JP2003183060A - Laminated glass and its production method - Google Patents
Laminated glass and its production methodInfo
- Publication number
- JP2003183060A JP2003183060A JP2001379455A JP2001379455A JP2003183060A JP 2003183060 A JP2003183060 A JP 2003183060A JP 2001379455 A JP2001379455 A JP 2001379455A JP 2001379455 A JP2001379455 A JP 2001379455A JP 2003183060 A JP2003183060 A JP 2003183060A
- Authority
- JP
- Japan
- Prior art keywords
- laminated glass
- resin composition
- group
- glass
- vinyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B32B17/1055—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
- B32B17/10697—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 being cross-linked
-
- 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
- B32B17/10788—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 containing ethylene vinylacetate
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、合わせガラス、特
に自動車、航空機等のウインドウ用ガラス、建築物の窓
ガラス等に用いる合わせガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass, and more particularly to a laminated glass used for window glass of automobiles, airplanes, etc., and window glass of buildings.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】自動
車、航空機等のウインドウ用ガラス、建築物の窓ガラス
等には、従来から合わせガラスが広く用いられている。
合わせガラスは、通常２枚のガラス板の間に樹脂膜（中
間膜）が挟持されており、衝撃等に対して高い安全性を
有することから、上記のような用途で安全ガラスとして
使用されている。2. Description of the Related Art Conventionally, laminated glass has been widely used as window glass for automobiles, aircrafts and the like, and window glass for buildings.
A laminated glass usually has a resin film (intermediate film) sandwiched between two glass plates and has high safety against impact and the like, and thus is used as a safety glass in the above-mentioned applications.
【０００３】合わせガラスは、外部から衝撃が加えられ
た場合に、ガラスの部分は破損するが、ガラス板間の中
間膜は、容易には破損されないため、破損したガラスは
中間膜に貼着されたままで、ガラスの破片が周囲に飛散
することはほとんどない。In laminated glass, when an impact is applied from the outside, the glass portion is damaged, but the interlayer film between the glass plates is not easily damaged. Therefore, the damaged glass is attached to the interlayer film. If left untouched, glass fragments are unlikely to scatter around.
【０００４】合わせガラスが、上記のような安全ガラス
としての機能を発揮するには、ガラス板と中間膜の接着
力をある範囲に調整することが必要である。ガラス板と
中間膜との接着力が小さい場合は、外部からの衝撃によ
り破損したガラス板が中間膜から剥がれて飛散しやす
く、一方、接着力が大きい場合はガラス板と中間膜が衝
撃と同時に共に破損して、破片が飛散してしまう。In order for the laminated glass to exhibit the function as the safety glass as described above, it is necessary to adjust the adhesive force between the glass plate and the interlayer film within a certain range. If the adhesive strength between the glass plate and the interlayer film is small, the glass plate damaged by an external impact is likely to peel off from the interlayer film and scatter. Both are damaged and the fragments are scattered.
【０００５】また、合わせガラスの中間膜は、上記機能
を有し、更にガラスの透明性を低下させないように、そ
れ自身に高い透明性が要求される。Further, the interlayer film of the laminated glass has the above-mentioned function and is required to have high transparency by itself so as not to lower the transparency of the glass.
【０００６】このような合わせガラスの中間膜として
は、ポリビニルアセタールと可塑剤とを主成分とする膜
が代表的であるが、上述のような特性を高いレベルで満
足する中間膜はまだ得られていない。As an interlayer film of such a laminated glass, a film containing polyvinyl acetal and a plasticizer as a main component is typical, but an interlayer film satisfying the above-mentioned characteristics at a high level is not yet obtained. Not not.
【０００７】特開平１１−１４７７３６号公報では、ポ
リビニルアセタール樹脂、可塑剤及び有機過酸化物を含
む組成物から形成された中間膜により合わせガラスを得
ているが、この中間膜は、中間膜の圧着時に１５０℃程
度の温度が必要であり、この場合、ガラスと樹脂材料と
の膨張係数の違いから反り、剥離等が発生してしまうこ
とがある。In Japanese Patent Application Laid-Open No. 11-147736, a laminated glass is obtained by an intermediate film formed of a composition containing a polyvinyl acetal resin, a plasticizer and an organic peroxide. A temperature of about 150 ° C. is required at the time of pressure bonding, and in this case, warping or peeling may occur due to the difference in expansion coefficient between the glass and the resin material.
