JPS58140349A - Sandwich glass - Google Patents

Sandwich glass

Info

Publication number
JPS58140349A
JPS58140349A JP2118882A JP2118882A JPS58140349A JP S58140349 A JPS58140349 A JP S58140349A JP 2118882 A JP2118882 A JP 2118882A JP 2118882 A JP2118882 A JP 2118882A JP S58140349 A JPS58140349 A JP S58140349A
Authority
JP
Japan
Prior art keywords
treatment
ethylene
vinyl acetate
glass
laminated glass
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.)
Granted
Application number
JP2118882A
Other languages
Japanese (ja)
Other versions
JPH0413303B2 (en
Inventor
Hideo Takechi
秀雄 武市
Itsuo Tanuma
逸夫 田沼
Yukio Fukuura
福浦 幸男
Tomio Oyachi
大矢知 富雄
Toshio Naito
寿夫 内藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
Original Assignee
Bridgestone Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Priority to JP2118882A priority Critical patent/JPS58140349A/en
Publication of JPS58140349A publication Critical patent/JPS58140349A/en
Publication of JPH0413303B2 publication Critical patent/JPH0413303B2/ja
Granted legal-status Critical Current

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  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

PURPOSE:To obtain superior sandwich glass by a simple method without requiring severe control of temp. and humidity, by interposing an interlayer consisting of an ethylene-vinyl acetate copolymer which is subjected to an adhering treatment between two sheets of glass plates. CONSTITUTION:An interlayer consisting essentially of an ethylene-vinyl acetate copolymer which is subjected to an adhering treatment is interposed between two sheets of glass plates. Methods such as compounding of adhesive polymers, electric discharge treatment by plasma at low temp. or irradiation of electron rays are adapted to the above-described adhering treatment. Ethylenic resins contg. hydroxyl groups or carboxyl groups in molecules are used as the adhesive polymers to be adapted for the adhering treatment. The ethylene-vinyl acetate copolymer to be used is preferably the copolymer contg. 19-40wt% vinyl acetate contents.

Description

【発明の詳細な説明】 せガラスに関する。[Detailed description of the invention] Concerning glass.

自動車のフロントガラス、建築物の窓ガラス等に用いら
ねる合せガラスとして従来から最も 一般的に製造され
て来たものはその中間膜(こポリビニルブチラール樹脂
を使用するものであった.、ポリビニルブチラール樹脂
は熱可塑性であり、合せガラスとした,場合にいくつか
の問題点を有している。すなわち片水率により接着力を
調整しているが、含水率が大きすきると発泡、白濁など
の光学特性Vこ問題がおこり、少なすきると接着力が高
くなり耐貫通性に問題を生ずる等のほかポリビニルブチ
ラール膜自体粘着性のためブロッキングを起すなど、樹
脂膜とL7ても合せガラスとしても品質管理が困難であ
った。
The most commonly manufactured laminated glass used for car windshields, building window glass, etc. has been the interlayer film (polyvinyl butyral resin). Resin is thermoplastic and has some problems when laminated with glass.In other words, the adhesive strength is adjusted by the water content, but if the water content is too high, foaming, clouding, etc. may occur. Optical properties V This problem occurs, and if there is a small gap, the adhesive strength increases, causing problems in penetration resistance, and the polyvinyl butyral film itself is sticky, causing blocking, etc., and the quality of the laminated glass is also poor even when the resin film and L7 are used. It was difficult to manage.

本発明者らはかかる問題を解決すべく梗々検討した結果
、エチレンー酢酸ビニル共重合体(以■E V Aと略
称することがある)を主成分とし、これに有機過酸化物
もしくは光増感剤を配合した組成物を中間膜とする合せ
ガラスを特願昭56−811915。
The inventors of the present invention have made extensive studies to solve this problem, and have found that the main component is ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVA), and organic peroxide or photosensitizer is added to this. Patent application No. 56-811915 for a laminated glass having an interlayer film made of a composition containing a sensitizing agent.

特願昭56−158723にて提案1−7、ポリビニル
ブチラール樹脂中間膜より優れた特性を見出した。
In Japanese Patent Application No. 56-158723, we discovered properties superior to Proposal 1-7, a polyvinyl butyral resin interlayer film.

l一かしその後の検討により、この中間膜にも若モの問
題点があることが見出された。それは高温度な場所や尤
のあたる状態での貯蔵安定性に関する点や配合した有機
過酸化物の分解温度から来る製造条件の制約等である。
However, subsequent studies revealed that this intermediate film also had some problems. These include restrictions on storage stability in high-temperature locations or in extreme conditions, and restrictions on manufacturing conditions resulting from the decomposition temperature of the organic peroxide blended.

