distribution (Mw / Mn) of the block copolymer hydride [2] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, the mechanical strength and heat resistance of the barrier layer are improved.

（変性ブロック共重合体水素化物［３］）
変性ブロック共重合体水素化物［３］は、上記ブロック共重合体水素化物［２］にアルコキシシリル基が導入されたものである。アルコキシシリル基は、上記ブロック共重合体水素化物［２］に直接結合していても、アルキレン基などの２価の有機基を介して結合していてもよい。 (Modified block copolymer hydride [3])
The modified block copolymer hydride [3] is obtained by introducing an alkoxysilyl group into the block copolymer hydride [2]. The alkoxysilyl group may be directly bonded to the block copolymer hydride [2] or may be bonded via a divalent organic group such as an alkylene group.

アルコキシシリル基の導入方法は、通常、上記のブロック共重合体水素化物［２］とエチレン性不飽和シラン化合物とを過酸化物の存在下で反応させる方法が好ましい。   As the method for introducing an alkoxysilyl group, a method in which the above block copolymer hydride [2] is reacted with an ethylenically unsaturated silane compound in the presence of a peroxide is usually preferred.

アルコキシシリル基の導入量は、通常、ブロック共重合体水素化物［２］１００質量部に対し、０．１〜１０質量部、好ましくは０．２〜５質量部、より好ましくは０．３〜３質量部である。アルコキシシリル基の導入量が多過ぎると、所望の形状に溶融成形する前に微量の水分等で分解されたアルコキシシリル基同士の架橋が進み、ゲルが発生したり、溶融時の流動性が低下して成形性が低下するなどの問題を生じる。アルコキシシリル基の導入量が少な過ぎると、他の層との十分な接着力が得られないという不具合が生じるため好ましくない。アルコキシシリル基の導入はＩＲスペクトルで確認することができ、導入量は１Ｈ−ＮＭＲによる測定において求めることができる。   The introduction amount of the alkoxysilyl group is usually 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, more preferably 0.3 to 100 parts by mass with respect to 100 parts by mass of the block copolymer hydride [2]. 3 parts by mass. If the amount of alkoxysilyl groups introduced is too large, cross-linking of alkoxysilyl groups decomposed with a small amount of moisture, etc., proceeds before melt molding into the desired shape, resulting in gel generation or poor fluidity at the time of melting. As a result, problems such as deterioration of moldability occur. When the introduction amount of the alkoxysilyl group is too small, it is not preferable because a problem that sufficient adhesive force with other layers cannot be obtained occurs. The introduction of the alkoxysilyl group can be confirmed by IR spectrum, and the amount introduced can be determined by measurement by 1H-NMR.

エチレン性不飽和シラン化合物としては、上記のブロック共重合体水素化物［２］とグラフト重合し、ブロック共重合体水素化物［２］にアルコキシシリル基を導入するものであれば特に限定されないが、例えばビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン、ｐ−スチリルトリメトキシシランが好適に用いられる。これらのエチレン性不飽和シラン化合物は、それぞれ単独で用いてもよいし、２種以上を組み合わせて使用してもよい。エチレン性不飽和シラン化合物の使用量は、上記アルコキシシリル基の導入量と同量とできる。   The ethylenically unsaturated silane compound is not particularly limited as long as it is graft-polymerized with the above-mentioned block copolymer hydride [2] and introduces an alkoxysilyl group into the block copolymer hydride [2]. For example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, and p-styryltrimethoxysilane are preferably used. These ethylenically unsaturated silane compounds may be used alone or in combination of two or more. The amount of the ethylenically unsaturated silane compound used can be the same as the amount of the alkoxysilyl group introduced.

過酸化物としては、１分間半減期温度が１７０〜１９０℃のものが好ましく使用される。過酸化物としては、例えば、ｔ−ブチルクミルパーオキシド、ジクミルパーオキサイド、ジ−ｔ−ヘキシルパーオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ジ−ｔ−ブチルパーオキシドなどが好適に用いられる。   As the peroxide, those having a one-minute half-life temperature of 170 to 190 ° C. are preferably used. Examples of the peroxide include t-butyl cumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di- T-butyl peroxide or the like is preferably used.

これらの過酸化物は、それぞれ単独で用いてもよいし、２種以上を組み合わせて使用してもよい。過酸化物の使用量は、ブロック共重合体水素化物［２］１００質量部に対して、通常０．０５〜２質量部、好ましくは０．１〜１質量部、より好ましくは０．２〜０．５質量部である。   These peroxides may be used alone or in combination of two or more. The amount of the peroxide used is usually 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the block copolymer hydride [2]. 0.5 parts by mass.

上記のブロック共重合体水素化物［２］とエチレン性不飽和シラン化合物とを過酸化物の存在下で反応させる方法は特に限定されない。例えば、ブロック共重合体水素化物［２］と所定量のエチレン性不飽和シラン化合物および過酸化物を、二軸混練機にて所望の温度で所望の時間混練することによりアルコキシシリル基を導入することができる。上記混練温度は、通常１８０〜２２０℃、好ましくは１８５〜２１０℃、より好ましくは１９０〜２００℃である。加熱混練時間は、通常０．１〜１０分間、好ましくは０．２〜５分間、より好ましくは０．３〜２分間程度である。温度、滞留時間が上記範囲になるようにして、連続的に混練、押出しをすればよい。   The method of reacting the block copolymer hydride [2] with the ethylenically unsaturated silane compound in the presence of a peroxide is not particularly limited. For example, an alkoxysilyl group is introduced by kneading a block copolymer hydride [2], a predetermined amount of an ethylenically unsaturated silane compound and a peroxide at a desired temperature with a biaxial kneader for a desired time. be able to. The kneading temperature is usually 180 to 220 ° C, preferably 185 to 210 ° C, more preferably 190 to 200 ° C. The heating and kneading time is usually about 0.1 to 10 minutes, preferably about 0.2 to 5 minutes, more preferably about 0.3 to 2 minutes. What is necessary is just to knead | mix and extrude continuously so that temperature and residence time may become the said range.

変性ブロック共重合体水素化物［３］の分子量は、導入されるアルコキシシリル基の量が少ないため、原料として用いたブロック共重合体水素化物［２］の分子量と実質的には変わらないが、過酸化物の存在下でエチレン性不飽和シラン化合物と反応させるため、重合体の架橋反応、切断反応も併発し、分子量分布は大きくなる。テトラヒドロフランを溶媒としたＧＰＣにより測定されるポリスチレン換算の重量平均分子量（Ｍｗ）で、通常３５，０００〜２００，０００、好ましくは４０，０００〜１５０，０００、より好ましくは４５，０００〜１００，０００、分子量分布（Ｍｗ／Ｍｎ）は、通常３．５以下、好ましくは２．５以下、特に好ましくは２．０以下である。ＭｗおよびＭｗ／Ｍｎがこの範囲であると、バリア層の機械強度や耐熱性が維持される。   The molecular weight of the modified block copolymer hydride [3] is substantially the same as the molecular weight of the block copolymer hydride [2] used as a raw material because the amount of the introduced alkoxysilyl group is small. Since it reacts with the ethylenically unsaturated silane compound in the presence of a peroxide, a cross-linking reaction and a cleavage reaction of the polymer occur together, and the molecular weight distribution becomes large. The polystyrene-reduced weight average molecular weight (Mw) measured by GPC using tetrahydrofuran as a solvent is usually 35,000 to 200,000, preferably 40,000 to 150,000, more preferably 45,000 to 100,000. The molecular weight distribution (Mw / Mn) is usually 3.5 or less, preferably 2.5 or less, particularly preferably 2.0 or less. When Mw and Mw / Mn are within this range, the mechanical strength and heat resistance of the barrier layer are maintained.