【０００８】また、熱硬化性中間膜としては、架橋エチ
レン−酢酸ビニル（ＥＶＡ）共重合体が用いられている
が、開始剤であるベンゾイルパーオキサイドの耐光性が
悪いという問題があり、得られた合わせガラスは屋外で
の使用には向かず、ベンゾイルパーオキサイド以外の有
機過酸化物を使用した中間膜も使用されていたが、物質
の安全性等の問題から使用に制約がある。Further, a cross-linked ethylene-vinyl acetate (EVA) copolymer is used as the thermosetting intermediate film, but there is a problem that the light resistance of benzoyl peroxide as an initiator is poor, and thus it is obtained. The laminated glass was not suitable for outdoor use, and an intermediate film using an organic peroxide other than benzoyl peroxide was also used, but there is a limitation in use due to problems such as material safety.
【０００９】本発明は、上記事情に鑑みなされたもので
あり、太陽光により強い紫外線が照射される屋外等にお
いても耐光性に優れ、硬化時の加熱による反り、剥離の
発生がない合わせガラス及びその製造方法を提供するこ
とを目的とする。The present invention has been made in view of the above circumstances, and has excellent light resistance even in the outdoors where strong ultraviolet rays are irradiated by sunlight, and does not cause warping or peeling due to heating during curing, and a laminated glass. It is an object to provide a manufacturing method thereof.
【００１０】[0010]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するため鋭意検討を重ねた結
果、エチレン−酢酸ビニル樹脂、ベンゾイルパーオキサ
イド系硬化剤、ベンゾフェノン系紫外線吸収剤及びアク
リロキシ基、メタクリロキシ基又はアリル基を有する化
合物を含有する樹脂組成物の硬化物からなる中間膜がガ
ラス板に挟持され、高圧水銀灯による１００時間の耐光
性促進試験の黄変度が３以下である合わせガラスが耐光
性に優れており、硬化時の加熱による反り、剥離の発生
がないこと、また、上記合わせガラスが、中間膜の硬化
温度を１２０℃以下とすることにより得られることを知
見し、本発明をなすに至った。Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that ethylene-vinyl acetate resin, benzoyl peroxide-based curing agent, and benzophenone-based ultraviolet absorbing agent. An intermediate film made of a cured product of a resin composition containing an agent and a compound having an acryloxy group, a methacryloxy group or an allyl group is sandwiched between glass plates, and a yellowing degree in a light resistance accelerated test of 100 hours by a high pressure mercury lamp is 3 or less. That the laminated glass is excellent in light resistance and does not warp or peel due to heating during curing, and that the laminated glass can be obtained by setting the curing temperature of the interlayer film to 120 ° C. or less. They found out the present invention and made the present invention.
【００１１】即ち、本発明は、エチレン−酢酸ビニル樹
脂、ベンゾイルパーオキサイド系硬化剤、ベンゾフェノ
ン系紫外線吸収剤、及びアクリロキシ基、メタクリロキ
シ基又はアリル基を有する化合物を含有する樹脂組成物
の硬化物からなる中間膜がガラス板に挟持されてなる合
わせガラスであって、高圧水銀灯による１００時間の耐
光性促進試験の黄変度が３以下であることを特徴とする
合わせガラス及びその製造方法を提供する。That is, the present invention relates to a cured product of a resin composition containing an ethylene-vinyl acetate resin, a benzoyl peroxide-based curing agent, a benzophenone-based UV absorber, and a compound having an acryloxy group, a methacryloxy group or an allyl group. A laminated glass in which the intermediate film is sandwiched between glass plates, the yellowing degree of which is 100 or less in a light resistance accelerated test with a high pressure mercury lamp for 3 hours or less, and a method for producing the same. .
【００１２】以下、本発明につき更に詳述する。本発明
の合わせガラス用樹脂組成物は、エチレン−酢酸ビニル
樹脂、ベンゾイルパーオキサイド系硬化剤、ベンゾフェ
ノン系紫外線吸収剤、及びアクリロキシ基、メタクリロ
キシ基又はアリル基を有する化合物を含有するものであ
る。The present invention will be described in more detail below. The resin composition for laminated glass of the present invention contains an ethylene-vinyl acetate resin, a benzoyl peroxide-based curing agent, a benzophenone-based ultraviolet absorber, and a compound having an acryloxy group, a methacryloxy group or an allyl group.