さらに+4 V A中間膜の接着力の調整に使用するシ
ランカップリング剤は接着力のコントロール、発泡防止
等に優れた効果を発揮する反面、水分による加水分解の
容易さから、加水分解表同時にシランの多購体を生ずる
可能性が大きく、このものがEVA中で系全体に相溶せ
ず、こわが原因で合せガラスに若干白濁を生ぜしめる懸
念があることである。
Furthermore, the silane coupling agent used to adjust the adhesive strength of the +4 V A interlayer film has excellent effects such as controlling adhesive strength and preventing foaming, but because it is easily hydrolyzed by moisture, the silane coupling agent is There is a high possibility that a large number of substances will be produced, and there is a concern that this substance will not be miscible with the entire system in EVA, and that stiffness will cause the laminated glass to become slightly cloudy.

このように先に提案した14 V A中間膜は温度管理
等貯蔵に際して細心の注意を要求されるばかりでなく接
着力を調整するだめの7ランカンプリング剤の高価な点
と相俟って経済的VCも有利とは言い難いものであった
In this way, the previously proposed 14VA interlayer film not only requires extreme care during storage such as temperature control, but also has the disadvantages of being economical due to the high cost of the 7-rank compres- ing agent used to adjust the adhesive strength. VC was also hardly advantageous.

そこで本発明者らはシランカップリング剤を使用l−な
くても充分な接着力が得られ、かつ厳重な湿度、温度コ
ントロールな必要としない比較的簡便な方法で優れたE
vA中間中間膜カゼガラスべく鋭意検討を市ねだ結果、
吐つの方法により目的を達することを踏出し本発明を范
成しだ。その第1は接着性ポリマーの配合であり、第2
は低温プラズマ放電処理、第:3は電イ線照射処理であ
る。
Therefore, the present inventors developed an excellent adhesive using a relatively simple method that provides sufficient adhesive strength even without the use of a silane coupling agent and does not require strict humidity and temperature control.
As a result of extensive research into the vA interlayer film,
The present invention was developed with the aim of achieving the objective by a method of vomiting. The first is the formulation of the adhesive polymer, and the second is the formulation of the adhesive polymer.
No. 3 is low-temperature plasma discharge treatment, and No. 3 is electric wire irradiation treatment.

以下に本発明の詳細な説明する1゜ 先ず中間膜主体となるI> V A樹脂について説明す
ると酢酸ビニル含有率が15〜50重!4j %である
ものが好ましく、さらに好ましくは19〜40重−係で
ある。酢酸ビニル含量が5()重V%を超えれば透明性
は良好であるが、E■、へ樹脂に架槁剤として役立つア
クリル酸またはメタクリル酸誘導体を添加した場合Vこ
も良好な耐貫通性能がイζ)られにくいので好″!it
、<ない。逆K l 5重&jt係未満では透明性改良
が困難となる。しかし透明性に重点をおかず、ガラスの
破損、飛散防止のみを目的とする合せガラスVCおいて
は15重W4未満であっても使用し得る。
The present invention will be explained in detail below. First, the I>VA resin, which is the main component of the interlayer film, will be explained. The vinyl acetate content is 15 to 50% by weight! It is preferably 4j%, more preferably 19 to 40%. If the vinyl acetate content exceeds 5% by weight, the transparency is good, but when an acrylic acid or methacrylic acid derivative is added to the resin to serve as a cross-linking agent, the penetration resistance is also good. ζ) I like it because it's hard to get caught''!
,<No. If the reverse K l is less than 5 times &jt ratio, it becomes difficult to improve transparency. However, in laminated glass VC whose purpose is only to prevent glass breakage and scattering without placing emphasis on transparency, it may be used even if the thickness is less than 15 W4.

本発明の第1の方法としての接着性ポリマーを配合する
のに′iI4 V A樹脂に接着性ポリマーと触媒とし
て過酸化物または光増感剤を添加する方法であり、この
場合の接着性ポリマーとしては分子内に水酸基またはカ
ルボキシル基を有するエチレン系樹脂である。水酸基を
有するエチレン系樹脂とシテハエチレンー酢酸ビニル共
重合体樹脂の部分ケン化物、エチレン−酢酸ビニル共重
合体のニスデル交換物、ポリビニルブチラール樹脂など
であり、カルボキシル基を有するエチレン系樹脂としテ
ハエチレンーアクリル酸共重合体、エチレン−メタクリ
ル酸共重合体、カルボキシル化エチレン−酢酸ビニル共
重合体、エチ、レンーアクリル酸またはエチレン−メタ
クリル酸共重合体の金属塩架橋物などである。
The first method of the present invention is to add an adhesive polymer and a peroxide or a photosensitizer as a catalyst to the iI4 V A resin, and in this case, the adhesive polymer It is an ethylene resin having a hydroxyl group or a carboxyl group in the molecule. Partially saponified products of ethylene resins having hydroxyl groups and ethylene-vinyl acetate copolymer resins, Nisdel-exchanged products of ethylene-vinyl acetate copolymers, polyvinyl butyral resins, etc. These include acid copolymers, ethylene-methacrylic acid copolymers, carboxylated ethylene-vinyl acetate copolymers, metal salt crosslinked products of ethylene-acrylic acid or ethylene-methacrylic acid copolymers, and the like.

