JPH07172878A - Intermediate film for laminated glass - Google Patents
Intermediate film for laminated glassInfo
- Publication number
- JPH07172878A JPH07172878A JP32468593A JP32468593A JPH07172878A JP H07172878 A JPH07172878 A JP H07172878A JP 32468593 A JP32468593 A JP 32468593A JP 32468593 A JP32468593 A JP 32468593A JP H07172878 A JPH07172878 A JP H07172878A
- Authority
- JP
- Japan
- Prior art keywords
- laminated glass
- resin film
- resin
- film
- parts
- 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
Landscapes
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、合わせガラス用中間膜
に関する。TECHNICAL FIELD The present invention relates to an interlayer film for laminated glass.
【０００２】[0002]
【従来の技術】従来、ガラス板間に中間膜が挟着されて
なる合わせガラスは、衝撃を受けて破損する際、ガラス
の破片が飛び散らず安全であるため、車輌、航空機、建
築物などの窓ガラス等に広く使用されている。このよう
な合わせガラスに用いられる中間膜のうち、可塑剤によ
り可塑化されたポリビニルブチラール樹脂中間膜は、ガ
ラスとの優れた接着性、強靭な引っ張り強度、高い透明
性を兼ね備えており、特に車輌の窓ガラスとして好適で
ある。2. Description of the Related Art Conventionally, a laminated glass having an interlayer film sandwiched between glass plates is safe because it does not scatter glass fragments when it is damaged by a shock and is not scattered. Widely used for window glass, etc. Among the interlayer films used for such laminated glass, the polyvinyl butyral resin interlayer film plasticized with a plasticizer has excellent adhesion to glass, tough tensile strength, and high transparency, and is particularly suitable for vehicles. It is suitable as a window glass.
【０００３】しかし、上記可塑化されたポリビニルブチ
ラール樹脂中間膜からなる合わせガラスでは、吸湿する
ことにより接着力が低下し、周辺からガラスと中間膜が
界面剥離していく現象が起こるという問題がある。However, in the laminated glass made of the plasticized polyvinyl butyral resin intermediate film, there is a problem in that the adhesive force is lowered by absorbing moisture, and a phenomenon occurs in which the glass and the intermediate film are separated from the periphery from the interface. .
【０００４】吸湿時の接着性が低下少ない合わせガラス
用中間膜として、特公昭４７−１６８２６号公報には、
エチレン／酢酸ビニル共重合体（以下「ＥＶＡ」とい
う）の鹸化物を用いた中間膜、特開昭４９−９９６１４
号公報には、中間膜とガラスの間に珪素化合物の被膜を
形成する合わせガラスが開示されている。Japanese Patent Publication No. 16826/1987 discloses an interlayer film for laminated glass, which has a small decrease in adhesiveness when absorbing moisture.
An intermediate film using a saponified product of an ethylene / vinyl acetate copolymer (hereinafter referred to as "EVA"), JP-A-49-99614.
The publication discloses a laminated glass in which a silicon compound film is formed between the intermediate film and the glass.
【０００５】しかし、上記ＥＶＡの鹸化物を用いる方法
では、合わせガラスの貫通強度が不充分であり、珪素化
合物を用いる方法では、被膜形成の工程を組み込む必要
があるため、簡便な方法ではなかった。However, the method using the saponified product of EVA is not sufficient in the penetration strength of the laminated glass, and the method using the silicon compound is not a simple method because it requires a step of forming a film. .
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記の欠点
に鑑みてなされたもので、その目的は、透明性、耐湿
性、衝撃エネルギー吸収性等の合わせガラスに必要な基
本特性を損なうことなく、吸湿してもガラスとの接着性
の低下がない合わせガラス用中間膜を提供することであ
る。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and its purpose is to impair the basic properties required for a laminated glass such as transparency, moisture resistance and impact energy absorption. Another object of the present invention is to provide an interlayer film for laminated glass, which does not deteriorate in adhesiveness with glass even when absorbing moisture.
【０００７】[0007]
【課題を解決するための手段】本発明で使用される樹脂
膜（Ａ）は、ポリビニルブチラ−ル樹脂（ａ）と可塑剤
からなる。The resin film (A) used in the present invention comprises a polyvinyl butyral resin (a) and a plasticizer.
【０００８】上記ポリビニルブチラール樹脂（ａ）のア
セタール化度は、６０モル％未満でも、７５モル％を越
えても得られる合わせガラスの耐貫通性が低下するの
で、６０〜７５モル％に限定される。If the degree of acetalization of the polyvinyl butyral resin (a) is less than 60 mol% or more than 75 mol%, the penetration resistance of the laminated glass obtained is lowered, so that it is limited to 60 to 75 mol%. It
【０００９】上記ポリビニルブチラール樹脂（ａ）の製
造方法は、任意の方法が採用され得るが、例えば、ポリ
ビニルアルコールを熱水に溶解し、得られた水溶液を１
０〜２０℃に保持しておいて、ブチルアルデヒドと触媒
を加えてアセタール化反応を進行させ、次いで７０℃に
昇温して保持した後、中和、水洗及び乾燥を経てポリビ
ニルブチラール樹脂粉末を得る方法が挙げられる。The polyvinyl butyral resin (a) can be produced by any method. For example, polyvinyl alcohol is dissolved in hot water to form an aqueous solution of 1
While maintaining at 0 to 20 ° C, butyraldehyde and a catalyst are added to proceed the acetalization reaction, and then the temperature is raised to 70 ° C and maintained, after which the polyvinyl butyral resin powder is neutralized, washed with water and dried. The method of obtaining is mentioned.
【００１０】上記ポリビニルアルコールの平均重合度
は、小さくなると得られる合わせガラス用中間膜の耐貫
通性能が劣り、大きくなると強度が高くなりすぎ、衝撃
強度が高くなりすぎるため、平均重合度８００〜３００
０のものが好ましい。When the average degree of polymerization of the polyvinyl alcohol is small, the resulting interlayer film for laminated glass has poor penetration resistance, and when it is large, the strength is too high and the impact strength is too high. Therefore, the average degree of polymerization is 800 to 300.
0 is preferable.
【００１１】上記ポリビニルアルコールはポリ酢酸ビニ
ルを鹸化して得られるものでその鹸化度は、得られる合
わせガラス用中間膜の透明度、耐熱性、耐光性を良好に
するために９５モル％以上であることが好ましい。The above-mentioned polyvinyl alcohol is obtained by saponifying polyvinyl acetate, and its saponification degree is 95 mol% or more in order to improve the transparency, heat resistance and light resistance of the obtained interlayer film for laminated glass. It is preferable.