【００１３】本発明の樹脂組成物のエチレン−酢酸ビニ
ル樹脂とは、エチレンと酢酸ビニルの共重合体からなる
樹脂であり、従来公知のエチレン−酢酸ビニル樹脂を用
いることができるが、特に、架橋性エチレン−酢酸ビニ
ル共重合体からなる樹脂が好ましい。また、共重合体の
酢酸ビニル含有量が１０〜５０重量％、特に１５〜４５
重量％であるものが好ましい。酢酸ビニル含有量が１０
重量％未満では、中間膜の透明度が不十分となる恐れが
あり、５０重量％を超えると、透明度は良好になるが耐
貫通性が悪くなったり、樹脂の軟化温度が低く貯蔵が困
難になる場合がある。The ethylene-vinyl acetate resin of the resin composition of the present invention is a resin composed of a copolymer of ethylene and vinyl acetate, and a conventionally known ethylene-vinyl acetate resin can be used, but particularly, a cross-linked resin. Resins composed of a soluble ethylene-vinyl acetate copolymer are preferred. Further, the vinyl acetate content of the copolymer is 10 to 50% by weight, especially 15 to 45%.
It is preferably in the range of wt%. Vinyl acetate content is 10
If it is less than 10% by weight, the transparency of the interlayer film may be insufficient, and if it exceeds 50% by weight, the transparency is good but the penetration resistance is poor, and the softening temperature of the resin is low and storage becomes difficult. There are cases.
【００１４】また、本発明の樹脂組成物には、組成物を
硬化させるための硬化剤としてベンゾイルパーオキサイ
ド系硬化剤を添加する。上記硬化剤としては、７０℃以
上の温度で分解してラジカルを発生するものであればい
ずれも使用可能であるが、半減期１０時間の分解温度が
５０℃以上のものが好ましく、調製条件、成膜温度、硬
化（貼り合わせ）温度、被着体の耐熱性、貯蔵安定性を
考慮して適宜選択できる。A benzoyl peroxide type curing agent is added to the resin composition of the present invention as a curing agent for curing the composition. As the above-mentioned curing agent, any one can be used as long as it decomposes at a temperature of 70 ° C. or higher to generate a radical, but it is preferable that the decomposition temperature with a half-life of 10 hours is 50 ° C. or higher. It can be appropriately selected in consideration of the film forming temperature, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability.
【００１５】使用可能なベンゾイルパーオキサイド系硬
化剤としては、例えば、ベンゾイルパーオキサイド、
２，５−ジメチルヘキシル−２，５−ビスパーオキシベ
ンゾエート、ｐ−クロロベンゾイルパーオキサイド、ｍ
−トルオイルパーオキサイド、２，４−ジクロロベンゾ
イルパーオキサイド、ｔ−ブチルパーオキシベンゾエー
ト等が挙げられる。ベンゾイルパーオキサイド系硬化剤
は１種でも２種以上を組み合わせて使用してもよく、そ
の配合量は、エチレン−酢酸ビニル樹脂１００重量部に
対して０．１〜５重量部であることが好ましい。また、
上記で例示したもの以外のパーオキサイドと混合して用
いることも可能である。Examples of benzoyl peroxide type curing agents that can be used include benzoyl peroxide and
2,5-dimethylhexyl-2,5-bisperoxybenzoate, p-chlorobenzoyl peroxide, m
-Toluoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxybenzoate and the like can be mentioned. The benzoyl peroxide-based curing agents may be used alone or in combination of two or more, and the compounding amount thereof is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin. . Also,
It is also possible to use it by mixing with a peroxide other than those exemplified above.
【００１６】更に、本発明の樹脂組成物には、ベンゾフ
ェノン系紫外線吸収剤を配合する。上記ベンゾフェノン
系紫外線吸収剤としては、公知のベンゾフェノン系紫外
線吸収剤を用いることができるが、例えば、２−ヒドロ
キシ−４−メトキシベンゾフェノン、２−ヒドロキシ−
４−ｎ−ドデシロキシベンゾフェノン、２，４−ジヒド
ロキシベンゾフェノン、２，２’−ジヒドロキシ−４−
メトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オ
クトキシベンゾフェノン等が好ましく挙げられる。な
お、上記ベンゾフェノン系紫外線吸収剤の配合量は、エ
チレン−酢酸ビニル樹脂１００重量部に対して０．０１
〜５重量部であることが好ましい。Further, the resin composition of the present invention contains a benzophenone type ultraviolet absorber. As the benzophenone-based UV absorber, a known benzophenone-based UV absorber can be used, and examples thereof include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-.