分イ内に水酸基またはカルボキシル基を有するエチレン
系樹脂の添加針はEvA樹脂に対し1〜20重v4、好
ましくは2〜lO重量係である。
The addition needle of the ethylene resin having a hydroxyl group or a carboxyl group in the part is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, to the EvA resin.

20重1jt fbを超えて添加すればEVAが有する
合せガラスとしての性能が低下することがある。また1
重I−チ未満では接着力の改良が認められない。
If more than 20wt fb is added, the performance of EVA as a laminated glass may deteriorate. Also 1
If the weight is less than I-H, no improvement in adhesion is observed.

)2 V A樹脂に上記エチレン系樹脂を添加するにけ
通常の機械的な混練り、例えばオープンロール、押出機
等により、過酸化物または光増感剤の触媒と共に混合す
ればよ−い。この際の混練り温度はそれぞわの樹脂の軟
化温度以−りの温度で混合する必要があり、それが極め
て高温で過酸化物等の分解温度以上である場合は、まず
主成分の樹脂を混練りし、シート形成をした後に特願昭
56−176551のように溶媒に溶解した過酸化物等
をデツピング法等により添加すればよい。
2) To add the above-mentioned ethylene resin to the VA resin, it may be mixed with a peroxide or a photosensitizer catalyst by conventional mechanical kneading, such as an open roll or an extruder. The kneading temperature at this time must be at a temperature higher than the softening temperature of each resin.If the kneading temperature is extremely high and is higher than the decomposition temperature of peroxides, etc., first After kneading and forming a sheet, peroxide or the like dissolved in a solvent may be added by a dipping method or the like as disclosed in Japanese Patent Application No. 176551/1983.

本発明VC使用する過酸化物としてはケトンパーオキサ
イド類、ハイドロパーオキサイド類、ジアルキルパーオ
キサイド類、ジアシルパーオキサイド類、ジアルキルパ
ーオキサイド類、パーオキシエステル類等がある。これ
らの過酸化物は単独または2棟以ヒあわせ用いられる。
Peroxides used in the VC of the present invention include ketone peroxides, hydroperoxides, dialkyl peroxides, diacyl peroxides, dialkyl peroxides, peroxy esters, and the like. These peroxides may be used alone or in combination.

また光増感剤としてハヘンゾイン、ベンゾフェノン、ジ
ベンジル、5−ニトロアセナフデン、ヘキサクロロシク
ロペンタジェン、バラニトロジフェニルs  112−
ベンズアントラキノンなどがある。これらの触媒はEV
A100東[11部に対し5重址部以下の割合で単独ま
たは2棟以ヒの併用として(重用される。浴液として添
υ(1する場合の溶剤と12てシ1脂肪族、芳香族、脂
環族の溶剤およびパラフィン系、ナフテン系油、フター
ル酸エステル系町塑剤、アジピン酸ニスデル系用塑剤、
セパチン酸エステル系可塑剤、リン酸系可塑剤、エーテ
ル系可塑剤等の可塑剤を1種また2欅以りの混合で使用
することができる。
Also, as photosensitizers, hachenzoin, benzophenone, dibenzyl, 5-nitroacenaphdene, hexachlorocyclopentadiene, valanitrodiphenyl s 112-
Examples include benzanthraquinone. These catalysts are EV
A100 east [11 parts to 5 parts or less, used alone or in combination of 2 or more parts (heavily used). , alicyclic solvents, paraffinic oils, naphthenic oils, phthalate ester plastics, adipate Nisdale plastics,
Plasticizers such as sepatic acid ester plasticizers, phosphoric acid plasticizers, and ether plasticizers can be used singly or in combination of two or more.

第2の低温プラズマ放電処理による場合は熱硬化性もし
くは光硬化性EV 、へ樹脂を主成分とする中間膜シー
トを低温プラズマ放電処理する方法である。熱硬化性も
しくは光硬化性1; V Aは第1の方法の場合と同様
にEvAに過酸化物もしくは光増感剤を5重lit 部
(b V A l (10重り!部に対し)以下の一添
加したものである。
The second low-temperature plasma discharge treatment is a method in which an intermediate film sheet containing thermosetting or photocurable EV resin as a main component is subjected to low-temperature plasma discharge treatment. Thermosetting or photocuring 1; VA is EvA and peroxide or photosensitizer in 5 parts by weight (b VA l (for 10 parts by weight) or less) as in the case of the first method. It has one addition of .