接着性樹脂組成物（Ｉ）は、変性ブロック共重合体水素化物［３］を含有する。接着性樹脂組成物（Ｉ）は、変性ブロック共重合体水素化物［３］以外のその他の成分を含有してもよい。   The adhesive resin composition (I) contains a modified block copolymer hydride [3]. The adhesive resin composition (I) may contain other components other than the modified block copolymer hydride [3].

その他の成分としては、接着性や遮音性能を向上させるための可塑剤、耐光性、遮光性、耐熱性などを向上させるための光安定剤、紫外線吸収剤、酸化防止剤などが挙げられる。   Examples of other components include a plasticizer for improving adhesiveness and sound insulation performance, a light stabilizer for improving light resistance, light shielding properties, heat resistance, and the like, an ultraviolet absorber, and an antioxidant.

以上、図１、２に示される合わせガラス１０を例にして本発明の合わせガラスについて説明したが、本発明はこれに限定されない。本発明の趣旨および範囲を逸脱することのない範囲で、設計を変更または変形することができる。実施形態の合わせガラスは、必要に応じて、３枚以上のガラス板を有する構成、例えば、合わせガラス１０のガラス板１Ａまたはガラス板１Ｂの大気側に、さらに１枚以上のガラス板をそれぞれ、中間接着層２Ａ、２Ｂとは別に準備された中間接着層を介して積層した合わせガラスであってもよい。また、実施形態の合わせガラスは、上記構成要素に加えて、本発明の効果を損なわい範囲で任意にその他の層を有してもよい。   As mentioned above, although the laminated glass 10 of this invention was demonstrated taking the laminated glass 10 shown by FIGS. 1, 2 as an example, this invention is not limited to this. The design can be changed or modified without departing from the spirit and scope of the present invention. The laminated glass of the embodiment has a configuration having three or more glass plates, if necessary, for example, one or more glass plates on the atmosphere side of the glass plate 1A or the glass plate 1B of the laminated glass 10, Laminated glass laminated via an intermediate adhesive layer prepared separately from the intermediate adhesive layers 2A and 2B may be used. Moreover, the laminated glass of embodiment may have another layer arbitrarily in the range which does not impair the effect of this invention in addition to the said component.

（その他の層）
実施形態の合わせガラスは、その他の層として、１対のガラス板の間に機能フィルムを有してもよい。機能フィルムを有する場合は、例えば、上記１対の中間接着層に加えて、さらに中間接着層を有し、ガラス板、中間接着層、その他の機能フィルム、中間接着層、ＳＰＤフィルムとバリア層を組み合せた層、中間接着層、ガラス板の順に積層して合わせガラスとされる。 (Other layers)
The laminated glass of the embodiment may have a functional film between a pair of glass plates as another layer. In the case of having a functional film, for example, in addition to the pair of intermediate adhesive layers, an intermediate adhesive layer is further provided, and a glass plate, an intermediate adhesive layer, other functional films, an intermediate adhesive layer, an SPD film and a barrier layer A laminated glass, an intermediate adhesive layer, and a glass plate are laminated in this order to form a laminated glass.

上記機能フィルムとしては、例えば、赤外線遮蔽フィルム等が挙げられる。赤外線遮蔽フィルムとして、具体的には、２５〜２００μｍ程度の厚みのＰＥＴフィルム等の支持フィルム上に、赤外線反射膜として膜厚１００〜５００ｎｍ程度の、誘電体多層膜、液晶配向膜、赤外線反射材含有コーティング膜、金属膜を含む単層または多層の赤外線反射膜等の従来公知の赤外線反射膜が形成されたものが挙げられる。赤外線遮蔽フィルムとしては、さらに屈折率の異なる樹脂フィルムを積層した合計膜厚が２５〜２００μｍ程度の誘電多層フィルム等が挙げられる。   Examples of the functional film include an infrared shielding film. As an infrared shielding film, specifically, a dielectric multilayer film, a liquid crystal alignment film, an infrared reflecting material having a thickness of about 100 to 500 nm as an infrared reflecting film on a support film such as a PET film having a thickness of about 25 to 200 μm. Examples thereof include those formed with a conventionally known infrared reflective film such as a coating film and a single-layer or multilayer infrared reflective film including a metal film. As an infrared shielding film, the dielectric multilayer film etc. whose total film thickness which laminated | stacked the resin film from which a refractive index differs further about 25-200 micrometers are mentioned.

合わせガラスにおいては、その枠体等への取り付け部分や配線導体等を隠蔽する目的と、外部からの水分によりＳＰＤフィルムの端部が経年劣化した場合の外観悪化の予防を目的として、合わせガラスを構成するガラス板の主面の周縁部の一部または全部に帯状に、黒色セラミックス層を設けることがある。実施形態の合わせガラスにおいても、その他の層として、このような黒色セラミックス層を設けてもよい。ただし、意匠性向上の観点から、本発明の合わせガラスにおいては黒色セラミックス層を有しない、または黒色セラミック層を有していてもその幅は狭く、具体的には３０ｍｍ以下である場合に、本発明の効果を最大限に享受できる。   In laminated glass, laminated glass is used for the purpose of concealing the attachment part to the frame and the wiring conductor, etc., and for preventing the deterioration of the appearance when the end of the SPD film is aged due to moisture from the outside. A black ceramic layer may be provided in a strip shape on a part or all of the peripheral edge of the main surface of the glass plate to be formed. Also in the laminated glass of the embodiment, such a black ceramic layer may be provided as another layer. However, from the viewpoint of improving designability, the laminated glass of the present invention does not have a black ceramic layer, or even if it has a black ceramic layer, its width is narrow, specifically when it is 30 mm or less. The effect of the invention can be enjoyed to the maximum.

［合わせガラスの製造］
本発明の実施形態の合わせガラスは、一般的に用いられる公知の技術により製造できる。合わせガラス１０においては、１対の中間接着層２Ａ、２Ｂの間にＳＰＤフィルム３およびバリア層４を所定の位置関係となるように配置した積層体を作製し、これを１対のガラス板１Ａ、１Ｂの間に挿入して、ガラス板１Ａ、中間接着層２Ａ、ＳＰＤフィルム３およびバリア層４からなる層、中間接着層２Ｂ、ガラス板１Ｂの順に積層された圧着前の合わせガラスである合わせガラス前駆体を準備する。その他の層を有する場合も、同様に得られる合わせガラスと同様の積層順にガラス板と各層を積層して合わせガラス前駆体を準備する。 [Manufacture of laminated glass]
The laminated glass of the embodiment of the present invention can be produced by a commonly used known technique. In the laminated glass 10, a laminate in which the SPD film 3 and the barrier layer 4 are arranged in a predetermined positional relationship between a pair of intermediate adhesive layers 2A and 2B is produced, and this is formed into a pair of glass plates 1A. 1B, laminated glass glass 1A, intermediate adhesive layer 2A, SPD film 3 and barrier layer 4 layer, intermediate adhesive layer 2B, laminated glass glass 1B laminated in this order before bonding A glass precursor is prepared. Also when it has another layer, a laminated glass precursor is prepared by laminating a glass plate and each layer in the same laminating order as the laminated glass similarly obtained.

この合わせガラス前駆体をゴムバッグのような真空バッグの中に入れ、この真空バッグを排気系に接続して、真空バッグ内の圧力が約−６５〜−１００ｋＰａの減圧度となるように減圧吸引（脱気）しながら温度約７０〜１１０℃で接着することで実施形態の合わせガラスを得ることができる。さらに、例えば、１００〜１１０℃、圧力０．６〜１．３ＭＰａの条件で加熱加圧する圧着処理を行うことで、より耐久性の優れた合わせガラスを得ることができる。   This laminated glass precursor is put in a vacuum bag such as a rubber bag, and this vacuum bag is connected to an exhaust system, and vacuum suction is performed so that the pressure in the vacuum bag is about −65 to −100 kPa. The laminated glass of the embodiment can be obtained by bonding at a temperature of about 70 to 110 ° C. while (degassing). Furthermore, for example, a laminated glass having more excellent durability can be obtained by performing a pressure-bonding treatment by heating and pressing under conditions of 100 to 110 ° C. and a pressure of 0.6 to 1.3 MPa.