【００１２】上記可塑剤は、合わせガラス用中間膜に一
般に使用されている任意の可塑剤が使用でき、例えば一
塩基酸エステル、多塩基酸エステル、有機リン酸または
有機亜リン酸等が挙げられる。As the plasticizer, any plasticizer generally used for interlayer films for laminated glass can be used, and examples thereof include monobasic acid esters, polybasic acid esters, organic phosphoric acid and organic phosphorous acid. .
【００１３】上記一塩基酸エステルは、例えば、酪酸、
イソ酪酸、カプロン酸、２−エチル酪酸、ヘプタン酸、
オクチル酸、２−エチルヘキシル酸、ペラルゴン酸（ノ
ニル酸）、デシル酸等の有機酸とトリエチレングリコー
ルとの反応によって得られるエステルが好ましい。より
好ましくは、トリエチレングリコールジ２−エチルブチ
レート、トリエチレングリコール−ジ２−エチルヘキソ
エート、トリエチレングリコールジカプロネート、トリ
エチレングリコールジオクトエート等である。The monobasic acid ester is, for example, butyric acid,
Isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid,
An ester obtained by reacting an organic acid such as octylic acid, 2-ethylhexyl acid, pelargonic acid (nonyl acid), and decyl acid with triethylene glycol is preferable. More preferred are triethylene glycol di2-ethylbutyrate, triethylene glycol-di2-ethylhexoate, triethylene glycol dicapronate, triethylene glycol dioctoate and the like.
【００１４】また、テトラエチレングリコール、トリプ
ロピレングリコールと上記の有機酸とのエステルも用い
られる。Esters of tetraethylene glycol and tripropylene glycol with the above organic acids are also used.
【００１５】上記多塩基酸エステルとしては、例えば、
アジピン酸、セバチン酸、アゼライン酸等の有機酸と、
炭素数４〜８の直鎖状または分枝状アルコールとの反応
によって得られるエステルが好ましい。より好ましく
は、ジブチルセバケート、ジオクチルアゼレート、ジブ
チルカルビトールアジペート等である。Examples of the polybasic acid ester include:
Organic acids such as adipic acid, sebacic acid, azelaic acid,
Esters obtained by reaction with straight-chain or branched alcohols having 4 to 8 carbon atoms are preferred. More preferred are dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like.
【００１６】上記有機リン酸としては、例えば、トリブ
トキシエチルホスフェート、イソデシルフェニルホスフ
ェート、トリイソプロピルホスフェート等が好ましい。As the above-mentioned organic phosphoric acid, for example, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like are preferable.
【００１７】上記可塑剤の添加量は、少くなると得られ
る合わせガラスの耐貫通性能が低下し、多くなると可塑
剤がブリードアウトして得られる合わせガラスの透明性
や得られる合わせガラス用中間膜のガラスとの接着力が
低下するため、上記ポリビニルブチラ−ル樹脂１００重
量部に対し、２０〜６０重量部が好ましく、より好まし
くは３０〜５５重量部である。When the amount of the plasticizer added is small, the penetration resistance of the laminated glass obtained is low, and when it is too large, the transparency of the laminated glass obtained by bleeding out the plasticizer and the resulting interlayer film for laminated glass of the obtained laminated glass are low. Since the adhesive strength to glass decreases, it is preferably 20 to 60 parts by weight, more preferably 30 to 55 parts by weight, based on 100 parts by weight of the polyvinyl butyral resin.
【００１８】本発明で用いられる樹脂膜（Ｂ）はポリビ
ニルブチラ−ル樹脂（ｂ）と可塑剤からなる。The resin film (B) used in the present invention comprises a polyvinyl butyral resin (b) and a plasticizer.
【００１９】上記ポリビニルブチラ−ル樹脂（ｂ）のア
セタール化度は、少なくなると可塑剤との相溶性が悪く
得られる合わせガラス用中間膜の充分な透明性が得られ
ず、多くなると吸湿時にガラスとの充分な接着力が得ら
れないため、５０〜６５モル％であり、前記ポリビニル
ブチラ−ル樹脂（ａ）と上記ポリビニルブチラ−ル樹脂
（ｂ）とのアセタール化度の差は、小さくなると吸湿時
の合わせガラス用中間膜とガラスとの接着性が低下し、
大きくなると可塑剤との相溶性の差が大きくなり、可塑
剤の移行や屈折率の差による透明性の低下が起こるた
め、２〜１５モル％であり、より好ましくは３〜１２モ
ル％である。When the degree of acetalization of the polyvinyl butyral resin (b) is low, the compatibility with the plasticizer is poor, and sufficient transparency of the interlayer film for laminated glass cannot be obtained. Since sufficient adhesive strength with glass cannot be obtained, it is 50 to 65 mol%, and the difference in the degree of acetalization between the polyvinyl butyral resin (a) and the polyvinyl butyral resin (b) is , If it becomes small, the adhesiveness between the interlayer film for laminated glass and the glass at the time of moisture absorption decreases,
When it is larger, the difference in compatibility with the plasticizer is larger, and the transparency is lowered due to migration of the plasticizer and the difference in refractive index. Therefore, it is 2 to 15 mol%, more preferably 3 to 12 mol%. .
【００２０】上記ポリビニルブチラール樹脂（ｂ）の製
造方法は、例えば、ポリビニルアルコールを熱水に溶解
し、得られたポリビニルアルコール水溶液とブチルアル
デヒドを２０〜６０℃の温度範囲で混合し、この混合液
と触媒とを６０〜９５℃の温度範囲で混合することによ
り、アセタール化反応を進行させ、冷却後、常法で中
和、水洗及び乾燥を経て顆粒状のポリビニルブチラール
樹脂を得る方法が挙げられる。In the method for producing the polyvinyl butyral resin (b), for example, polyvinyl alcohol is dissolved in hot water, the obtained aqueous solution of polyvinyl alcohol and butyraldehyde are mixed in a temperature range of 20 to 60 ° C., and the mixed solution is obtained. And a catalyst are mixed in a temperature range of 60 to 95 ° C. to promote an acetalization reaction, and after cooling, neutralization, washing with water and drying are carried out by a conventional method to obtain a granular polyvinyl butyral resin. .
【００２１】上記ポリビニルアルコ−ルは、前記樹脂膜
（Ａ）を構成するポリビニルブチラ−ル樹脂の製造に用
いられるのと同様のものが使用される。The same polyvinyl alcohol as that used in the production of the polyvinyl butyral resin constituting the resin film (A) is used.