4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-
Preferable examples include methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone. The blending amount of the benzophenone-based ultraviolet absorber is 0.01 with respect to 100 parts by weight of ethylene-vinyl acetate resin.
It is preferably ˜5 parts by weight.
【００１７】また更に、本発明の樹脂組成物には、中間
膜の種々の物性（機械的強度、接着性、透明性等の光学
的特性、耐熱性、耐光性、架橋速度等）の改良又は調
整、特に、機械的強度の改良のため、アクリロキシ基、
メタクリロキシ基又はアリル基を有する化合物を添加す
る。Furthermore, the resin composition of the present invention is improved or improved in various physical properties of the intermediate film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, and crosslinking rate). For adjustment, especially for improving mechanical strength, an acryloxy group,
A compound having a methacryloxy group or an allyl group is added.
【００１８】アクリロキシ基又はメタクリロキシ基を有
する化合物としては、一般にアクリル酸又はメタクリル
酸誘導体であり、例えば、アクリル酸又はメタクリル酸
のエステルやアミドを挙げることができる。エステル残
基の例としては、メチル基、エチル基、ドデシル基、ス
テアリル基、ラウリル基等の直鎖状のアルキル基、シク
ロヘキシル基、テトラヒドロフルフリル基、アミノエチ
ル基、２−ヒドロキシエチル基、３−ヒドロキシプロピ
ル基、３−クロロ−２−ヒドロキシプロピル基等を挙げ
ることができる。The compound having an acryloxy group or a methacryloxy group is generally an acrylic acid or methacrylic acid derivative, and examples thereof include esters or amides of acrylic acid or methacrylic acid. Examples of the ester residue include linear alkyl groups such as methyl group, ethyl group, dodecyl group, stearyl group and lauryl group, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3 -Hydroxypropyl group, 3-chloro-2-hydroxypropyl group and the like can be mentioned.
【００１９】また、グリセリン、エチレングリコール、
トリエチレングリコール、ポリプロピレングリコール、
ポリエチレングリコール、トリメチロールプロパン、ペ
ンタエリスリトール等の多価アルコール１分子とアクリ
ル酸又はメタクリル酸１分子又は２分子以上とがエステ
ル化したエステルを挙げることもできる。Further, glycerin, ethylene glycol,
Triethylene glycol, polypropylene glycol,
An ester obtained by esterifying one molecule of a polyhydric alcohol such as polyethylene glycol, trimethylolpropane, or pentaerythritol with one or more molecules of acrylic acid or methacrylic acid can also be mentioned.
【００２０】一方、アリル基を有する化合物としてはジ
アリルフタレート、トリアリルイソシアヌレート、トリ
アリルシアヌレート等が挙げられる。On the other hand, examples of the compound having an allyl group include diallyl phthalate, triallyl isocyanurate and triallyl cyanurate.
【００２１】なお、上記化合物は、単独で使用しても、
２種以上組み合わせて用いてもよく、その配合量は、エ
チレン−酢酸ビニル樹脂１００重量部に対して０．５〜
２０重量部、特に０．５〜２０重量部であることが好ま
しい。配合量が０．５重量部未満の場合、中間膜の物性
（機械的強度、接着性、光学特性、耐熱性、耐光性等）
が十分に発現されない恐れがあり、また２０重量部を超
えると組成物の調製時の作業性や中間膜の成膜性が悪化
する場合がある。Even if the above compounds are used alone,
You may use it in combination of 2 or more types, and the compounding quantity is 0.5 to 100 weight part of ethylene vinyl acetate resins.
It is preferably 20 parts by weight, particularly 0.5 to 20 parts by weight. When the compounding amount is less than 0.5 part by weight, the physical properties of the interlayer film (mechanical strength, adhesiveness, optical characteristics, heat resistance, light resistance, etc.)