本発明において行なわれる低温プラズマ放電にはコロナ
放電、グロー放電、高周波放電、マイクロ波放電等があ
り、そのいずれも本発明に適用し1するものである。特
にコロナ放電処理はシートの連続処理も可能で工業的に
効率の高い処理法である。I(V A樹脂中間膜シート
の接着処理に好ましい処理電力はコロナ放電処理の場合
を例にとると3〜20 W /rイ論以して充分である
The low-temperature plasma discharge performed in the present invention includes corona discharge, glow discharge, high frequency discharge, microwave discharge, etc., all of which are applicable to the present invention. In particular, corona discharge treatment is an industrially highly efficient treatment method that allows continuous treatment of sheets. In the case of corona discharge treatment, the preferred treatment power for adhesion treatment of the resin interlayer sheet is 3 to 20 W/r, which is theoretically sufficient.

この低温プラズマ処理を行なうことによりガラスと合せ
た場合ガラスとの間に適1、すな接着力が発現しガラス
の飛散を防止すると共に血・1斑通性の良好な合せガラ
スができる。
By carrying out this low-temperature plasma treatment, a suitable adhesive force is developed between the glass and the glass, which prevents the glass from scattering and provides a laminated glass with good blood and spot permeability.

第3の′電子線照射処理はEV、A樹脂を主成分とする
中間膜シートに電子線照射する方法である。
The third 'electron beam irradiation treatment' is a method of irradiating an interlayer film sheet containing EV, A resin as a main component with an electron beam.

この場合の中間膜kt EV A樹脂もしくはIル〜′
A樹脂にアクリロキシ基捷たはメタクリロキシ基を含有
する化合物を添加したものであり、過酸化物または光増
感剤の添加を要しない。
In this case, the intermediate film kt EV A resin or Iru~'
This is a resin in which a compound containing an acryloxy group or a methacryloxy group is added to resin A, and does not require the addition of a peroxide or a photosensitizer.

アクリロキシ基またはメタクリロキシ基を含有する化合
物としてはアクリル酸、メタクリル酸およびそれらの誘
導体、すなわちエステル、アミド類が一般的であり、こ
れらの化合物はEVA樹脂VC対して20重ttt%以
下の割合で添加される。
Acrylic acid, methacrylic acid, and their derivatives, namely esters and amides, are generally used as compounds containing an acryloxy group or methacryloxy group, and these compounds are added in a proportion of 20 wttt% or less to the EVA resin VC. be done.

本発明で行なわれる電子線照射は中間膜の厚さによって
も異なるが通常300〜750Ke〜′の加速電圧で行
なわねる。実用的な架橋度に達するだめの照射線量は0
.5〜20メガラド(八1rad)、好ましく&:i2
,5〜15メガラドである。
The electron beam irradiation carried out in the present invention is usually carried out at an accelerating voltage of 300 to 750 Ke~', although this varies depending on the thickness of the intermediate film. The irradiation dose required to reach a practical degree of crosslinking is 0.
.. 5-20 megarads (81 rad), preferably &:i2
, 5 to 15 megarads.

ト記組成のものを押出機、カレンダーロール、インフレ
ーションあるいはホットプレス等によりシート化【1.
たものに片面より電子線照射装置で適当な練りの電子線
を照射すれば目的の中間膜が得られる。また電子線照射
をシート両面に行なってもよい。
The composition described above is made into a sheet using an extruder, calendar roll, inflation, hot press, etc. [1.
The desired interlayer film can be obtained by irradiating one side of the material with a suitable electron beam using an electron beam irradiation device. Further, electron beam irradiation may be performed on both sides of the sheet.

電子線照射によりガラスとの接着力が向、ヒすると共V
こ架橋が行なわれ、透明性の改良に寄与し物性も一段と
向ヒする。この際電子線照射に先立ってシートを熱変形
しない程度に予め加温しておくと効果はさらに著しい。
Electron beam irradiation increases or decreases the adhesive strength with glass.
This crosslinking contributes to improved transparency and further improves physical properties. At this time, the effect is even more remarkable if the sheet is previously heated to an extent that it will not be thermally deformed prior to electron beam irradiation.

さらにアクリロキシ基またはメタクリロキシ基を含有す
る化合物の添加は架橋度を向1−させる効果を有する。
Furthermore, addition of a compound containing an acryloxy group or a methacryloxy group has the effect of increasing the degree of crosslinking.