【００２２】上記可塑剤としては、樹脂膜（Ａ）で用い
られるのと同様のものが使用できる。The same plasticizer as that used in the resin film (A) can be used.
【００２３】上記可塑剤の添加量は、少なくなると得ら
れる合わせガラスの耐貫通性が低下し、多くなると可塑
剤がブリードアウトして合わせガラスの透明性や得られ
る合わせガラス用中間膜とガラスとの接着力が低下する
ため、上記ポリビニルブチラ−ル樹脂１００重量部に対
して１０〜８０重量部が好ましく、より好ましくは２０
〜６０重量部である。If the amount of the plasticizer added is small, the penetration resistance of the laminated glass obtained is low, and if it is too large, the plasticizer bleeds out, and the transparency of the laminated glass and the interlayer film for laminated glass and the glass obtained are obtained. 10 to 80 parts by weight, more preferably 20 parts by weight, based on 100 parts by weight of the polyvinyl butyral resin.
-60 parts by weight.
【００２４】本発明の合わせガラス用中間膜の層構成
は、例えば、樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜
（Ｂ）、樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜（Ｂ）／
樹脂膜（Ａ）／樹脂膜（Ｂ）のように、吸湿時の接着力
を維持するため、樹脂膜（Ｂ）を最外層に配置するもの
である。The layer structure of the interlayer film for laminated glass of the present invention is, for example, resin film (B) / resin film (A) / resin film (B), resin film (B) / resin film (A) / resin film. (B) /
Like the resin film (A) / resin film (B), the resin film (B) is arranged as the outermost layer in order to maintain the adhesive force when absorbing moisture.
【００２５】本発明の合わせガラス用中間膜の厚さは、
薄くなると得られる合わせガラスの耐貫通強度が低下
し、厚くなると破壊衝撃強度が高くなりすぎ脳障害の様
な弊害を引き起こし、また、コストの面からも好ましく
ないので、０．２〜１．６ｍｍが好ましく、より好まし
くは０．３〜１．２ｍｍである。The thickness of the interlayer film for laminated glass of the present invention is
If it becomes thin, the penetration resistance of the obtained laminated glass will decrease, and if it becomes thick, the fracture impact strength will become too high, causing harmful effects such as brain damage, and it is also not preferable from the viewpoint of cost, so it is 0.2-1.6 mm. Is preferable, and more preferably 0.3 to 1.2 mm.
【００２６】また、樹脂膜（Ａ）の厚さは、透明性、貫
通強度及び力学特性に寄与するため薄くなると得られる
合わせガラスの耐貫通性が低下し、厚くなると破壊衝撃
強度が高くなりすぎ脳障害の様な弊害を引き起こし、ま
た、コストの面からも好ましくないので、０．０５〜
１．２ｍｍが好ましく、より好ましくは０．１〜１．０
ｍｍである。Further, since the thickness of the resin film (A) contributes to transparency, penetration strength and mechanical properties, if the thickness is thin, the penetration resistance of the obtained laminated glass is lowered, and if it is thick, the fracture impact strength becomes too high. Since it causes harmful effects such as brain damage and is not preferable from the viewpoint of cost, 0.05-
1.2 mm is preferable, and 0.1 to 1.0 is more preferable.
mm.
【００２７】また、樹脂膜（Ｂ）は、吸湿時の接着性を
向上させるのに寄与するため、薄くなると得られる合わ
せガラスの吸湿時のガラスとの接着性が低下し、厚くな
ると、破壊衝撃強度が高くなりすぎ脳障害の様な弊害を
引き起こし、また、コストの面からも好ましくないので
０．０１〜１．０ｍｍが好ましく、より好ましくは０．
０３〜０．８ｍｍである。Further, since the resin film (B) contributes to improving the adhesiveness when absorbing moisture, the adhesiveness of the laminated glass obtained when it becomes thin decreases with the glass when absorbing moisture, and when it becomes thick, the breaking impact The strength is too high, causing harmful effects such as brain damage, and is also not preferable from the viewpoint of cost. Therefore, the thickness is preferably 0.01 to 1.0 mm, more preferably 0.
It is 03 to 0.8 mm.
【００２８】樹脂膜（Ａ）および樹脂膜（Ｂ）には、上
記以外に、ポリビニルブチラール樹脂の劣化を防止する
ための安定剤、酸化防止剤、紫外線吸収剤等が、ポリビ
ニルブチラール樹脂の製造過程またはポリビニルブチラ
ール樹脂と可塑剤等との混合時に、必要に応じて添加さ
れてもよい。In addition to the above, in the resin film (A) and the resin film (B), a stabilizer for preventing the deterioration of the polyvinyl butyral resin, an antioxidant, an ultraviolet absorber, etc. are added in the production process of the polyvinyl butyral resin. Alternatively, it may be added as needed when the polyvinyl butyral resin and the plasticizer are mixed.
【００２９】上記安定剤としては、例えば、ラウリル硫
酸ナトリウム、アルキルベンゼンスルホン酸等の界面活
性剤が挙げられ、上記酸化防止剤としては、例えば、ｔ
−ブチル−ヒドロキシトルエン（ＢＨＴ）、テトラキス
−［メチレン−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］メタン（チバ
ガイギー製、商品名；イノガノックス１０１０）等が挙
げられ、上記紫外線吸収剤としては、例えば、２−
（２’−ヒドロキシ−５’−メチルフェニル）ベンゾト
リアゾール（チバガイギー製、商品名；チヌビンＰ）、
２−（２’−ヒドロキシ−３’，５’−ジｔ−ブチルフ
ェニル）ベンゾトリアゾール（チバガイギー製、商品
名；チヌビン３２０）、２−（２’−ヒドロキシ−３’
−ｔ−ブチル−５’−メチルフェニル）−５−クロロベ
ンゾトリアゾール（チバガイギー製、商品名；チヌビン
３２６）、２−（２’−ヒドロキシ−３’，５−ジｔ−
アミルフェニル）ベンゾトリアゾール（チバガイギー
製、商品名：チヌビン３２８）等のベンゾトリアゾール
系及びアデカアーガス製、商品名；ＬＡ−５７の様なヒ
ンダードアミン系のものが挙げられる。Examples of the stabilizer include surfactants such as sodium lauryl sulfate and alkylbenzene sulfonic acid, and examples of the antioxidant include t.