May not be sufficiently expressed, and if it exceeds 20 parts by weight, workability during preparation of the composition and film forming property of the intermediate film may be deteriorated.
【００２２】本発明の樹脂組成物には、更に、接着促進
剤を添加することが好ましい。接着促進剤は、樹脂組成
物の接着性を向上させるために添加することができ、従
来公知のものを用いることが可能であるが、例えば、γ
−クロロプロピルトリメトキシシラン、ビニルトリクロ
ロシラン、ビニルトリエトキシシラン、ビニル−トリス
（β−メトシキエトキシ）シラン、γ−メタクリロキシ
プロピルトリメトキシシラン、β−（３，４−エトキシ
シクロヘキシル）エチル−トリメトキシシラン、γ−グ
リシドキシプロピルトリメトキシシラン、ビニルトリア
セトキシシラン、γ−メルカプトプロピルトリメトキシ
シラン、γ−アミノプロピルトリエトキシシラン、Ｎ−
β−（アミノエチル）−γ−アミノプロピルトリメトキ
シシラン等のシランカップリング剤が好ましく挙げられ
る。It is preferable to add an adhesion promoter to the resin composition of the present invention. The adhesion promoter can be added to improve the adhesiveness of the resin composition, and conventionally known compounds can be used. For example, γ
-Chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-ethoxycyclohexyl) ethyl-tri Methoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
Preferable examples are silane coupling agents such as β- (aminoethyl) -γ-aminopropyltrimethoxysilane.
【００２３】なお、上記接着促進剤は、単独で使用して
も、２種以上組み合わせて用いてもよく、その配合量
は、エチレン−酢酸ビニル樹脂１００重量部に対して
０．０１〜５重量部であることが好ましい。The above adhesion promoters may be used alone or in combination of two or more kinds, and the compounding amount thereof is 0.01 to 5 parts by weight with respect to 100 parts by weight of ethylene-vinyl acetate resin. It is preferably part.
【００２４】また、本発明の樹脂組成物には、耐光性の
向上のために、光安定剤を添加することができる。光安
定剤としてはヒンダードアミン系と呼ばれる光安定剤を
用いることが好ましく、例えば、ＬＡ−５２、ＬＡ−５
７、ＬＡ−６２、ＬＡ−６３ＬＡ―６３ｐ、ＬＡ−６
７、ＬＡ−６８（いずれも旭電化（株）製）、Ｔｉｎｕ
ｖｉｎ ７４４、Ｔｉｎｕｖｉｎ ７７０、Ｔｉｎｕｖ
ｉｎ ７６５、Ｔｉｎｕｖｉｎ １４４、Ｔｉｎｕｖｉ
ｎ ６２２ＬＤ、ＣＨＩＭＡＳＳＯＲＢ ９４４ＬＤ
（いずれもチバ・ガイギー社製）、ＵＶ−３０３４
（Ｂ．Ｆ．グッドリッチ社製）等を挙げることができ
る。なお、上記光安定剤は、単独で使用しても、２種以
上組み合わせて用いてもよく、その配合量は、エチレン
−酢酸ビニル樹脂１００重量部に対して０．０１〜５重
量部であることが好ましい。A light stabilizer may be added to the resin composition of the present invention in order to improve light resistance. As the light stabilizer, it is preferable to use a light stabilizer called a hindered amine type, for example, LA-52, LA-5.
7, LA-62, LA-63LA-63p, LA-6
7, LA-68 (all manufactured by Asahi Denka Co., Ltd.), Tinu
vin 744, Tinuvin 770, Tinuv
in 765, Tinuvin 144, Tinuvi
n 622LD, CHIMASSORB 944LD
(All manufactured by Ciba-Geigy), UV-3034
(Manufactured by BF Goodrich) and the like. The light stabilizers may be used alone or in combination of two or more, and the compounding amount thereof is 0.01 to 5 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate resin. It is preferable.
【００２５】以上の添加剤のほか、本発明には、老化防
止剤、染料、加工助剤等を本発明の効果に支障をきたさ
ない範囲で用いてもよい。In addition to the above additives, antiaging agents, dyes, processing aids and the like may be used in the present invention within a range that does not impair the effects of the present invention.