本発明の第1〜第3の方法において必要ならば記述した
添加剤以外にも着色剤−1紫外線吸収剤、老化μB +
)−剤、変色防止剤等を適量添加することができる3゜ かくして第1の方法ではト; V A樹脂に接着性ポリ
マーおよび過酸化物または光増感剤を配合]−た組成物
をシートに1、て中間膜と【7、第2の方法ではt3 
V A樹脂に過酸化物−または光増感剤を配合1゜た組
成物をシートvこして低温プラズマ放電処理【7て中間
膜とし、第3の方法ではl・: V A樹脂あるいは1
(VA樹脂とアクリロキシ基捷たはメタクリロキシ基を
含有する化合物を配合17てシートにし、これに電子線
照射1〜で中間膜としたものを後は常法に従ってエアー
抜圧着し、第30方法ではそのまま、第1と第2の方法
ではこの後加熱硬化処理を行ない接着性がよく高い透明
性の合せガラスがit)られる。
In addition to the additives described in the first to third methods of the present invention, if necessary, colorant-1 ultraviolet absorber, aging μB +
) - agent, discoloration inhibitor, etc. can be added in appropriate amounts.Thus, in the first method; 1. In the second method, the interlayer film and the t3
A composition prepared by blending 1 degree of peroxide or photosensitizer with VA resin is passed through a sheet v and subjected to low temperature plasma discharge treatment [7] to form an interlayer film.
(VA resin and a compound containing an acryloxy group or a methacryloxy group are blended 17 to form a sheet, and this is subjected to electron beam irradiation 1 to 1 to form an interlayer film. After that, air is evacuated and pressure bonded according to a conventional method. In the first and second methods, a heat curing treatment is then performed to produce a laminated glass with good adhesion and high transparency.

本発明の接着処理によれば接着性ポリマーを配合する場
合は14 V A本来の性能を損うことなくガラスと中
間膜との接着性を改良することができ、低温プラズマ放
電処理の場合はカラス面に対し安定した充分な接着性が
発現し、圧着ユ、程における作業性、合せガラスの透明
性、耐衝撃性を何ら実質的に損うことはなく、さらに電
子線照射の場合は中間膜とガラスの接着力が向上し、併
せて過酸化物や光増感剤を使用しないため製造1.程し
ζおける温度的制約を受けることなく生産性が向にLs
According to the adhesive treatment of the present invention, when an adhesive polymer is blended, the adhesion between the glass and the interlayer film can be improved without impairing the original performance of 14 V A. It exhibits stable and sufficient adhesion to the surface, does not substantially impair the workability during pressure bonding and processing, the transparency of the laminated glass, and the impact resistance. Furthermore, in the case of electron beam irradiation, the interlayer film The adhesion between glass and glass is improved, and since no peroxides or photosensitizers are used, manufacturing process 1. Productivity increases in the direction of Ls without being subject to temperature constraints in the process.
.

1.かも加熱硬化や光硬化の必要がないので製造工程が
簡略化できる。
1. Moreover, since there is no need for heat curing or light curing, the manufacturing process can be simplified.

次に本発明を実′施例を挙げてさらに具体的に説明する
Next, the present invention will be explained in more detail with reference to Examples.

実施例1 (以下余白) 第    1    表 1、)東洋曹達社M1ハ/A  酢酸ビニル含hJ2.
512)ダウケミカル社製エチレン−アクリル酸共重合
体樹脂3)三片ポリケミカル社製アイオノマー(隔タイ
プ)4)蔵出薬品工業社製部分ケン化EVA5)三菱油
化社製カルボキシル化EVA6)γ−グリシドキシ7′
ロビルトリメトキシシランー、−゛ 第1表の配合表に従い115℃に加熱したオープンロー
ルにて各成分を混練り1.た。その後各配合のものをそ
れぞれポリエステルフィルム(厚さ50 /I )にを
まさみ、さらにそのLドt/c60メツシユのステンレ
ス金網を置き120℃のプレスを用いて厚さ0.41I
IIの両面エンボス模様のシートラ得た。ポリニスデル
フィルムを剥がしたシートを300 m角゛、厚さ3m
のフロートガラス間に挾み、ゴム袋中で真空ポンプにて
減圧下に120 ℃の熱板、ヒに置き、エアー抜圧着[
2だ合せガラスを得た。
Example 1 (Hereinafter blank) 1 Table 1,) Toyo Soda M1 Ha/A Vinyl acetate-containing hJ2.
512) Ethylene-acrylic acid copolymer resin manufactured by Dow Chemical Company 3) Ionomer (separate type) manufactured by Mikata Polychemical Company 4) Partially saponified EVA manufactured by Kurade Pharmaceutical Co., Ltd. 5) Carboxylated EVA manufactured by Mitsubishi Yuka Company 6) γ- Glycidoxy7'
Lobiltrimethoxysilane - Knead each component with an open roll heated to 115°C according to the recipe in Table 1. 1. Ta. After that, each composition was wrapped in a polyester film (thickness: 50/I), and then a stainless steel wire mesh of L/T/C 60 mesh was placed on it and pressed at 120°C to a thickness of 0.41I.
A sheet of paper II with embossed patterns on both sides was obtained. A sheet with polynisdel film removed is 300 m square and 3 m thick.
Place it between two pieces of float glass in a rubber bag under reduced pressure with a vacuum pump, place it on a hot plate at 120°C, and press it to release the air [
A double laminated glass was obtained.