本発明の合わせガラスは、ＳＰＤフィルムの経時的な劣化、特に端部における水分の侵入による劣化を抑制することで、長期に亘って透過率の切り替え特性が良好な合わせガラスであって、例えば、車両用の窓ガラスに好適に使用される。   The laminated glass of the present invention is a laminated glass having good transmittance switching characteristics over a long period of time by suppressing deterioration over time of the SPD film, particularly deterioration due to moisture intrusion at the edge, It is suitably used for a window glass for vehicles.

以下に、本発明を実施例によりさらに詳細に説明する。本発明は、以下で説明する実施形態および実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the embodiments and examples described below.

［実験例１］
以下のようにして、ＳＰＤフィルムの代わりに含水量が測定可能なＰＶＢを有する評価用サンプルを作製して、本発明の合わせガラスに適用されるバリア層の防湿性を評価した。 [Experimental Example 1]
In the following manner, a sample for evaluation having PVB capable of measuring water content was prepared instead of the SPD film, and the moisture resistance of the barrier layer applied to the laminated glass of the present invention was evaluated.

（評価用サンプルの作製）
図３に正面図を、図４に端部の断面図を示す評価用サンプル２０を以下のように作製した。 (Preparation of sample for evaluation)
An evaluation sample 20 having a front view in FIG. 3 and a sectional view of an end in FIG. 4 was produced as follows.

２枚のソーダライムガラスからなるガラス板Ｇ（２ｍｍ厚、１００ｍｍ角）の間に、９４×９７ｍｍ、０．７６ｍｍ厚のＰＶＢフィルムおよび同サイズで０．３８ｍｍ厚のＰＶＢフィルム（イーストマンケミカル社製、ＲＫ１１（商品名））を積層したＰＶＢ積層フィルムＰを、対向する２辺がガラス板Ｇの外周端からそれぞれ内側に１ｍｍと５ｍｍとなるように、および別の対向する２辺がガラス板の外周端Ｇからそれぞれ内側に０ｍｍと３ｍｍとなるように配置した。また、２枚のガラス板Ｇの間のＰＶＢ積層フィルムＰが欠けた部分を補填する形の、帯状領域がコの字型に形成されたバリア層Ｓを配置した。なお、バリア層Ｓはコの字型の内側の端面がガラス板Ｇの１辺と一致しないＰＶＢ積層フィルムＰの３辺の端面に接するように、コの字型の外側がガラス板Ｇの外周と一致するように配置されている。なお、バリア層Ｓが有する帯状領域のコの字型の３辺の幅は、それぞれ１ｍｍ、３ｍｍおよび５ｍｍである。   Between a glass plate G (2 mm thick, 100 mm square) made of two soda lime glasses, a 94 × 97 mm, 0.76 mm thick PVB film and a 0.38 mm thick PVB film (made by Eastman Chemical Co., Ltd.) , RK11 (trade name)), the opposing two sides of the glass plate G are 1 mm and 5 mm inward from the outer peripheral edge of the glass plate G, and the other two opposing sides are glass plates. Arranged to be 0 mm and 3 mm inside from the outer peripheral edge G, respectively. In addition, a barrier layer S in which a band-like region was formed in a U-shape so as to compensate for a portion where the PVB laminated film P between the two glass plates G was missing was disposed. The outer side of the U-shape is the outer periphery of the glass plate G so that the inner end surface of the U-shape is in contact with the end surfaces of the three sides of the PVB laminated film P that do not coincide with one side of the glass plate G. Are arranged to match. The widths of the three U-shaped sides of the belt-like region of the barrier layer S are 1 mm, 3 mm, and 5 mm, respectively.

上記で得られたガラス板Ｇ、ＰＶＢ積層フィルムＰ、バリア層Ｓからなる積層体を、真空バックに入れて脱気したのち、１２０℃に保持したオーブンに投入し、３０分放置して、圧着することで、評価用サンプル２０を得た。なお、上記において同様の評価用サンプル２０を２個作製した。   The laminated body composed of the glass plate G, PVB laminated film P, and barrier layer S obtained above is put in a vacuum bag and degassed, then placed in an oven maintained at 120 ° C., left to stand for 30 minutes, and crimped. Thus, an evaluation sample 20 was obtained. Two similar evaluation samples 20 were produced in the above.

なお、バリア層Ｓの積層構造は、図４に示すように、０．３８ｍｍ厚のバリア層用フィルムｓ１、ｓ２、ｓ３の３層積層構造である。また、バリア層用フィルムｓ１、ｓ２、ｓ３は、全て以下により作製された接着性樹脂組成物（Ｉａ）からなるフィルムであった。   The laminated structure of the barrier layer S is a three-layer laminated structure of barrier layer films s1, s2, and s3 having a thickness of 0.38 mm, as shown in FIG. Further, the barrier layer films s1, s2, and s3 were all films made of the adhesive resin composition (Ia) produced as follows.

＜接着性樹脂組成物（Ｉａ）フィルムの作製＞
以下の様にして製造した変性ブロック共重合体水素化物［３］−１を用いて接着性樹脂組成物（Ｉａ）フィルムを以下のとおり作製した。 <Production of Adhesive Resin Composition (Ia) Film>
An adhesive resin composition (Ia) film was produced as follows using the modified block copolymer hydride [3] -1 produced as follows.

（１）ブロック共重合体［１］−１の合成
充分に窒素置換された、撹拌装置を備えた反応器に脱水シクロヘキサン５５０部、脱水スチレン２５．０部およびｎ−ジブチルエーテル０．４７５部を入れ、６０℃で撹拌しながらｎ−ブチルリチウム（１５％シクロヘキサン溶液）０．６２部を加えて重合を開始した。撹拌しながら６０℃で６０分反応させた。ガスクロマトグラフィーにより測定した、この時点で重合転化率は９９．５％であった。 (1) Synthesis of block copolymer [1] -1 To a reactor equipped with a stirrer sufficiently purged with nitrogen, 550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene and 0.475 part of n-dibutyl ether were added. While stirring at 60 ° C., 0.62 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. The mixture was reacted at 60 ° C. for 60 minutes with stirring. At this point in time, measured by gas chromatography, the polymerization conversion was 99.5%.

次に、脱水イソプレン５０．０部を加えそのまま３０分撹拌を続けた。この時点で重合転化率は９９．５％であった。
その後、さらに、脱水スチレンを２５．０部加え、６０分撹拌した。この時点での重合転化率はほぼ１００％であった。ここでイソプロピルアルコール０．５部を加えて反応を停止した。得られたブロック共重合体［１］−１の重量平均分子量（Ｍｗ）は７８，０００、分子量分布（Ｍｗ／Ｍｎ）は１．０３、ｗＡ：ｗＢ＝５０：５０であった。 Next, 50.0 parts of dehydrated isoprene was added and stirring was continued for 30 minutes. At this time, the polymerization conversion rate was 99.5%.
Thereafter, 25.0 parts of dehydrated styrene was further added and stirred for 60 minutes. The polymerization conversion rate at this point was almost 100%. Here, 0.5 part of isopropyl alcohol was added to stop the reaction. The obtained block copolymer [1] -1 had a weight average molecular weight (Mw) of 78,000, a molecular weight distribution (Mw / Mn) of 1.03, and wA: wB = 50: 50.