【００２６】本発明の合わせガラスは、上記樹脂組成物
からなる中間膜の硬化物がガラス板に挟持されてなる合
わせガラスであって、高圧水銀灯による１００時間の耐
光性促進試験の黄変度が３以下、好ましくは２以下のも
のである。上記耐光性促進試験とは、１００ｍＷ／ｃｍ
2高圧水銀灯を用いたＪＩＳ Ｒ ３２１２記載の耐光
性試験であり、黄変度はＪＩＳ Ｋ ７１０３記載の方
法に準拠して測定した試験前後の黄色度（ＹＩ：イエロ
ーインデックス 下記式参照）の差である。The laminated glass of the present invention is a laminated glass in which a cured product of an interlayer film made of the above resin composition is sandwiched between glass plates, and has a yellowing degree in a 100 hour light resistance accelerated test using a high pressure mercury lamp. It is 3 or less, preferably 2 or less. The light resistance accelerated test is 100 mW / cm
2 It is a light resistance test according to JIS R 3212 using a high pressure mercury lamp, and the degree of yellowing is the difference in yellowness before and after the test (YI: yellow index, refer to the formula below) measured according to the method described in JIS K 7103. is there.
【００２７】[0027]
【数１】
（Ｘ，Ｙ，Ｚ…標準光Ｃにおける試験用試料又は試験片
の三刺激値）
黄変度が３を超えると、屋外で合わせガラスを使用した
場合、変色が激しく実用的な合わせガラスとはならな
い。[Equation 1] (X, Y, Z ... Tristimulus value of test sample or test piece under standard light C) When the degree of yellowing exceeds 3, when laminated glass is used outdoors, discoloration is severe and it is a practical laminated glass. I won't.
【００２８】本発明の合わせガラスの製造には、従来公
知の製造方法が適用できるが、例えば、上述の樹脂組成
物の各成分をロールミル等にて十分に混和し、例えば、
通常の押出成形、カレンダー成形等により成形して得た
シート、又は樹脂組成物を溶剤に溶解させ、この溶液を
適当な塗布機（コーター）で適当な支持体上に塗布、乾
燥して得た塗膜状のシート等を２枚のガラス板間に挟み
込み、真空脱気により中間膜とガラス板との間の空気を
脱気し、加熱下で予備圧着し、更に、オートクレーブ中
で加圧加熱処理して、樹脂層を架橋硬化させることによ
り得ることができるが、上記樹脂組成物の硬化温度を１
２０℃以下、特に７０〜１２０℃、とりわけ８０〜１１
０℃とすることが好ましい。硬化温度が１２０℃を超え
ると、合わせガラスに反りや剥離が発生する恐れがあ
る。Conventionally known production methods can be applied to the production of the laminated glass of the present invention. For example, the components of the resin composition described above are thoroughly mixed by a roll mill or the like, and, for example,
A sheet obtained by molding by ordinary extrusion molding, calender molding, or the like, or a resin composition is dissolved in a solvent, and the solution is applied onto an appropriate support by an appropriate coating machine (coater) and dried. A film-like sheet is sandwiched between two glass plates, the air between the interlayer film and the glass plates is degassed by vacuum degassing, pre-compression bonding is performed under heating, and pressure heating is performed in an autoclave. It can be obtained by treating the resin layer to crosslink and cure it, but the curing temperature of the resin composition is 1
20 ° C or less, especially 70 to 120 ° C, especially 80 to 11
The temperature is preferably 0 ° C. If the curing temperature exceeds 120 ° C., the laminated glass may warp or peel.
【００２９】なお、合わせガラスのガラス板表面には、
金属及び／又は金属酸化物からなる透明の導電層を設け
ても良い。On the surface of the glass plate of the laminated glass,
A transparent conductive layer made of metal and / or metal oxide may be provided.
【００３０】[0030]
【実施例】以下、実施例及び比較例を挙げて本発明を具
体的に説明するが、本発明は下記実施例に限定されるも
のではない。The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００３１】［実施例１〜５、比較例１〜３］表１に示
す配合成分をロールミルにて５５℃で混練して樹脂組成
物を調製し、得られた組成物を２枚のＰＥＴフィルムの
間に挟んで７０℃、１０分の条件でプレス成形し、放冷
後、ＰＥＴフィルムを剥がして厚さ０．８ｍｍのシート
を得た。[Examples 1 to 5 and Comparative Examples 1 to 3] The compounding components shown in Table 1 were kneaded in a roll mill at 55 ° C to prepare a resin composition, and the obtained composition was used as two PET films. It was sandwiched between and pressed at 70 ° C. for 10 minutes, allowed to cool, and the PET film was peeled off to obtain a sheet having a thickness of 0.8 mm.