この合せガラスをさらに160℃に加熱した熱板l二に
20分間放置し中間膜を架楡硬化したものをサンプルと
し、JIS)t3211および:う212による耐貫通
性試験を実施したところ、その落球高さ1.5mはすべ
て合格1−12mはすべて貫通した。
This laminated glass was further left on a hot plate heated to 160°C for 20 minutes to cross-cure the interlayer film, and the sample was subjected to penetration resistance tests according to JIS) t3211 and 212. Passed all heights of 1.5m and passed through all heights of 1-12m.

またこの時の剥離ガラスリは表vC示す通りで接着性付
醇剤としてγ−グリシドキシプロビルトリメトキシシラ
ンを添加したサンプルと比較して遜色のないものであっ
た。しかし接着性エチレン系樹脂を配合せずl(V A
のみの中間膜の合せガラスの接着性は不良であることが
わかる。
Further, the peeling glass resistance at this time was as shown in Table VC, and was comparable to that of the sample to which γ-glycidoxypropyltrimethoxysilane was added as an adhesion additive. However, without blending adhesive ethylene resin (V A
It can be seen that the adhesion of the interlayer film to the laminated glass is poor.

実施例2 第2表に示す配合、■の組成物をロールミルで混練りし
た後プレス法にて厚さ0,1mの:う旧)X30(1諭
サイズの均一なエンボスシートを作成17た。これをコ
ロナ放電処理装fi (VI4TAPIIONl;社製
 ジェネレーター最大出力(1,9kW、有効処理幅9
)G)にて下記条件で連続的に表面処理を行なった。
Example 2 The composition shown in Table 2 (1) was kneaded in a roll mill and then pressed to form a uniform embossed sheet with a thickness of 0.1 m and a size of 30 x 1 inch. This is corona discharge treatment equipment fi (VI4TAPIIONl; manufactured by Generator maximum output (1.9kW, effective treatment width 9
)G) The surface treatment was performed continuously under the following conditions.

電fij:回転絶縁電極 所要電カニ 1,3.lkW/m″/顯実際の処理操作
は装置のバンキングロールにシートを貼り付け、室温に
て表、裏面それぞれ1回ずつ処理を行なった。処理後の
シートは処理前のシートに比して外観、形状共時VC変
化は認めらtlなかった。
Electric fij: Rotating insulated electrode required electricity crab 1, 3. lkW/m''/Hyundai In the actual processing operation, the sheet was attached to the banking roll of the device, and the front and back sides were treated once each at room temperature.The appearance of the sheet after treatment was different from that of the sheet before treatment. , no shape synchronized VC change was observed.

(以上余白) 第    2   表 1)酢酸ビニル含量28係  メルトフローインデック
ス152)2.5−ジメチル−2,5−ジ(t−ブチル
パーオキシ)ヘキサン :()シランカップリング剤 4)東シ;テ′亀色社製 積分式濁度計’1’C−8P
型にて測定処理後の/−トを厚さ0,4wnの3 (1
0x 31111胴サイズのフロートガラス2枚の間に
挟着し、ゴム袋にて脱気しなから11(1℃l/こ加熱
した後、取り出さhた合せガラスを16(1℃の熱板上
iIi1mて20分間熱処理17、完全Vこエアーのな
い透明性の潰れた合せガラスを得た。
(Leaving space above) Table 2 1) Vinyl acetate content 28 Melt flow index 152) 2,5-dimethyl-2,5-di(t-butylperoxy)hexane: () Silane coupling agent 4) Toshi; Integral type turbidity meter '1'C-8P made by Te'Kameirosha
After measurement with a mold, the /-t is 0.4wn thick 3 (1
Place the laminated glass between two pieces of float glass of 0x 31111 body size, degas it in a rubber bag, heat it to 11 (1°C), and then take it out and place it on a hot plate at 16 (1°C). After heat treatment at 1 m for 20 minutes, a completely transparent crushed laminated glass without air was obtained.