（２）ブロック共重合体水素化物［２］−１の合成
次に、上記重合体溶液を、撹拌装置を備えた耐圧反応器に移送し、水素化触媒として珪藻土担持型ニッケル触媒（製品名「Ｔ−８４００ＲＬ」、ズードケミー触媒社製）３．０部および脱水シクロヘキサン１００部を添加して混合した。反応器内部を水素ガスで置換し、さらに溶液を撹拌しながら水素を供給し、温度１９０℃、圧力４．５ＭＰａにて６時間水素化反応を行った。水素化反応後のブロック共重合体水素化物［２］−１の重量平均分子量（Ｍｗ）は７８，８００、分子量分布（Ｍｗ／Ｍｎ）は１．０４であった。 (2) Synthesis of block copolymer hydride [2] -1 Next, the polymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name “ T-8400RL "(manufactured by Zude Chemie Catalysts) 3.0 parts and dehydrated cyclohexane 100 parts were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours. The weight average molecular weight (Mw) of the block copolymer hydride [2] -1 after the hydrogenation reaction was 78,800, and the molecular weight distribution (Mw / Mn) was 1.04.

水素化反応終了後、反応溶液をろ過して水素化触媒を除去した後、フェノール系酸化防止剤であるペンタエリスリチル・テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（製品名「Ｓｏｎｇｎｏｘ１０１０」、ＳＯＮＧＷＯＮ社製）０．１部を溶解したキシレン溶液１．０部を添加して溶解させた。   After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate] (product name “Songnox 1010”, manufactured by SONGWON) 1.0 part of xylene solution in which 0.1 part was dissolved was added and dissolved.

次いで、上記溶液を、金属ファイバー製フィルター（孔径０．４μｍ、ニチダイ社製）にてろ過して微小な固形分を除去した後、円筒型濃縮乾燥器（製品名「コントロ」、日立製作所社製）を用いて、温度２６０℃、圧力０．００１ＭＰａ以下で、溶液から、溶媒であるシクロヘキサン、キシレンおよびその他の揮発成分を除去した。連続して溶融ポリマーを、濃縮乾燥器に連結した孔径５μｍのステンレス製焼結フィルターを備えたポリマーフィルター（富士フィルター製）により、温度２６０℃でろ過した後、ダイから溶融ポリマーをストランド状に押出し、冷却後、ペレタイザーによりブロック共重合体水素化物［２］−１のペレット９６部を作製した。得られたブロック共重合体水素化物［２］−１の重量平均分子量（Ｍｗ）は７７，８００、分子量分布（Ｍｗ／Ｍｎ）は１．０４であった。水素化率はほぼ１００％であった。   Next, the above solution was filtered with a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai) to remove minute solids, and then a cylindrical concentration dryer (product name “Contro”, manufactured by Hitachi, Ltd.) ), The solvent cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less. The molten polymer is continuously filtered at a temperature of 260 ° C. by a polymer filter (manufactured by Fuji Filter) equipped with a stainless sintered filter having a pore diameter of 5 μm connected to a concentration dryer, and then the molten polymer is extruded into a strand form from a die. After cooling, 96 parts of pellets of block copolymer hydride [2] -1 were prepared by a pelletizer. The resulting block copolymer hydride [2] -1 had a weight average molecular weight (Mw) of 77,800 and a molecular weight distribution (Mw / Mn) of 1.04. The hydrogenation rate was almost 100%.

（３）変性ブロック共重合体水素化物［３］−１の合成
得られたブロック共重合体水素化物［２］−１のペレット１００部に対してビニルトリメトキシシラン２．０部および２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（製品名「パーヘキサ（登録商標）２５Ｂ」、日油社製）０．２部を添加し、この混合物を、二軸押出機（製品名「ＴＥＭ３７Ｂ」、東芝機械社製）を用いて、樹脂温度２００℃、滞留時間６０〜７０秒で混練し、ストランド状に押出し、空冷した後、ペレタイザーによりカッティングし、アルコキシシリル基を有する変性ブロック共重合体水素化物［３］−１のペレット９７部を得た。 (3) Synthesis of modified block copolymer hydride [3] -1 2.0 parts of vinyltrimethoxysilane and 2,5 with respect to 100 parts of pellets of the obtained block copolymer hydride [2] -1 -0.2 part of dimethyl-2,5-di (t-butylperoxy) hexane (product name "Perhexa (registered trademark) 25B", manufactured by NOF Corporation) was added, and this mixture was added to a twin-screw extruder ( A product name “TEM37B” manufactured by Toshiba Machine Co., Ltd.) is kneaded at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds, extruded into a strand, air-cooled, and then cut with a pelletizer to have an alkoxysilyl group. 97 parts of pellets of hydrogenated block copolymer [3] -1 were obtained.

得られたアルコキシシリル基を有するブロック共重合体水素化物［３］−１のペレット１０部をシクロヘキサン１００部に溶解した後、脱水したメタノール４００部中に注いでアルコキシシリル基を有するブロック共重合体水素化物［３］−１を凝固させ、濾別した後、２５℃で真空乾燥してアルコキシシリル基を有するブロック共重合体水素化物［３］−１のクラム９．５部を単離した。ＦＴ−ＩＲスペクトルでは、１０９０ｃｍ−１にＳｉ−ＯＣＨ３基、８２５ｃｍ−１と７３９ｃｍ−１にＳｉ−ＣＨ２基に由来する新たな吸収帯が、ビニルトリメトキシシランのそれらの１０７５ｃｍ−１、８０８ｃｍ−１、および７６６ｃｍ−１と異なる位置に観察された。また、１Ｈ−ＮＭＲスペクトル（重クロロホルム中）では３．６ｐｐｍにメトキシ基のプロトンに基づく吸収帯が観察され、ピーク面積比からブロック共重合体水素化物［２］−１の１００部に対してビニルトリメトキシシラン１．７部が結合したことが確認された。 The obtained block copolymer hydride [3] -1 pellets having an alkoxysilyl group were dissolved in 100 parts of cyclohexane, and then poured into 400 parts of dehydrated methanol to block the block copolymer having an alkoxysilyl group. The hydride [3] -1 was coagulated and filtered, and then vacuum dried at 25 ° C. to isolate 9.5 parts of crumb of the block copolymer hydride [3] -1 having an alkoxysilyl group. The FT-IR spectra, Si-OCH 3 groups to 1090cm -1, 825cm -1 and 739cm new absorption band derived from Si-CH 2 group at -1, their 1075 cm -1 of vinyltrimethoxysilane, 808Cm −1 and 766 cm −1 were observed at different positions. Further, in 1H-NMR spectrum (in deuterated chloroform), an absorption band based on proton of methoxy group was observed at 3.6 ppm, and from the peak area ratio, vinyl relative to 100 parts of block copolymer hydride [2] -1 was observed. It was confirmed that 1.7 parts of trimethoxysilane was bonded.

（４）接着性樹脂組成物（Ｉａ）およびフィルムの作製
上記で得られた変性ブロック共重合体水素化物［３］−１のペレット１００重量部に紫外線吸収剤である２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン（製品名「アデカスタブ（登録商標）１４１３」、ＡＤＥＫＡ社製）０．５部を添加し、９０ｍｍφのスクリューを備えた押出し機を有するＴダイ式フィルム溶融押出し成形機（Ｔダイ幅１２００ｍｍ）および梨地パターンのエンボスロールを備えたシート引取機を使用し、溶融樹脂温度１９０℃、Ｔダイ温度１９０℃、ロール温度５０℃の成形条件にて、厚さ１．２ｍｍ、幅１０００ｍｍの接着性樹脂組成物（Ｉａ）のシートを押出し成形した。得られたシートはロールに巻き取り回収した。得られたシートを厚さ０．３８ｍｍのフィルムに成形した。 (4) Production of Adhesive Resin Composition (Ia) and Film 2-hydroxy-4-n which is an ultraviolet absorber is added to 100 parts by weight of the pellet of the modified block copolymer hydride [3] -1 obtained above. -Octoxy benzophenone (product name "Adekastab (registered trademark) 1413", manufactured by ADEKA) 0.5 part and a T-die film melt extrusion machine (T-die width) having an extruder equipped with a 90 mmφ screw 1200 mm) and a satin pattern embossing roll, and using a sheet take-up machine with a melt resin temperature of 190 ° C., a T-die temperature of 190 ° C., and a roll temperature of 50 ° C., and bonding with a thickness of 1.2 mm and a width of 1000 mm A sheet of the functional resin composition (Ia) was extruded. The obtained sheet was wound up and collected on a roll. The obtained sheet was formed into a film having a thickness of 0.38 mm.