【００３２】次に、洗浄乾燥した３ｍｍ厚の２枚のガラ
ス板の間に上記シートを挟み、これをゴム袋に入れて真
空脱気し、８０℃の温度で予備圧着する。更に、これを
オートクレーブに入れ、圧力５ｋｇｆ／ｃｍ2、温度１
００℃の条件で３０分間加圧加熱処理して、合わせガラ
スを得た。合わせガラスの諸特性を試験した結果を表１
に併記する。Next, the above sheet is sandwiched between two glass plates having a thickness of 3 mm that have been washed and dried, placed in a rubber bag, deaerated under vacuum, and pre-pressed at a temperature of 80 ° C. Furthermore, this was put into an autoclave, and the pressure was 5 kgf / cm 2 and the temperature was 1
Pressure heat treatment was performed for 30 minutes under the condition of 00 ° C. to obtain a laminated glass. Table 1 shows the results of testing various properties of the laminated glass.
Also described in.
【００３３】[0033]
【表１】 [Table 1]
【００３４】ＵＲ７５０Ｒ：エチレン−酢酸ビニル樹脂
（東ソー（株）製）
ナイパーＦＦ：ベンゾイルパーオキサイド（日本油脂
（株）製）
ユビナールＤ−４９：２，２’−ジヒドロキシ−４，
４’−ジメトキシベンゾフェノン（ＢＡＳＦ社製）
ＫＥＭＩＳＯＲＢ１０，ＫＥＭＩＳＯＲＢ１１：ベンゾ
フェノン系紫外線吸収剤（ケミプロ化成（株）製）
スミソルブ１３０：ベンゾフェノン系紫外線吸収剤（住
友化学工業（株）製）
スミソルブ２５０：ベンゾトリアゾール系紫外線吸収剤
（住友化学工業（株）
製）
ＬＡ−３６：ベンゾトリアゾール系紫外線吸収剤（旭電
化工業（株）製）
ＬＡ−６３ｐ：光安定剤（旭電化工業（株）製）
ＴＭＰＴ：トリメチロールプロパンメタクリレート（新
中村化学工業（株）製）
ＴＡＩＣ：トリアリルイソシアヌレート（日本化成
（株）製）
ＫＢＭ５０３：γ−メタクリロキシプロピルトリメトキ
シシラン（信越化学工業（株）製）
ＬＴＰ−２：リン酸エステルポリマー（川研ファインケ
ミカル（株）製）UR750R: ethylene-vinyl acetate resin (manufactured by Tosoh Corp.) Niper FF: benzoyl peroxide (manufactured by NOF CORPORATION) Ubinal D-49: 2,2'-dihydroxy-4,
4'-dimethoxybenzophenone (manufactured by BASF) KEMISORB10, KEMISORB11: Benzophenone-based UV absorber (manufactured by Chemipro Kasei Co., Ltd.) Sumisolv 130: Benzophenone-based UV absorber (manufactured by Sumitomo Chemical Co., Ltd.) Sumisolv 250: Benzotriazole-based UV absorber (Sumitomo Chemical Co., Ltd.) LA-36: Benzotriazole-based UV absorber (Asahi Denka Kogyo KK) LA-63p: Light stabilizer (Asahi Denka Kogyo KK) TMPT: Bird Methylolpropane methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) KBM503: γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) LTP-2: Phosphate ester polymer (Kawaken Fine Chemicals (Made by Co., Ltd.)
【００３５】試験方法
キュラスト：キュラスト試験機を用い、サンプル量５
ｇ、温度１００℃で、３０分及び６０分のトルク値（ｋ
ｇｆ・ｃｍ）を測定。
接着力：得られた合わせガラスを２５ｍｍ幅の短冊状に
裁断し、１８０°ピーリング試験と同様にして引っ張り
試験機にて１００ｍｍ／分の引張速度で剥離強度を測
定。
全光線透過率：ＪＩＳ Ｒ ３２１２記載の可視光線透
過率試験に準拠して測定。
ＹＩ：カラーコンピューター（スガ試験機（株）製）を
用いて測定。 Test method Curast: Sample amount 5 using a Curast tester
g, temperature 100 ° C., torque values (k
gf · cm) is measured. Adhesive strength: The obtained laminated glass was cut into strips with a width of 25 mm, and the peel strength was measured by a tensile tester at a pulling speed of 100 mm / min in the same manner as in the 180 ° peeling test. Total light transmittance: Measured in accordance with the visible light transmittance test described in JIS R 3212. YI: Measured using a color computer (manufactured by Suga Test Instruments Co., Ltd.).