次に比較例として第2表に示す配合に、I、の合せガラ
スを上記方法にて作成し、これら三者についてJ Is
 R:(205K基づき重さ225 f(D鋼球を30
0 X 30Omサイズの合せガラス中央部に高さ5m
より落下させ、耐貫通性を測定した結束を第2表に示す
Next, as a comparative example, laminated glasses I and I were prepared according to the above method according to the composition shown in Table 2, and J Is
R: (Weight 225 f based on 205K (30 D steel balls)
0 x 30 Om size laminated glass with a height of 5 m in the center
Table 2 shows the bundles whose penetration resistance was measured after being dropped.

第2表より本発明の実施例は合せガラス中間膜として要
求される性能、すなわち透明性、耐衝撃性、ガラスとの
接看性を十分兼ね備えていることがわかる。
From Table 2, it can be seen that the examples of the present invention sufficiently have the performance required as an interlayer film for laminated glass, that is, transparency, impact resistance, and ease of contact with glass.

比較例I EvA樹脂系合せガラスにおけるシランカップリング剤
に対する水分の影響を調べるために第2表の配合しのプ
レスシート(厚さ0.1闇の311 (1X :(01
) mサイズ)について、これを10分間、純水中VC
浸漬し充分に風乾した後、実施例2の方法(コロナ放電
処理は行なわない)にて合せガラスを作成したところ、
明らかに透明性の低下が認められた。(−・イズ測定値
()、6、透過率83チ)実施例3 第    3   表 第3表記合のものをM、Nは100℃、Pは130℃の
オープンロールにて混練りした後、厚さ50μのホリエ
ステルシートの間に挾んで鉄製モールドに入れ、N1、
Nは100 ℃、P &−11311℃のホントプレス
にて成形し1m厚のシートを得た。
Comparative Example I In order to investigate the influence of moisture on the silane coupling agent in EvA resin laminated glass, a press sheet with the formulation shown in Table 2 (thickness 0.1 Dark 311 (1X: (01
) m size) in pure water for 10 minutes.
After soaking and thoroughly air-drying, a laminated glass was created using the method of Example 2 (without corona discharge treatment).
A clear decline in transparency was observed. (-Is measured value (), 6, transmittance 83cm) Example 3 After kneading the products listed in Table 3 using an open roll at 100°C for M and N and 130°C for P, Sandwiched between 50μ thick hollyester sheets and placed in an iron mold, N1,
N was molded using a real press at 100°C and P & -11311°C to obtain a 1 m thick sheet.

このシートの片面より電子線照射装置を用いて加速電圧
500KeVで5 N1rad、 10 Mradの線
111を照射し、それぞれ未照射のサンプルと共にDI
N 3号ダンベルで打抜いてチャック間20m+、引張
りスピード200m1=で行なった。引張試験の結果を
第4表に示す。
One side of this sheet was irradiated with a beam 111 of 5 N1 rad and 10 Mrad at an accelerating voltage of 500 KeV using an electron beam irradiation device, and was subjected to DI together with the unirradiated sample.
Punching was performed using a No. 3 dumbbell with a chuck distance of 20 m+ and a pulling speed of 200 m1=. The results of the tensile test are shown in Table 4.

(以下余白) 以ヒの結果から各サンプルとも電子線照射による架橋が
起っていることがわかる。
(Left below) From the results shown below, it can be seen that crosslinking occurs in each sample due to electron beam irradiation.

実施例4 実施例3で混練り1.7だ各サンプルをポリエステルフ
ィルム間に挾み、さらにその上下より60メソシユの金
網で挾んだ後、M、Nは1(10℃、Pは130℃に加
熱したホットプレスでスペーサを用いて厚さ0.4 t
aの厚さにプレスした。
Example 4 Each sample kneaded at 1.7 in Example 3 was sandwiched between polyester films, and then sandwiched between 60 mesh wire mesh from above and below. 0.4 t thick using a spacer in a hot press heated to
It was pressed to a thickness of a.

得られたシートは両面に金網によるエンボス模様がつい
ている。このシートを実施例3と同様に線量5 Mra
d、  10 Mradの電子線を照射した。未照射の
ものを含めて、それぞれ厚さ3aon、300X300
+wす゛イズのフロートガラスを用いてゴム袋による真
空脱気法にてエアー抜圧着させて合せガラスを得た。
The resulting sheet has an embossed pattern made of wire mesh on both sides. This sheet was prepared at a dose of 5 Mra in the same manner as in Example 3.
d. Irradiation with an electron beam of 10 Mrad. Each thickness is 3aon, 300X300 including unirradiated ones.
A laminated glass was obtained by press-bonding +W-size float glass to remove air using a vacuum degassing method using a rubber bag.