得られたフィルムについて、ガラスとの接着力をＪＩＳ Ｋ ６８５４−２：１９９９に準拠した接着性（Ａ）と同様の上述の方法にて測定した結果、６７．８[Ｎ／２５ｍｍ]であった。なお、ガラス板との接着性測定用サンプルは以下のように作製した。ガラス板（ソーダライムガラス、２ｍｍ厚×６０×２５ｍｍサイズ）、接着性樹脂組成物（Ｉａ）フィルム、１００μｍ厚ＰＥＴフィルム、厚み２ｍｍのソーダライムガラス板（いずれも１００×２５ｍｍサイズ）をこの順に重ね合わせ、この積層体を真空バッグに入れた。その後、真空バッグ内が−６０ｋＰａ以下の減圧度となるように脱気しながら１１０℃で圧着した。
一方、得られたフィルムの透湿性についてＪＩＳ Ｚ ０２０８：１９７６に準拠した透湿性（Ｂ）と同様の上述の方法にて測定した結果、１[ｇ／ｍ２・ｄａｙ]であった。 About the obtained film, as a result of measuring the adhesive force with glass by the above-mentioned method similar to the adhesiveness (A) based on JISK6854-2: 1999, it was 67.8 [N / 25mm]. . In addition, the sample for adhesiveness measurement with a glass plate was produced as follows. A glass plate (soda lime glass, 2 mm thickness × 60 × 25 mm size), adhesive resin composition (Ia) film, 100 μm thickness PET film, and 2 mm thick soda lime glass plate (both 100 × 25 mm size) are stacked in this order. The laminated body was put in a vacuum bag. Thereafter, pressure bonding was performed at 110 ° C. while degassing so that the inside of the vacuum bag had a reduced pressure of −60 kPa or less.
On the other hand, the moisture permeability of the obtained film was 1 [g / m 2 · day] as a result of measurement by the same method as described above for moisture permeability (B) based on JIS Z 0208: 1976.

（防湿性評価）
上記で得られた評価用サンプル２０の１個を８０℃、湿度９５％ＲＨの恒温恒湿槽に、１１０時間、１個を５０℃、湿度９５％ＲＨの恒温恒湿槽に、３７６時間投入した。
恒温恒湿槽から取出し常温まで戻した後、バリア層Ｓが配設された側のガラス板Ｇの２辺から、バリア層の幅が１ｍｍである辺については３．５ｍｍ内側のＡ点を中心に、バリア層の幅が３ｍｍである辺については５．５ｍｍ内側のＢ点を中心に、バリア層の幅が５ｍｍである辺については７．５ｍｍ内側のＣ点を中心に、パーキンエルマー社製Ｓｐｅｃｔｒｕｍ Ｔｗｏを用いて分光測定を行うことで、Ａ点、Ｂ点およびＣ点におけるＰＶＢ積層フィルムＰの含水率（％）を測定した。各測定点において得られた含水率（％）から、恒温恒湿槽に投入する前に予め測定したＰＶＢ積層フィルムＰの初期含水率（％）をそれぞれひいた値を含水率増加量（％）として評価に用いた。 (Dampproof evaluation)
One of the evaluation samples 20 obtained above was placed in a thermostatic chamber at 80 ° C. and a humidity of 95% RH for 110 hours, and one was placed in a thermostatic chamber at 50 ° C. and a humidity of 95% RH for 376 hours. did.
After taking out from the thermo-hygrostat and returning to room temperature, from the two sides of the glass plate G on the side where the barrier layer S is disposed, the side where the width of the barrier layer is 1 mm is centered on the point A inside 3.5 mm In addition, the side where the width of the barrier layer is 3 mm is centered around the point B inside 5.5 mm, and the side where the width of the barrier layer is 5 mm is centered around the point C inside 7.5 mm, made by Perkin Elmer By performing spectroscopic measurement using Spectrum Two, the moisture content (%) of the PVB laminated film P at points A, B, and C was measured. From the moisture content (%) obtained at each measurement point, the value obtained by subtracting the initial moisture content (%) of the PVB laminated film P measured in advance before being put into the constant temperature and humidity chamber is the moisture content increase (%). Used for evaluation.

なお、図４においてＬ２はバリア層の幅（１ｍｍ、３ｍｍまたは５ｍｍ）を示す。また、図４においてＬ１は２ｍｍであり、バリア層の内側から２ｍｍの位置で分光測定を行ったことを示すものである。測定結果を含水率増加量（％）については表１に示す。   In FIG. 4, L2 indicates the width of the barrier layer (1 mm, 3 mm or 5 mm). In FIG. 4, L1 is 2 mm, which indicates that the spectroscopic measurement was performed at a position 2 mm from the inside of the barrier layer. The measurement results are shown in Table 1 for the moisture content increase (%).

［実験例２］
上記実験例１の評価用サンプル２０において、バリア層Ｓの代わりに、厚み０．４ｍｍのＥＶＡフィルム（東ソー・ニッケミ社製、メルセンＧ７０５５（商品名））の３枚を積層した３層積層フィルムを用いた以外は同様にして実験用の評価用サンプルを作製し、上記同様の防湿性評価を行った。測定結果を表１に示す。 [Experiment 2]
In the evaluation sample 20 of Experimental Example 1, instead of the barrier layer S, a three-layer laminated film obtained by laminating three sheets of EVA film having a thickness of 0.4 mm (Mersen G7055 (trade name) manufactured by Tosoh Nikkemi Co., Ltd.) An experimental evaluation sample was prepared in the same manner except that it was used, and the same moisture-proof evaluation as described above was performed. The measurement results are shown in Table 1.

なお、当該ＥＶＡフィルムについては、ガラスとの接着力を上述の実験例１と同様の方法にてガラス板との接着性測定用サンプルを作製し測定した結果、１４３．７[Ｎ／２５ｍｍ]であった。一方、得られたフィルムについて、透湿性を上述の実験例１と同様の方法にて測定した結果、１４[ｇ／ｍ２・ｄａｙ]であった。 In addition, about the said EVA film, as a result of producing and measuring the adhesive force with glass by the method similar to the above-mentioned Experimental example 1 and measuring a glass plate, it is 143.7 [N / 25mm]. there were. On the other hand, the moisture permeability of the obtained film was measured by the same method as in Experimental Example 1, and as a result, it was 14 [g / m 2 · day].

[比較実験例１]
上記実験例１の評価用のサンプル２０において、バリア層Ｓの代わりに、厚み０．４ｍｍのＥＶＡフィルム（東ソー・ニッケミ社製、メルセンＧ７０６０（商品名））の３枚を積層した３層積層フィルムを用いた以外は同様にして比較実験用の評価用サンプルを作製し、上記同様の防湿性評価を行った。測定結果を表１に示す。 [Comparative Experiment Example 1]
In the sample 20 for evaluation of Experimental Example 1, instead of the barrier layer S, a three-layer laminated film in which three sheets of an EVA film having a thickness of 0.4 mm (Mersen G7060 (trade name) manufactured by Tosoh Nikkemi Co., Ltd.) are laminated. Samples for evaluation for comparative experiments were produced in the same manner except that was used, and the same moisture-proof evaluation as described above was performed. The measurement results are shown in Table 1.