-Butyl-hydroxytoluene (BHT), tetrakis- [methylene-3- (3'-5'-di-t-butyl-4 ']
-Hydroxyphenyl) propionate] methane (manufactured by Ciba-Geigy, trade name; Inoganox 1010) and the like. Examples of the ultraviolet absorber include 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole (manufactured by Ciba-Geigy, trade name; Tinuvin P),
2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (manufactured by Ciba-Geigy, trade name; Tinuvin 320), 2- (2′-hydroxy-3 ′)
-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole (manufactured by Ciba-Geigy, trade name; Tinuvin 326), 2- (2'-hydroxy-3 ', 5-di-t-).
Amylphenyl) benzotriazole (manufactured by Ciba Geigy, trade name: Tinuvin 328) and the like, and ADEKA ARGUS product, trade name; hindered amines such as LA-57.
【００３０】本発明の合わせガラス用中間膜は、例え
ば、下記の様にして製造される。The interlayer film for laminated glass of the present invention is produced, for example, as follows.
【００３１】ポリビニルブチラール樹脂と可塑剤をミキ
シングロールに供給し、混練して得られた混練物をプレ
ス成形機、カレンダ−ロ−ル、押出し機等でシ−ト状に
成形し樹脂膜（Ａ）製造する。A polyvinyl butyral resin and a plasticizer are supplied to a mixing roll and kneaded to obtain a kneaded product, which is then molded into a sheet by a press molding machine, a calendar roll, an extruder or the like to form a resin film (A). ) Produce.
【００３２】次いで、上記と同様の方法で樹脂膜（Ｂ）
を製造し、得られた樹脂膜（Ａ）および樹脂膜（Ｂ）
を、例えば、樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜
（Ｂ）のように重ね、プレス成形機、ラミネ−トロ−ル
などで加熱しながら積層し合わせガラス用中間膜を得るThen, a resin film (B) is prepared in the same manner as above.
And the obtained resin film (A) and resin film (B)
Are laminated in the order of, for example, resin film (B) / resin film (A) / resin film (B), and laminated while being heated with a press molding machine, a laminator, or the like to obtain an intermediate film for laminated glass.
【００３３】他の製造法としては、樹脂膜（Ａ）および
樹脂膜（Ｂ）の構成成分をそれぞれ別個に混合混練し、
一般的に用いられるストランド金型から押し出し、ペレ
タイザ−でペレットにし、２個以上のシリンダ−を有す
る押出機のシリンダ−にそれぞれ別個に供給し、シ−ト
金型を用いて多層成形する方法が挙げられる。As another manufacturing method, the constituent components of the resin film (A) and the resin film (B) are separately mixed and kneaded,
A method of extruding from a commonly used strand mold, pelletizing with a pelletizer, feeding each to a cylinder of an extruder having two or more cylinders separately, and performing multi-layer molding using a sheet mold is known. Can be mentioned.
【００３４】更に他の製造方法としては、上記樹脂膜
（Ａ）の両面に樹脂膜（Ｂ）の構成成分を適当な溶剤に
溶解し、塗工液とし、塗料の塗工に一般に使用されるロ
−ルコ−ト法、バ−コ−ト法で塗工し、溶剤を乾燥除去
し合わせガラス用中間膜得る方法が挙げられる。As another production method, the constituents of the resin film (B) are dissolved in a suitable solvent on both sides of the resin film (A) to prepare a coating solution, which is generally used for coating a coating material. Examples thereof include a roll coating method and a bar coating method, and the solvent is dried and removed to obtain an interlayer film for laminated glass.
【００３５】本発明の合わせガラス用中間膜を用いて合
わせガラスを製造する方法は、従来用いられている方法
が採用できるが、例えば、合わせガラス用中間膜をフロ
ートガラスにて挾着し、この挾着体を真空バッグに入れ
て、真空にしたままオーブン内で９０℃で３０分間保持
し、真空バッグから取り出した挾着体を、オートクレー
ブ内で圧力１２ｋｇ／ｃｍ2 ，温度１３５℃にて熱圧プ
レスし、透明な合わせガラスを得る方法が挙げられる。As a method for producing a laminated glass using the interlayer film for a laminated glass of the present invention, a conventionally used method can be adopted. For example, the interlayer film for a laminated glass is attached by float glass, Put the clad body in a vacuum bag and hold it in an oven at 90 ° C for 30 minutes while keeping it in a vacuum. The clad body taken out from the vacuum bag is heated in an autoclave at a pressure of 12 kg / cm 2 and a temperature of 135 ° C. A method of obtaining a transparent laminated glass by pressure pressing is mentioned.
【００３６】[0036]
【実施例】次に、本発明の実施例を説明する。尚、以下
「部」とあるのは「重量部」を意味する。EXAMPLES Next, examples of the present invention will be described. In the following, "parts" means "parts by weight".
【００３７】（実施例１） （１）樹脂膜（Ａ）を構成するポリビニルブチラール樹
脂の製造 イオン交換水２９００部、平均重合度１７００でケン化
度９９．２モル％のポリビニルアルコール１９８部（ビ
ニルアルコール成分４．５モル％）を撹拌装置付き反応
器に供給し、撹拌しながら９５℃に加熱して溶解した。
この溶液の温度を３０℃に冷却し、３５重量％塩酸１９
６部（１．９モル）とブチルアルデヒド１３５部（１．
９モル）を加え、次いで、液温を２℃に下げてこの温度
を保持し、ポリビニルブチラール樹脂が析出した後、液
温３０℃に昇温して５時間保持した。保持した後、炭酸
水素ナトリウム１４７部（１．７モル）を加えて中和
し、水洗及び乾燥を行いアセタール化度６５モル％のポ
リビニルブチラール樹脂を得た。(Example 1) (1) Production of polyvinyl butyral resin constituting resin film (A) 2900 parts of ion-exchanged water, 198 parts of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% (vinyl) The alcohol component (4.5 mol%) was supplied to a reactor equipped with a stirrer, and heated to 95 ° C. with stirring to dissolve.
The temperature of this solution was cooled to 30 ° C. and 35% by weight of hydrochloric acid 19
6 parts (1.9 mol) and 135 parts butyraldehyde (1.
(9 mol) was added, and then the liquid temperature was lowered to 2 ° C. and kept at this temperature. After the polyvinyl butyral resin was deposited, the liquid temperature was raised to 30 ° C. and kept for 5 hours. After holding, 147 parts (1.7 mol) of sodium hydrogen carbonate was added for neutralization, followed by washing with water and drying to obtain a polyvinyl butyral resin having an acetalization degree of 65 mol%.