また別に第5表に示すQ−8の配合の合せガラスを作成
した。
Separately, a laminated glass having the composition Q-8 shown in Table 5 was prepared.

(以下余白) 第    5   表 こねは電+l111!は未照射フィルムでエアー抜圧着
後、各160℃の温度の熱板−ヒ÷2θ分間加熱硬化し
たものである。これらの合せガラスを用いてJI81L
3211および3212に基〈耐貫通性試験を実施し、
耐貫通高さ、剥離ガラスb(を測定した。
(Left below) Part 5 Knead the table with electricity +l111! These are unirradiated films that were air-released and pressure-bonded, and then cured by heating on a hot plate at a temperature of 160° C. for ÷2θ minutes. JI81L using these laminated glasses
Based on 3211 and 3212, a penetration resistance test was conducted,
The penetration resistance height and peelable glass b() were measured.

また全く同様のサンプルを用いて、日本車色工業社製 
ヘイズメーターにて各サンプルのヘイズ値を測定した。
In addition, using exactly the same sample, Nippon Shairo Kogyo Co., Ltd.
The haze value of each sample was measured using a haze meter.

結果を第6表に示す。The results are shown in Table 6.

(以下余白)(Margin below)

Claims (2)

【特許請求の範囲】[Claims] (1)2枚のガラス板間に接着処理を施したエチレン−
酢酸ビニル共重合体を主成分とする中間膜を介在させて
なる合せガラス
(1) Ethylene bonded between two glass plates
Laminated glass with an interlayer film mainly composed of vinyl acetate copolymer
(2)接着処理が接着性ポリマーを配合するものである
特許請求の範囲第(11項記載の合せガラス(3)接着
性ポリマーが分子内に水酸基またはカルボキシル基を有
するエチレン系樹脂である特許請求の範囲第(2)項記
載の合せガラス(4)接着処理が低温プラズマ放電処理
である特許請求の範囲第(1)項記載の合せガラス(5
)接着処理が電子線照射処理である特許請求の範囲第(
])項記載の合せガラス
(2) The laminated glass according to claim 11 (3) The adhesive polymer is an ethylene resin having a hydroxyl group or a carboxyl group in the molecule. The laminated glass (5) according to claim (1), wherein the bonding treatment is a low-temperature plasma discharge treatment.
) The adhesion treatment is an electron beam irradiation treatment.
]) Laminated glass described in section
JP2118882A 1982-02-15 1982-02-15 Sandwich glass Granted JPS58140349A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2118882A JPS58140349A (en) 1982-02-15 1982-02-15 Sandwich glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2118882A JPS58140349A (en) 1982-02-15 1982-02-15 Sandwich glass

Publications (2)

Publication Number Publication Date
JPS58140349A true JPS58140349A (en) 1983-08-20
JPH0413303B2 JPH0413303B2 (en) 1992-03-09

Family

ID=12047973

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2118882A Granted JPS58140349A (en) 1982-02-15 1982-02-15 Sandwich glass

Country Status (1)

Country Link
JP (1) JPS58140349A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6250131A (en) * 1985-08-29 1987-03-04 旭硝子株式会社 Safety glass
JPS62223042A (en) * 1986-03-25 1987-10-01 Tosoh Corp Laminated glass
JPH0214855A (en) * 1988-06-30 1990-01-18 Showa Denko Kk Laminate safety glass
JP2004316319A (en) * 2003-04-18 2004-11-11 Nitomuzu:Kk Heat insulating sheet for window glass
JP2007335725A (en) * 2006-06-16 2007-12-27 Toshiba Industrial Products Manufacturing Corp Molded coil
CN111113871A (en) * 2020-01-13 2020-05-08 中山市华泽包装有限公司 Preparation method of EVA vacuum adhesive film with corona treatment process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6250131A (en) * 1985-08-29 1987-03-04 旭硝子株式会社 Safety glass
JPS62223042A (en) * 1986-03-25 1987-10-01 Tosoh Corp Laminated glass
JPH0214855A (en) * 1988-06-30 1990-01-18 Showa Denko Kk Laminate safety glass
JP2004316319A (en) * 2003-04-18 2004-11-11 Nitomuzu:Kk Heat insulating sheet for window glass
JP4533595B2 (en) * 2003-04-18 2010-09-01 株式会社ニトムズ Insulation sheet for window glass
JP2007335725A (en) * 2006-06-16 2007-12-27 Toshiba Industrial Products Manufacturing Corp Molded coil
CN111113871A (en) * 2020-01-13 2020-05-08 中山市华泽包装有限公司 Preparation method of EVA vacuum adhesive film with corona treatment process

Also Published As

Publication number Publication date
JPH0413303B2 (en) 1992-03-09

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