なお、当該ＥＶＡフィルムについては、ガラスとの接着力を上述の実験例１と同様の方法にてガラス板との接着性測定用サンプルを作製し測定した結果、７４．８[Ｎ／２５ｍｍ]であった。一方、得られたフィルムについて、透湿性を上述の実験例１と同様の方法にて測定した結果、５３[ｇ／ｍ２・ｄａｙ]であった。 In addition, about the said EVA film, as a result of producing and measuring the adhesive force with glass by the method similar to the above-mentioned Experimental example 1 and measuring a glass plate, it is 74.8 [N / 25mm]. there were. On the other hand, as a result of measuring the moisture permeability of the obtained film by the same method as in Experimental Example 1, it was 53 [g / m 2 · day].

[比較実験例２]
上記実験例１の評価用のサンプル２０において、バリア層Ｓの代わりに、厚み０．３８ｍｍのＰＶＢフィルム（イーストマンケミカル社製、ＲＫ１１（商品名））の３枚を積層した３層積層フィルムを用いた以外は同様にして比較実験用の評価用サンプルを作製し、上記同様の防湿性評価を行った。測定結果を表１に示す。 [Comparative Experiment 2]
In the sample 20 for evaluation of the experimental example 1, instead of the barrier layer S, a three-layer laminated film obtained by laminating three sheets of PVB film having a thickness of 0.38 mm (manufactured by Eastman Chemical Co., Ltd., RK11 (trade name)). A sample for evaluation for comparison experiment was prepared in the same manner except that it was used, and the same moisture-proof evaluation as above was performed. The measurement results are shown in Table 1.

なお、当該ＰＶＢフィルムについては、ガラスとの接着力を上述の実験例１と同様の方法にて測定した結果、３８．７[Ｎ／２５ｍｍ]であった。なお、ガラス板との接着性測定用サンプルは、真空バッグ内が−６０ｋＰａ以下の減圧度となるように脱気した条件下にて、温度１１０℃で予備圧着をし、その後温度１１０℃、圧力１．３ＭＰａの圧力下で本圧着を行った以外は、上記実験例１と同じとした。一方、得られたフィルムについて、透湿性を上述の実験例１と同様の方法にて測定した結果、１１０[ｇ／ｍ２・ｄａｙ]であった。 In addition, about the said PVB film, as a result of measuring the adhesive force with glass with the method similar to the above-mentioned Experimental example 1, it was 38.7 [N / 25mm]. The sample for measuring the adhesion to the glass plate was preliminarily pressure-bonded at a temperature of 110 ° C. under a deaerated condition so that the inside of the vacuum bag had a reduced pressure of −60 kPa or less. It was the same as Experimental Example 1 except that the main pressure bonding was performed under a pressure of 1.3 MPa. On the other hand, the moisture permeability of the obtained film was measured by the same method as in Experimental Example 1 and was 110 [g / m 2 · day].

Figure 2017186229
Figure 2017186229

表１から、前記接着性（Ａ）と耐湿性（Ｂ）を示す中間接着層からなる帯状に形成されたバリア層を用いれば、従来合わせガラスにおいて中間接着層に用いられる樹脂を同様に帯状に形成した層を用いた場合に比べて、防湿性に優れることがわかる。   From Table 1, if a barrier layer formed in an intermediate adhesive layer showing the adhesiveness (A) and moisture resistance (B) is used, the resin used for the intermediate adhesive layer in the conventional laminated glass is similarly in the belt shape. It turns out that it is excellent in moisture-proofness compared with the case where the formed layer is used.

［実施例１〜３］
上記で実施形態の一例として説明した図１、２に示す合わせガラス１０と同様の構成の、図５に正面図、図６にそのＹ−Ｙ線断面図を示す合わせガラス１０ｓを以下のように作製した。なお、合わせガラス１０ｓにおいては、ＳＰＤフィルム３ａを用いた。 [Examples 1 to 3]
The laminated glass 10s having the same configuration as the laminated glass 10 shown in FIGS. 1 and 2 described above as an example of the embodiment and shown in FIG. 5 as a front view and as shown in FIG. Produced. In addition, SPD film 3a was used in the laminated glass 10s.

（合わせガラスの作製）
１枚のソーダライムガラスからなるガラス板１Ａ（１５０ｍｍ×１５０ｍｍ、２ｍｍ厚）の上に、１５０×１５０ｍｍ、０．３８ｍｍ厚の上記で作製された接着性樹脂組成物（Ｉａ）のフィルムからなる中間接着層２Ａを、その４辺がガラス板１Ａの４辺に略一致するように配置した。 (Production of laminated glass)
On the glass plate 1A (150 mm × 150 mm, 2 mm thickness) made of one piece of soda lime glass, the intermediate made of the adhesive resin composition (Ia) film of 150 × 150 mm, 0.38 mm thickness prepared above. The adhesive layer 2A was arranged so that its four sides substantially coincided with the four sides of the glass plate 1A.

ＳＰＤフィルム３ａとして、０．３２ｍｍ厚の日立化成社製、ＬＣＦ−１１０３ＤＨＡ ６５（商品名）を１３０×１３０ｍｍの大きさにカットして、その一辺に動作用の２本のバスバー５ａ、５ｂとケーブル（図示せず）を付属したＳＰＤフィルムを準備した。ＳＰＤフィルム３ａのバスバー５ａ、５ｂを有しない隣り合う２辺の位置が、ガラス板１Ａおよび中間接着層２Ａの隣り合う２辺からそれぞれ内側に距離Ｌ３（単位［ｍｍ］）となるようにＳＰＤフィルム３ａを中間接着層２Ａの上に配置した。これにより、ＳＰＤフィルム３ａのバスバー５ａ、５ｂを有する辺とその隣の辺の位置は、対応するガラス板１Ａおよび中間接着層２Ａの辺から、内側に１５０−１３０−Ｌ３＝Ｌ４［ｍｍ］の位置となった。   As SPD film 3a, LCF-1103DHA 65 (trade name) manufactured by Hitachi Chemical Co., Ltd. having a thickness of 0.32 mm is cut into a size of 130 × 130 mm, and two bus bars 5a, 5b for operation and a cable are provided on one side An SPD film attached (not shown) was prepared. The SPD film 3a does not have the bus bars 5a and 5b so that the positions of the two adjacent sides are the distance L3 (unit [mm]) inward from the two adjacent sides of the glass plate 1A and the intermediate adhesive layer 2A. 3a was disposed on the intermediate adhesive layer 2A. Thereby, the position of the side having the bus bars 5a and 5b of the SPD film 3a and the position of the adjacent side are 150-130-L3 = L4 [mm] inward from the corresponding glass plate 1A and the side of the intermediate adhesive layer 2A. Became the position.

ここで、実施例１においてはＬ３を３ｍｍ（Ｌ４は１７ｍｍ）、実施例２においてはＬ３を５ｍｍ（Ｌ４は１５ｍｍ）、実施例３においてはＬ３を１０ｍｍ（Ｌ４は１０ｍｍ）として、それぞれ合わせガラスを作製した。   Here, in Example 1, L3 is 3 mm (L4 is 17 mm), in Example 2, L3 is 5 mm (L4 is 15 mm), and in Example 3, L3 is 10 mm (L4 is 10 mm). Produced.