【００３８】（２）樹脂膜（Ａ）の製造 得られたポリビニルブチラール樹脂１００部、トリエチ
レングリコール−ジ２−エチルブチレート４０部、ｔ−
ブチル−ヒドロキシトルエン０．１６部及び紫外線吸収
剤（チバガイギー製、商品名：チヌビンＰ）０．１６部
をミキシングロールに供給し、混練して得られた混練物
をプレス成形機にて１５０℃、１２０ｋｇ／ｃｍ2 の条
件で３０分間プレス成形し、厚さ０．５ｍｍの樹脂膜
（Ａ）を得た。(2) Production of resin film (A) 100 parts of the obtained polyvinyl butyral resin, 40 parts of triethylene glycol-di-2-ethylbutyrate, t-
0.16 parts of butyl-hydroxytoluene and 0.16 parts of an ultraviolet absorber (manufactured by Ciba-Geigy, trade name: Tinuvin P) were supplied to a mixing roll, and the resulting kneaded product was kneaded at 150 ° C. with a press molding machine. The resin film (A) having a thickness of 0.5 mm was obtained by press molding for 30 minutes under the condition of 120 kg / cm 2 .
【００３９】（３）樹脂膜（Ｂ）を構成するポリビニル
ブチラール樹脂の製造 平均重合度１５００及び鹸化化度９９．８モル％のポリ
ビニルアルコール３３１部（ビニルアルコール成分７．
５モル％相当量）をイオン交換水２８８５部に分散し、
９４℃で撹拌溶解させ、濃度９．７重量％のポリビニル
アルコール溶液を調製した。次いで、ポリビニルアルコ
ール水溶液を３０℃まで冷却し、この水溶液にブチルア
ルデヒド１８３部を加えて１０分間撹拌し、混合液を得
た。(3) Production of polyvinyl butyral resin constituting the resin film (B) 331 parts of polyvinyl alcohol having an average polymerization degree of 1500 and a saponification degree of 99.8 mol% (vinyl alcohol component 7.
5 mol% equivalent amount) is dispersed in 2885 parts of ion-exchanged water,
The mixture was stirred and dissolved at 94 ° C. to prepare a polyvinyl alcohol solution having a concentration of 9.7% by weight. Then, the polyvinyl alcohol aqueous solution was cooled to 30 ° C., 183 parts of butyraldehyde was added to this aqueous solution, and the mixture was stirred for 10 minutes to obtain a mixed solution.
【００４０】上記混合液と濃度３．６重量％の塩酸２５
０部を、濃度０．２重量％の塩酸５４５部の入った９０
℃に保たれた反応槽にそれぞれ同時滴下した。滴下は９
０分で終わるようにし、滴下終了後から９０分間９０℃
に保った。その後、冷却水洗し、次いで、炭酸水素ナト
リウムで液のｐＨが７〜８となるように、７０℃、３時
間で中和した。その後、水洗、脱水、乾燥を行ってポリ
ビニルブチラール樹脂を得た。得られたポリビニルブチ
アール樹脂のアセタール化度は６４モル％であった。25% hydrochloric acid having a concentration of 3.6% by weight with the above mixed solution
90 parts of 0 part of 545 parts of hydrochloric acid having a concentration of 0.2% by weight
Simultaneously added dropwise to the reaction tanks kept at ℃. 9 drops
It should be completed in 0 minutes, and 90 minutes after the dropping is completed at 90 ° C.
Kept at. Then, it was washed with cooling water and then neutralized with sodium hydrogencarbonate at 70 ° C. for 3 hours so that the pH of the liquid became 7-8. Then, it was washed with water, dehydrated and dried to obtain a polyvinyl butyral resin. The degree of acetalization of the obtained polyvinyl butyral resin was 64 mol%.
【００４１】（４）樹脂膜（Ｂ）の製造 上記で得られたポリビニルブチラール樹脂１００部，ト
リエチレングリコール−ジ２−エチルブチレート４０
部、ｔ−ブチル−ヒドロキシトルエン０．１６部及び紫
外線吸収剤（チバガイギー製、商品名；チヌビンＰ）
０．１６部をミキシングロールに供給して混練し、得ら
れた混練物をプレス成形機にて１５０℃、１２０ｋｇ／
ｃｍ2 で３０分間プレス成形し、厚さ０．１ｍｍの樹脂
膜（Ｂ）を得た。(4) Production of resin film (B) 100 parts of the polyvinyl butyral resin obtained above and 40 parts of triethylene glycol-di-2-ethylbutyrate.
Parts, t-butyl-hydroxytoluene 0.16 parts and an ultraviolet absorber (manufactured by Ciba-Geigy, trade name; Tinuvin P)
0.16 parts was supplied to a mixing roll and kneaded, and the resulting kneaded product was pressed by a press molding machine at 150 ° C. and 120 kg /
The resin film (B) having a thickness of 0.1 mm was obtained by press molding at cm 2 for 30 minutes.
【００４２】（５）合わせガラスの製造 樹脂膜（Ａ）及び（Ｂ）を、樹脂膜（Ｂ）／ 樹脂膜
（Ａ）／樹脂膜（Ｂ）の層構成で積層し、プレス成形機
にて１５０℃、１２０ｋｇ／ｃｍ2 で３０分間プレス成
形し、合わせガラス用中間膜を製造した。得られた合わ
せガラス用中間膜を１辺１０ｃｍで厚さ３ｍｍの２枚の
フロートガラスにて挾着し、この挾着体を真空バッグに
入れて真空度２０ｔｏｒｒで２０分間保持し、真空にし
たままオーブン内で９０℃で３０分間保持した。真空バ
ッグから取り出した挾着体を、オートクレーブ内で圧力
１２ｋｇ／ｃｍ2 、温度１３５℃にて熱圧プレスし、合
わせガラスを得た。(5) Manufacture of laminated glass The resin films (A) and (B) are laminated in a layer structure of resin film (B) / resin film (A) / resin film (B), and a press molding machine is used. By press molding at 150 ° C. and 120 kg / cm 2 for 30 minutes, an interlayer film for laminated glass was manufactured. The obtained interlayer film for laminated glass was sandwiched between two float glasses each having a side length of 10 cm and a thickness of 3 mm, and the sandwiched body was placed in a vacuum bag and held at a vacuum degree of 20 torr for 20 minutes to form a vacuum. It was kept in the oven at 90 ° C for 30 minutes as it was. The clinging body taken out from the vacuum bag was hot-pressed in an autoclave at a pressure of 12 kg / cm 2 and a temperature of 135 ° C. to obtain a laminated glass.