【００３６】表１から実施例においては、黄変が少なく
光学的歪みの少ない合わせガラスが得られたことがわか
る。From Table 1, it can be seen that in the Examples, a laminated glass having less yellowing and less optical distortion was obtained.
【００３７】[0037]
【発明の効果】本発明の合わせガラスは、耐光性に優れ
ており、反りや剥離の発生がない合わせガラスを得るこ
とができる。INDUSTRIAL APPLICABILITY The laminated glass of the present invention is excellent in light resistance, and it is possible to obtain a laminated glass which is free from warpage and peeling.
フロントページの続き (72)発明者 森村 泰大 東京都小平市小川東町３−１−１ Ｆターム(参考） 4G061 AA02 AA04 AA29 AA30 BA01 BA02 CA02 CB16 CD02 CD18 DA23 DA32 DA38 DA46 Continued front page (72) Inventor Taidai Morimura 3-1-1 Ogawahigashi-cho, Kodaira-shi, Tokyo F-term (reference) 4G061 AA02 AA04 AA29 AA30 BA01 BA02 CA02 CB16 CD02 CD18 DA23 DA32 DA38 DA46
Claims (4)
パーオキサイド系硬化剤、ベンゾフェノン系紫外線吸収
剤、及びアクリロキシ基、メタクリロキシ基又はアリル
基を有する化合物を含有する樹脂組成物からなる中間膜
の硬化物がガラス板に挟持されてなる合わせガラスであ
って、高圧水銀灯による１００時間の耐光性促進試験の
黄変度が３以下であることを特徴とする合わせガラス。1. A cured product of an intermediate film comprising an ethylene-vinyl acetate resin, a benzoyl peroxide-based curing agent, a benzophenone-based ultraviolet absorber, and a resin composition containing a compound having an acryloxy group, a methacryloxy group or an allyl group. A laminated glass sandwiched between glass plates, which has a yellowing degree of 3 or less in a 100-hour light resistance accelerated test using a high-pressure mercury lamp.
ることを特徴とする請求項１記載の合わせガラス。2. The laminated glass according to claim 1, wherein the resin composition further contains an adhesion promoter.
ことを特徴とする請求項１又は２記載の合わせガラス。3. The laminated glass according to claim 1 or 2, wherein the resin composition further contains a light stabilizer.
の硬化物がガラスに挟持されてなる合わせガラスの製造
方法であって、該中間膜の硬化温度が１２０℃以下であ
ることを特徴とする請求項１乃至３のいずれか１項記載
の合わせガラスの製造方法。4. A method for producing a laminated glass, comprising a cured product of an intermediate film formed by molding a resin composition into a sheet, and sandwiching the cured product between the glasses, wherein the curing temperature of the intermediate film is 120 ° C. or lower. The method for producing a laminated glass according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001379455A JP2003183060A (en) | 2001-12-13 | 2001-12-13 | Laminated glass and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001379455A JP2003183060A (en) | 2001-12-13 | 2001-12-13 | Laminated glass and its production method |
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| Publication Number | Publication Date |
|---|---|
| JP2003183060A true JP2003183060A (en) | 2003-07-03 |
Family
ID=27591039
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005029588A (en) * | 2003-07-07 | 2005-02-03 | Bridgestone Corp | Transparent film |
| JP2009190947A (en) * | 2008-02-15 | 2009-08-27 | Sekisui Chem Co Ltd | Method for manufacturing laminated glass and laminate glass |
-
2001
- 2001-12-13 JP JP2001379455A patent/JP2003183060A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005029588A (en) * | 2003-07-07 | 2005-02-03 | Bridgestone Corp | Transparent film |
| JP2009190947A (en) * | 2008-02-15 | 2009-08-27 | Sekisui Chem Co Ltd | Method for manufacturing laminated glass and laminate glass |
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