次いで、中間接着層２Ａの上に、ガラス板１Ａおよび中間接着層２Ａと同一外寸（１５０ｍｍ×１５０ｍｍ）であり、内寸がＳＰＤフィルム３ａと同一（１３０×１３０ｍｍ）の額縁状のバリア層４（４辺にそれぞれ、Ｌ３ｍｍ、Ｌ３ｍｍ、Ｌ４ｍｍ、Ｌ４ｍｍの幅を有する。）を、その４辺がガラス板１Ａの４辺に一致するとともに、内縁がＳＰＤフィルム３ａの外縁と接するように配置した。なお、バリア層４は、０．３８ｍｍ厚の上記で作製された接着性樹脂組成物（Ｉａ）のフィルムにより構成した。   Next, on the intermediate adhesive layer 2A, a frame-shaped barrier layer 4 having the same outer dimensions (150 mm × 150 mm) as the glass plate 1A and the intermediate adhesive layer 2A and the inner dimension being the same (130 × 130 mm) as the SPD film 3a. (The four sides have widths of L3 mm, L3 mm, L4 mm, and L4 mm, respectively) are arranged so that the four sides coincide with the four sides of the glass plate 1A and the inner edge is in contact with the outer edge of the SPD film 3a. In addition, the barrier layer 4 was comprised with the film of the adhesive resin composition (Ia) produced by the above of 0.38 mm thickness.

さらに、バリア層４とＳＰＤフィルム３ａの主面の全体を覆うように、これらの上に、上記中間接着層２Ａで用いたのと同じ接着性樹脂組成物（Ｉａ）のフィルムの１枚を中間接着層２Ｂとして、さらにその上に上記ガラス板１Ａで用いたのと同じガラス板の１枚をガラス板１Ｂとして順にずれがないように重ね合せ、ずれ防止テープで４辺を固定して積層体を作製した。   Furthermore, one of the films of the same adhesive resin composition (Ia) as used in the intermediate adhesive layer 2A is placed on the barrier layer 4 and the SPD film 3a so as to cover the entire main surface. As the adhesive layer 2B, one of the same glass plates used for the glass plate 1A is laminated on the glass plate 1B in order so that there is no deviation, and four sides are fixed with a slip prevention tape, and a laminate. Was made.

この積層体を真空バッグに入れ、真空バッグ内が−６０ｋＰａ以下の減圧度となるように脱気しながら１１０℃で予備圧着を行った後、温度１１０℃、圧力１．３ＭＰaの条件でさらに本圧着を行うことにより、額縁状のバリア層４とその内側にＳＰＤフィルム３ａを有する合わせガラス１０ｓを得た。   This laminate is put into a vacuum bag, pre-pressed at 110 ° C. while degassing so that the inside of the vacuum bag has a reduced pressure of −60 kPa or less, and then further heated under conditions of a temperature of 110 ° C. and a pressure of 1.3 MPa. By performing the pressure bonding, a laminated glass 10s having the frame-like barrier layer 4 and the SPD film 3a on the inside thereof was obtained.

［比較例１〜３］
実施例１〜３における合わせガラス１０ｓの中間接着層２Ａ、中間接着層２Ｂおよびバリア層を、厚さ０．４ｍｍのＥＶＡフィルム（東ソーニッケミ社製、メルセンＧ７０６０（商品名））とした以外は実施例１〜３と同様にして、比較例１〜３の合わせガラスを作製した。 [Comparative Examples 1-3]
Implemented except that the intermediate adhesive layer 2A, the intermediate adhesive layer 2B, and the barrier layer of the laminated glass 10s in Examples 1 to 3 were EVA films having a thickness of 0.4 mm (Mersen G7060 (trade name) manufactured by Tosoh Nickemi Co., Ltd.) The laminated glass of Comparative Examples 1-3 was produced like Example 1-3.

（防湿性評価）
上記実施例１〜３および比較例１〜３で得られた合わせガラスについて、ＳＰＤフィルム３ａのバリア層の幅がＬ３の２辺と接する２辺で形成される角から２０ｍｍ角の部分を測定部（図５中、Ｍで示す。）として、ＢＹＫガードナー社製、ヘイズガードプラスを用いて全光線透過率（Ｔｖ）を測定した。なお、Ｔｖの測定は、ＳＰＤフィルム３ａが透明状態の場合と、着色状態の場合の両方の場合について行った。ＳＰＤフィルム３ａの透明状態、着色状態は、上記合わせガラス１０ｓにおいて、２本のケーブルをＡＣ電源に接続して電源のオン／オフにより、オンのときを透明状態、オフのときを着色状態とした。電源オン時の電圧は１００Ｖとした。 (Dampproof evaluation)
For the laminated glasses obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the part of the SPD film 3a whose barrier layer is 20 mm square from the angle formed by the two sides in contact with the two sides of L3 is a measuring unit. (Indicated as M in FIG. 5), the total light transmittance (Tv) was measured using a haze guard plus manufactured by BYK Gardner. In addition, the measurement of Tv was performed about the case where both the case where the SPD film 3a is a transparent state, and a colored state. The transparent state and the colored state of the SPD film 3a are the transparent state when the two cables are connected to an AC power source and the power is turned on / off in the laminated glass 10s, and the colored state when the power is off. . The voltage when the power was turned on was 100V.

上記の測定で得られたＴｖを初期状態のＴｖ（ｂ）とした。その後、上記実施例１〜３および比較例１〜３で得られた合わせガラスについて、６０℃、湿度９５％ＲＨの恒温恒湿槽中に１０００時間放置する試験を行った。試験後の各合わせガラスを、恒温恒湿槽から取出し常温まで戻した後、上記同様にＳＰＤフィルム３ａが透明状態の場合と、着色状態の場合の両方の場合についてＴｖを測定した。試験後のＴｖをＴｖ（ａ）とした。各例の各条件におけるＴｖ（ａ）およびＴｖ（ｂ）から、下記式（Ｘ）によりＴｖ変化率（％）を求めた。各例の各条件におけるＴｖの初期値（Ｔｖ（ｂ））、試験後の値（Ｔｖ（ａ））および、Ｔｖ変化率（％）を、測定部Ｍ周辺におけるバリア層４の幅Ｌ３とともに表２に示す。
Ｔｖ変化率（％）＝Ｔｖ（ａ）／Ｔｖ（ｂ） × １００ …（Ｘ） Tv obtained by the above measurement was defined as Tv (b) in the initial state. Thereafter, the laminated glass obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was subjected to a test in which the laminated glass was left in a constant temperature and humidity chamber at 60 ° C. and a humidity of 95% RH for 1000 hours. Each laminated glass after the test was taken out from the constant temperature and humidity chamber and returned to room temperature, and then Tv was measured in both cases where the SPD film 3a was in a transparent state and in a colored state as described above. Tv after the test was defined as Tv (a). From the Tv (a) and Tv (b) under each condition in each example, the Tv change rate (%) was obtained by the following formula (X). The initial value of Tv (Tv (b)), the value after the test (Tv (a)), and the Tv change rate (%) in each condition of each example are shown together with the width L3 of the barrier layer 4 around the measurement unit M. It is shown in 2.
Tv change rate (%) = Tv (a) / Tv (b) × 100 (X)

Figure 2017186229
Figure 2017186229

表２から、接着性樹脂組成物（Ｉ）からなる額縁状に形成されたバリア層を用いれば、従来合わせガラスにおいて中間接着層に用いられる樹脂を同様に額縁状に形成した層を用いた場合に比べて、ＳＰＤフィルムの劣化が抑制されることがわかる。   From Table 2, if a barrier layer formed in a frame shape made of the adhesive resin composition (I) is used, a layer in which a resin used for an intermediate adhesive layer in a conventional laminated glass is similarly formed in a frame shape is used. It can be seen that the deterioration of the SPD film is suppressed as compared with FIG.