【００４３】上記で得られた合わせガラス用中間膜を用
いて２枚のフロートガラスのうち１枚をポリエチレンテ
レフタレ−トフィルムに換え上記と同様の方法でピ−ル
強度測定用の合わせガラスを製造した。Using the interlayer film for laminated glass obtained above, one of the two float glasses was replaced with a polyethylene terephthalate film to produce a laminated glass for measuring peel strength by the same method as above. did.
【００４４】（実施例２）ブチルアルデヒドの添加量を
１７４部としてポリビニルブチラ−ル樹脂（ｂ）のアセ
タ−ル化度を６１モル％とし、樹脂膜（Ｂ）のトリエチ
レングリコール−ジ２−エチルブチレートの添加量を４
５部とした以外は実施例１と同様にして合わせガラスお
よびピ−ル強度測定用の合わせガラスを製造した。(Example 2) The amount of butyraldehyde added was 174 parts, and the degree of acetalization of the polyvinyl butyral resin (b) was 61 mol%, and the amount of triethylene glycol-di-2 of the resin film (B) was adjusted. -The addition amount of ethyl butyrate is 4
A laminated glass and a laminated glass for measuring peel strength were manufactured in the same manner as in Example 1 except that the amount was 5 parts.
【００４５】（実施例３）ブチルアルデヒドの添加量を
１５４部としてポリビニルブチラ−ル樹脂（ｂ）のアセ
タ−ル化度を５４モル％とし、樹脂膜（Ｂ）のトリエチ
レングリコール−ジ２−エチルブチレートの添加量を５
０部とした以外は実施例１と同様にして合わせガラスお
よびピ−ル強度測定用の合わせガラスを製造した。(Example 3) The amount of butyraldehyde added was 154 parts and the degree of acetalization of the polyvinyl butyral resin (b) was 54 mol%, and triethylene glycol di-2 was used for the resin film (B). -The addition amount of ethyl butyrate is 5
A laminated glass and a laminated glass for peel strength measurement were produced in the same manner as in Example 1 except that the amount was 0 part.
【００４６】（実施例４）ブチルアルデヒドの添加量を
１７４部としてポリビニルブチラ−ル樹脂（ｂ）のアセ
タ−ル化度を６１モル％とし、樹脂膜（Ｂ）のトリエチ
レングリコール−ジ２−エチルブチレートの添加量を４
５部とし、樹脂膜（Ａ）の厚さを０．２ｍｍ、樹脂膜
（Ｂ）の厚さを０．１ｍｍとし、合わせガラス用中間膜
の層構成を樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜（Ｂ）
／樹脂膜（Ａ）／樹脂膜（Ｂ）の５層とした以外は実施
例１と同様にして合わせガラスおよびピ−ル強度測定用
の合わせガラスを製造した。(Example 4) The amount of butyraldehyde added was 174 parts, and the degree of acetalization of the polyvinyl butyral resin (b) was 61 mol%, and triethylene glycol di-2 was used for the resin film (B). -The addition amount of ethyl butyrate is 4
5 parts, the resin film (A) has a thickness of 0.2 mm, the resin film (B) has a thickness of 0.1 mm, and the interlayer structure for laminated glass has a layer structure of resin film (B) / resin film (A). ) / Resin film (B)
A laminated glass and a laminated glass for measuring the peel strength were manufactured in the same manner as in Example 1 except that the five layers of / resin film (A) / resin film (B) were used.
【００４７】（実施例５）ブチルアルデヒドの添加量を
１７４部としてポリビニルブチラ−ル樹脂（ｂ）のアセ
タ−ル化度を６１モル％とし、樹脂膜（Ｂ）のトリエチ
レングリコール−ジ２−エチルブチレートの添加量を４
５部とし、樹脂膜（Ａ）の厚さを１．０ｍｍ、樹脂膜
（Ｂ）の厚さを０．０２ｍｍとし、合わせガラス用中間
膜の層構成を樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜
（Ｂ）の３層とした以外は実施例１と同様にして合わせ
ガラスおよびピ−ル強度測定用の合わせガラスを製造し
た。(Example 5) The amount of butyraldehyde added was 174 parts, and the degree of acetalization of the polyvinyl butyral resin (b) was 61 mol%. -The addition amount of ethyl butyrate is 4
5 parts, the resin film (A) has a thickness of 1.0 mm, the resin film (B) has a thickness of 0.02 mm, and the interlayer structure for laminated glass has a layer structure of resin film (B) / resin film (A). ) / Resin film (B) except that three layers were prepared in the same manner as in Example 1 to produce a laminated glass and a laminated glass for measuring the peel strength.
【００４８】（比較例１）実施例１で得られた樹脂膜
（Ａ）のみを合わせガラス用中間膜とした以外は実施例
１と同様にして合わせガラスおよびピ−ル強度測定用の
合わせガラスを製造した。(Comparative Example 1) A laminated glass and a laminated glass for peel strength measurement were conducted in the same manner as in Example 1 except that only the resin film (A) obtained in Example 1 was used as an intermediate film for laminated glass. Was manufactured.
【００４９】（比較例２）ブチルアルデヒドの添加量を
１９２部としてポリビニルブチラ−ル樹脂（ｂ）のアセ
タ−ル化度を６７モル％とし、樹脂膜（Ｂ）のトリエチ
レングリコール−ジ２−エチルブチレートの添加量を３
５部とし、樹脂膜（Ａ）の厚さを０．５ｍｍ、樹脂膜
（Ｂ）の厚さを０．１ｍｍとし、合わせガラス用中間膜
の層構成を樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜（Ｂ）
の３層とした以外は実施例１と同様にして合わせガラス
およびピ−ル強度測定用の合わせガラスを製造した。(Comparative Example 2) The amount of butyraldehyde added was 192 parts, and the degree of acetalization of the polyvinyl butyral resin (b) was 67 mol%, and triethylene glycol-di-2 of the resin film (B) was used. -The addition amount of ethyl butyrate is 3
5 parts, the resin film (A) has a thickness of 0.5 mm, the resin film (B) has a thickness of 0.1 mm, and the interlayer structure for laminated glass has a layer structure of resin film (B) / resin film (A). ) / Resin film (B)
A laminated glass and a laminated glass for peel strength measurement were manufactured in the same manner as in Example 1 except that the three layers were prepared.