１０，１０ｓ…合わせガラス、１Ａ，１Ｂ…ガラス板、２Ａ，２Ｂ…中間接着層、３…ＳＰＤフィルム、３ａ…ＳＰＤフィルム、４…バリア層、５ａ，５ｂ…バスバー。 DESCRIPTION OF SYMBOLS 10,10s ... Laminated glass, 1A, 1B ... Glass plate, 2A, 2B ... Intermediate adhesive layer, 3 ... SPD film, 3a ... SPD film, 4 ... Barrier layer, 5a, 5b ... Busbar.

Claims (9)

互いに対向する１対のガラス板と、
前記１対のガラス板の対向面にそれぞれ接する１対の中間接着層と、
前記１対の中間接着層の間の、前記ガラス板の主面における周縁部の少なくとも一部の帯状領域を除く領域に対応する領域内の所定領域に配置される懸濁粒子デバイスフィルムと、
前記１対の中間接着層の間に前記帯状領域に配置され、以下に示す所定の接着性（Ａ）と以下に示す所定の透湿性（Ｂ）とを共に有するバリア層と、
を備える車両用合わせガラス。
接着性（Ａ）：ＪＩＳ Ｋ ６８６４−２：１９９９に準拠し、接着温度１１０℃、試験片の幅２５ｍｍ、試験速度が毎分３００ｍｍ、引き剥がし角度が１８０度の条件下で測定したガラス板に対する接着力が、４０Ｎ／２５ｍｍ以上。
透湿性（Ｂ）：ＪＩＳ Ｚ ０２０８：１９７６に準じて測定した温度４０℃、湿度９０％ＲＨにおける透湿度が５０ｇ／ｍ２・ｄａｙ以下。 A pair of glass plates facing each other;
A pair of intermediate adhesive layers in contact with opposing surfaces of the pair of glass plates,
A suspended particle device film disposed in a predetermined region in a region corresponding to a region excluding at least a part of a belt-like region of a peripheral edge portion of the main surface of the glass plate between the pair of intermediate adhesive layers;
A barrier layer disposed between the pair of intermediate adhesive layers in the belt-like region and having both the following predetermined adhesiveness (A) and the predetermined moisture permeability (B) shown below:
Laminated glass for vehicles comprising
Adhesiveness (A): According to JIS K 6864-2: 1999, with respect to a glass plate measured under conditions of an adhesion temperature of 110 ° C., a test piece width of 25 mm, a test speed of 300 mm per minute, and a peel angle of 180 degrees Adhesive strength is 40N / 25mm or more.
Moisture permeability (B): Moisture permeability at a temperature of 40 ° C. and a humidity of 90% RH measured according to JIS Z 0208: 1976 is 50 g / m 2 · day or less. 前記バリア層の平面形状が額縁状であり、前記懸濁粒子デバイスフィルムは、前記所定領域が前記ガラス板の主面に対応する領域から前記バリア層の配置領域を除く全領域であって、端面が前記バリア層の内側の端面と接するように配置される請求項１記載の車両用合わせガラス。   The planar shape of the barrier layer is a frame shape, and the suspended particle device film is an entire region excluding the region where the barrier layer is disposed from a region corresponding to the main surface of the glass plate, The laminated glass for vehicles according to claim 1, which is disposed so as to be in contact with an inner end face of the barrier layer. 前記1対の中間接着層の少なくとも一方が、前記所定の接着性（Ａ）および前記所定の透湿性（Ｂ）とを共に有する請求項１または２に記載の車両用合わせガラス。   The laminated glass for vehicles according to claim 1 or 2, wherein at least one of the pair of intermediate adhesive layers has both the predetermined adhesiveness (A) and the predetermined moisture permeability (B). 前記バリア層が、芳香族ビニル化合物由来の繰り返し単位を主成分とする、少なくとも２つの重合体ブロック［Ａ］と、鎖状共役ジエン化合物由来の繰り返し単位を主成分とする、少なくとも１つの重合体ブロック［Ｂ］とからなり、全重合体ブロック［Ａ］のブロック共重合体全体に占める質量分率をｗＡとし、全重合体ブロック［Ｂ］のブロック共重合体全体に占める質量分率をｗＢとしたときに、ｗＡとｗＢとの比（ｗＡ：ｗＢ）が３０：７０〜６０：４０であるブロック共重合体［１］の、全不飽和結合の９０％以上を水素化したブロック共重合体水素化物［２］にアルコキシシリル基が導入されてなる、変性ブロック共重合体水素化物［３］を含有する樹脂である、請求項１〜３いずれかに１項に記載の車両用合わせガラス。   The barrier layer has at least two polymer blocks [A] whose main component is a repeating unit derived from an aromatic vinyl compound and at least one polymer whose main component is a repeating unit derived from a chain conjugated diene compound. Block [B], and the mass fraction of the entire polymer block [A] in the entire block copolymer is wA, and the mass fraction of the entire polymer block [B] in the entire block copolymer is wB. Block copolymer [1] in which the ratio of wA to wB (wA: wB) is 30:70 to 60:40, in which 90% or more of all unsaturated bonds are hydrogenated. The laminated glass for vehicles according to any one of claims 1 to 3, which is a resin containing a modified block copolymer hydride [3], in which an alkoxysilyl group is introduced into the combined hydride [2]. . 前記１対の中間接着層の少なくとも一方が、芳香族ビニル化合物由来の繰り返し単位を主成分とする、少なくとも２つの重合体ブロック［Ａ］と、鎖状共役ジエン化合物由来の繰り返し単位を主成分とする、少なくとも１つの重合体ブロック［Ｂ］とからなり、全重合体ブロック［Ａ］のブロック共重合体全体に占める質量分率をｗＡとし、全重合体ブロック［Ｂ］のブロック共重合体全体に占める質量分率をｗＢとしたときに、ｗＡとｗＢとの比（ｗＡ：ｗＢ）が３０：７０〜６０：４０であるブロック共重合体［１］の、全不飽和結合の９０％以上を水素化したブロック共重合体水素化物［２］にアルコキシシリル基が導入されてなる、変性ブロック共重合体水素化物［３］を含有する樹脂である、請求項１〜４いずれか１項に記載の車両用合わせガラス。   At least one of the pair of intermediate adhesive layers is composed mainly of at least two polymer blocks [A] having a repeating unit derived from an aromatic vinyl compound as a main component and a repeating unit derived from a chain conjugated diene compound. The entire block copolymer of the entire polymer block [B] is composed of at least one polymer block [B], and the mass fraction of the entire polymer block [A] in the entire block copolymer is wA. 90% or more of all unsaturated bonds of the block copolymer [1] in which the ratio of wA to wB (wA: wB) is 30: 70-60: 40 5. The resin according to claim 1, which is a resin containing a modified block copolymer hydride [3], in which an alkoxysilyl group is introduced into a hydrogenated block copolymer hydride [2]. Listed car Use laminated glass. 前記バリア層の幅が１０ｍｍ以下である箇所が存在する請求項１〜５のいずれか１項に記載の車両用合わせガラス。   The laminated glass for vehicles of any one of Claims 1-5 in which the location where the width | variety of the said barrier layer is 10 mm or less exists. 前記バリア層の最大幅が１０ｍｍである請求項１〜６のいずれか１項に記載の車両用合わせガラス。   The laminated glass for vehicles according to any one of claims 1 to 6, wherein a maximum width of the barrier layer is 10 mm. 黒色セラミックス層を有しない請求項１〜７のいずれか１項に記載の車両用合わせガラス。   The laminated glass for vehicles according to any one of claims 1 to 7, which does not have a black ceramic layer. 前記１対のガラスと前記１対の中間接着層の間に、機能フィルムを有する請求項１〜８のいずれか１項に記載の車両用合わせガラス。   The laminated glass for vehicles according to any one of claims 1 to 8, wherein a functional film is provided between the pair of glasses and the pair of intermediate adhesive layers.
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