【００５０】（比較例３）ブチルアルデヒドの添加量を
１４４部としてポリビニルブチラ−ル樹脂（ｂ）のアセ
タ−ル化度を４０モル％とし、樹脂膜（Ｂ）のトリエチ
レングリコール−ジ２−エチルブチレートの添加量を５
５部とし、樹脂膜（Ａ）の厚さを０．５ｍｍ、樹脂膜
（Ｂ）の厚さを０．１ｍｍとし、合わせガラス用中間膜
の層構成を樹脂膜（Ｂ）／樹脂膜（Ａ）／樹脂膜（Ｂ）
の３層とした以外は実施例１と同様にして合わせガラス
およびピ−ル強度測定用の合わせガラスを製造した。(Comparative Example 3) The amount of butyraldehyde added was 144 parts, and the degree of acetalization of the polyvinyl butyral resin (b) was 40 mol%, and triethylene glycol-di-2 of the resin film (B) was used. -The addition amount of ethyl butyrate is 5
5 parts, the resin film (A) has a thickness of 0.5 mm, the resin film (B) has a thickness of 0.1 mm, and the interlayer structure for laminated glass has a layer structure of resin film (B) / resin film (A). ) / Resin film (B)
A laminated glass and a laminated glass for peel strength measurement were manufactured in the same manner as in Example 1 except that the three layers were prepared.
【００５１】実施例１〜５、比較例１〜３で得られた合
わせガラス、ピ−ル強度測定用合わせガラスを用いて耐
湿性試験、ピール強度試験、透明性試験及び耐貫通性試
験を行い、各試験結果を表１に示した。The laminated glass obtained in Examples 1 to 5 and Comparative Examples 1 to 3 and the laminated glass for peel strength measurement were subjected to a moisture resistance test, a peel strength test, a transparency test and a penetration resistance test. The test results are shown in Table 1.
【００５２】[0052]
【表１】 [Table 1]
【００５３】上記試験方法は下記の通りである。 （１）耐湿性試験 温度５０±３℃で９５±３％の相対湿度に保った恒温恒
湿層内で、２週間静置し、周辺の接着力を評価するため
に、合わせガラスを−１８℃で２時間以上冷却した後、
支持鉄板上４５度の角度に保持し、重量０．５ポンドの
鉄製ハンマーで合わせガラスを打ち砕き、ガラス破砕の
付着状態を調べた。ガラス破砕非付着部分がある場合、
端部からの非付着部分の距離が最大のものを「接着力ゼ
ロの距離」として測定した。The above test method is as follows. (1) Humidity resistance test A laminated glass was placed in a constant temperature and humidity layer kept at a relative humidity of 95 ± 3% at a temperature of 50 ± 3 ° C. for 2 weeks to evaluate the adhesive strength of the surrounding glass with −18. After cooling at ℃ for 2 hours or more,
The laminated glass was held at an angle of 45 degrees on the supporting iron plate, and the laminated glass was crushed with an iron hammer having a weight of 0.5 pounds, and the adhesion state of the glass crush was examined. If there is a glass crushing non-adhesive part,
The maximum distance from the end to the non-adhesive portion was measured as "distance without adhesive force".
【００５４】（２）ピール強度試験 ピール強度測定用合わせガラスを幅２ｃｍ長さ１０ｃｍ
にカットし、オリエンテック製の商品名「テンシロンＵ
ＣＥ５００」を用いて、引っ張りスピード５００ｍｍ／
ｍｉｎで乾燥状態及び耐湿試験後の９０度ピール強度を
測定した。(2) Peel strength test Laminated glass for peel strength measurement is 2 cm wide and 10 cm long.
Cut into pieces and the product name "Tensilon U" manufactured by Orientec
CE500 ", pulling speed 500mm /
The dry state and the 90-degree peel strength after the moisture resistance test were measured at min.
【００５５】（３）透明度試験 東京電色社製の商品名「積分式濁度計」を用い、実施例
１〜５、比較例１〜３で得られた合わせガラスの全光線
透過率とヘイズを測定した。(3) Transparency Test Using a trade name “Integral turbidimeter” manufactured by Tokyo Denshoku Co., Ltd., the total light transmittance and haze of the laminated glass obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were measured. Was measured.
【００５６】（４）耐貫通性試験 耐貫通性試験は、ＪＩＳ−Ｒ３２１２「自動車用安全ガ
ラスの試験方法」に準拠して実施した。すなわち、合わ
せガラスの縁を支持枠に固定してこれを水平に保持し、
重さ２．２６ｋｇの鋼球を４ｍの高さから、合わせガラ
スの中央に自由落下させた。６枚の合わせガラスについ
て、６枚とも衝撃後５秒以内に鋼球が貫通しない場合は
合格、１枚でも貫通した場合は不合格とした。さらに、
鋼球を落下させる高さを０．５ｍ単位で変化させ、同じ
高さで繰り返し試験を行った。合わせガラスの数の５０
％において鋼球の貫通が妨げられる高さを求め、この時
の鋼球とガラス板面との距離をもって「平均貫通高さ」
とした。従って、平均貫通高さの数値が大であるほど、
耐貫通性能が大であることを示している。なお、この試
験は合わせガラスの温度を２３℃に保持して実施した。(4) Penetration resistance test The penetration resistance test was carried out in accordance with JIS-R3212 "Test method for automobile safety glass". That is, the edge of the laminated glass is fixed to the support frame and held horizontally,
A steel ball weighing 2.26 kg was dropped freely from the height of 4 m to the center of the laminated glass. Regarding 6 sheets of laminated glass, all 6 sheets were judged to be acceptable when the steel balls did not penetrate within 5 seconds after the impact, and were judged to be unacceptable when even 1 sheet was penetrated. further,
The height at which the steel ball was dropped was changed by 0.5 m, and the test was repeated at the same height. Number of laminated glass 50
%, The height at which the penetration of the steel ball is obstructed is calculated, and the distance between the steel ball and the glass plate surface at this time is the "average penetration height"
And Therefore, the larger the average penetration height is,
It shows that the penetration resistance is high. Note that this test was carried out while maintaining the temperature of the laminated glass at 23 ° C.
【００５７】[0057]
【発明の効果】本発明の合わせガラス用中間膜は、以上
の通り特定のポリビニルブチラ−ル樹脂と特定量の可塑
剤からなる樹脂膜の多層構造を有する構成であるから、
吸湿後も接着性の低下がなく優れた貫通強度が保持さ
れ、かつ、膜の合わせ加工工程において作業性がよい合
わせガラス用中間膜を製造することができるので、建物
用、車輌用の合わせガラス用中間膜として使用できる。As described above, the interlayer film for laminated glass of the present invention has a multi-layer structure of a resin film composed of a specific polyvinyl butyral resin and a specific amount of a plasticizer as described above.
Since it is possible to manufacture an interlayer film for laminated glass that retains excellent penetration strength even after absorbing moisture and has good workability in the film laminating process, it is possible to manufacture laminated glass for buildings and vehicles. It can be used as an intermediate film.
Claims (1)
ニルブチラール樹脂（ａ）１００重量部および可塑剤２
０〜６０重量部からなる樹脂膜（Ａ）と、アセタール化
度５０〜６５モル％のポリビニルブチラール樹脂（ｂ）
１００重量部および可塑剤１０〜８０重量部からなる樹
脂膜（Ｂ）とが、最外層に樹脂膜（Ｂ）を有するように
交互に積層された合わせガラス用中間膜であって、上記
ポリビニルブチラール樹脂（ｂ）のアセタール化度が上
記ポリビニルブチラール樹脂（ａ）のアセタール化度よ
り２〜１５モル％低いことを特徴とする合わせガラス用
中間膜。1. A 100 parts by weight of a polyvinyl butyral resin (a) having an acetalization degree of 60 to 75 mol% and a plasticizer 2.
Resin film (A) consisting of 0 to 60 parts by weight, and polyvinyl butyral resin (b) having an acetalization degree of 50 to 65 mol%.
An interlayer film for laminated glass, wherein 100 parts by weight and a resin film (B) comprising 10 to 80 parts by weight of a plasticizer are alternately laminated so as to have the resin film (B) as the outermost layer, and the polyvinyl butyral is An interlayer film for laminated glass, wherein the degree of acetalization of the resin (b) is 2 to 15 mol% lower than the degree of acetalization of the polyvinyl butyral resin (a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32468593A JPH07172878A (en) | 1993-12-22 | 1993-12-22 | Intermediate film for laminated glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32468593A JPH07172878A (en) | 1993-12-22 | 1993-12-22 | Intermediate film for laminated glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07172878A true JPH07172878A (en) | 1995-07-11 |
Family
ID=18168585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32468593A Pending JPH07172878A (en) | 1993-12-22 | 1993-12-22 | Intermediate film for laminated glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07172878A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931124A (en) * | 1994-11-24 | 1997-02-04 | Sekisui Chem Co Ltd | Production of polyvinyl acetal, polyvinyl acetal, interlayer for laminated glass and laminated glass |
| JPH101335A (en) * | 1996-04-16 | 1998-01-06 | Sekisui Chem Co Ltd | Laminated glass |
| US6559212B1 (en) | 1995-12-29 | 2003-05-06 | Monsanto Company | Plasticized polyvinyl butyral and sheet |
| US7462664B2 (en) | 2002-07-31 | 2008-12-09 | E. I. Du Pont De Nemours And Company | Polyvinylbutyral interlayer sheet with improved adhesion to glass and a process for preparing same |
| JP2009513804A (en) * | 2005-11-01 | 2009-04-02 | ソリユテイア・インコーポレイテツド | Poly (vinyl butyral) pellets |
| JP2010525967A (en) * | 2007-04-30 | 2010-07-29 | ソリユテイア・インコーポレイテツド | Impact resistant polymer interlayer |
| WO2015152243A1 (en) * | 2014-03-31 | 2015-10-08 | 積水化学工業株式会社 | Thermoplastic resin film and laminated glass |
| WO2016052674A1 (en) * | 2014-09-30 | 2016-04-07 | 積水化学工業株式会社 | Thermoplastic resin film and laminated glass |
| WO2019168173A1 (en) * | 2018-03-01 | 2019-09-06 | 株式会社クラレ | Multilayer structure in which plasticizer-containing sheets are stacked |
| JP2021054702A (en) * | 2019-09-26 | 2021-04-08 | 長春石油化學股▲分▼有限公司 | Polymer film and laminate glass containing the same |
-
1993
- 1993-12-22 JP JP32468593A patent/JPH07172878A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931124A (en) * | 1994-11-24 | 1997-02-04 | Sekisui Chem Co Ltd | Production of polyvinyl acetal, polyvinyl acetal, interlayer for laminated glass and laminated glass |
| US6559212B1 (en) | 1995-12-29 | 2003-05-06 | Monsanto Company | Plasticized polyvinyl butyral and sheet |
| JPH101335A (en) * | 1996-04-16 | 1998-01-06 | Sekisui Chem Co Ltd | Laminated glass |
| US7462664B2 (en) | 2002-07-31 | 2008-12-09 | E. I. Du Pont De Nemours And Company | Polyvinylbutyral interlayer sheet with improved adhesion to glass and a process for preparing same |
| JP2009513804A (en) * | 2005-11-01 | 2009-04-02 | ソリユテイア・インコーポレイテツド | Poly (vinyl butyral) pellets |
| JP2010525967A (en) * | 2007-04-30 | 2010-07-29 | ソリユテイア・インコーポレイテツド | Impact resistant polymer interlayer |
| CN106163801A (en) * | 2014-03-31 | 2016-11-23 | 积水化学工业株式会社 | Thermoplastic resin film and laminated glass |
| WO2015152243A1 (en) * | 2014-03-31 | 2015-10-08 | 積水化学工業株式会社 | Thermoplastic resin film and laminated glass |
| JPWO2015152243A1 (en) * | 2014-03-31 | 2017-04-13 | 積水化学工業株式会社 | Thermoplastic resin film and laminated glass |
| US10173397B2 (en) | 2014-03-31 | 2019-01-08 | Sekisui Chemical Co., Ltd. | Thermoplastic resin film and laminated glass |
| JP2019151548A (en) * | 2014-03-31 | 2019-09-12 | 積水化学工業株式会社 | Thermoplastic resin and glass laminate |
| WO2016052674A1 (en) * | 2014-09-30 | 2016-04-07 | 積水化学工業株式会社 | Thermoplastic resin film and laminated glass |
| JPWO2016052674A1 (en) * | 2014-09-30 | 2017-07-13 | 積水化学工業株式会社 | Thermoplastic resin film and laminated glass |
| WO2019168173A1 (en) * | 2018-03-01 | 2019-09-06 | 株式会社クラレ | Multilayer structure in which plasticizer-containing sheets are stacked |
| JPWO2019168173A1 (en) * | 2018-03-01 | 2021-03-11 | 株式会社クラレ | Multi-layer structure with overlapping plasticizer-containing sheets |
| JP2021054702A (en) * | 2019-09-26 | 2021-04-08 | 長春石油化學股▲分▼有限公司 | Polymer film and laminate glass containing the same |
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