JPH0433750B2 - - Google Patents
Info
- Publication number
- JPH0433750B2 JPH0433750B2 JP59118769A JP11876984A JPH0433750B2 JP H0433750 B2 JPH0433750 B2 JP H0433750B2 JP 59118769 A JP59118769 A JP 59118769A JP 11876984 A JP11876984 A JP 11876984A JP H0433750 B2 JPH0433750 B2 JP H0433750B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- laminated glass
- component
- intermediate layer
- copolymer
- 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.)
- Expired - Lifetime
Links
- 239000005340 laminated glass Substances 0.000 claims description 23
- 229920000578 graft copolymer Polymers 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- -1 acrylic ester Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 12
- 230000035515 penetration Effects 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N Diethylhexyl phthalate Natural products CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000005336 safety glass Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BJQHLKABXJIVAM-BGYRXZFFSA-N 1-o-[(2r)-2-ethylhexyl] 2-o-[(2s)-2-ethylhexyl] benzene-1,2-dicarboxylate Chemical compound CCCC[C@H](CC)COC(=O)C1=CC=CC=C1C(=O)OC[C@H](CC)CCCC BJQHLKABXJIVAM-BGYRXZFFSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- B32B17/1055—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
- B32B17/10743—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 acrylate (co)polymers or salts thereof
-
- 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
Description
【発明の詳細な説明】
Ａ 本発明の技術分野
本発明はグラフト共重合体を中間層とする合せ
ガラスに関する。更にくわしくは特に低温におけ
る耐貫通強度、接着力に優れ、かつ耐光性、耐貫
通強度、耐水性に優れた合せガラスを提供するも
のである。
Ｂ 従来技術およびその問題点
従来、合せガラスとして２枚のガラス板を可塑
化ポリビニルブチラール樹脂を介して熱圧着した
ものがあり、自動車用、航空機用、建築用の安全
ガラスに広く利用されている。
しかし、ポリビニルブチラールは常温における
膜表面の粘着性が極めて強い為製膜後に膜同志が
粘着するという性質（以下自着性という）を有
し、かかる粘着を防ぐ目的で膜表面にエンボス加
工を施し、更に重炭酸ソーダ等の粘着防止剤を散
布している。従つてポリビニルブチラール層とガ
ラスとを接着するに際しては、あらかじめ水洗な
どにより粘着防止剤を除去しなければならない。
しかしながらポリビニルブチラールは分子内に−
OH基をふくむ為、吸湿し易い傾向にあり、接合
時の発泡に原因となり易い為乾燥工程が不可欠と
なる。この乾燥工程において接着性、透明性の低
下をともない実用上のトラブルとなつている。又
安全ガラスとしての合せガラスは特に低温での耐
貫通性が要求されるものである。ポリビニルブチ
ラールを中間層として用いる時は低温での耐貫通
性を満足させようとすると特に多量の可塑剤を添
加する必要がある。多量の可塑剤を添加した場合
は樹脂の自着性が大きくなりすぎて前述のごとき
接合工程でのトラブルが増幅される結果となり、
合せガラスに必要な諸性能がかえつて低下してし
まうという制限があつた。
本発明者らは、上記のごとき従来の問題点に鑑
み、これを解決すべく、鋭意検討の結果、本発明
を完成したものである。
Ｃ 本発明の構成、目的および作用効果
すなわち本発明は複数のガラス板をエチレン成
分とアクリル酸エステルもしくは酢酸ビニル成分
との共重合体にエチレン性不飽和カルボン酸もし
くは該カルボン酸無水物成分をグラフトして得
た、前記不飽和カルボン酸もしくは該カルボン酸
無水物の含有量がグラフト共重合体に対し0.1〜
５重量％であるグラフト共重合体を中間層として
接合した合せガラスであり、得られた合せガラス
は、特に低温での耐貫通性にすぐれ、更に耐湿度
性、耐水性、耐熱性、にすぐれるとともに、耐光
性、透明度が従来の合わせガラスとくらべ何ら劣
らないのみならず、その製造工程において接着加
工作業性にすぐれたものである。
中間層に用いるグラフト共重合体はアクリル酸
エステルもしくは酢酸ビニル成分を含有する。含
有量はその構造によつても異なるが、10〜45重量
％より好ましくは20〜40重量％である。同成分と
してはアクリル酸メチルエステル、アクリル酸エ
チルエステル、アクリル酸ブチルエステル、アク
リル酸２−エチルヘキシルエステルなどのアクリ
ル酸エステルが好適に用いられるが、より好適に
はアクリル酸エチルエステルが用いられる。本発
明に用いるグラフト共重合体は、これらのアクリ
ル酸エステルもしくは酢酸ビニルをエチレンとラ
ンダム共重合し、次いでこの共重合体にエチレン
性不飽和カルボン酸もしくは無水物をグラフトす
ることによつて得られる。
グラフト共重合体中のエチレン性不飽和カルボ
ン酸もしくは該カルボン酸無水物成分の含有量は
0.1〜５重量％であり、より好ましくは0.5〜４重
量％である。同成分としてはアクリル酸、メタク
リル酸、イタコン酸、マレイン酸、無水マレイン
酸、クロトン酸、無水イタコン酸などがある。ま
たグラフトする際スチレンを共グラフトすること
が好ましい場合がある。前記ランダム共重合体の
製法さらにはグラフト共重合体の製法には特に制
限はない。グラフト共重合体の中ではエチレン−
アクリル酸エチルエステル共重合体に無水マレイ
ン酸を単独でグラフトして得たもの、もしくはス
チレン類と共グラフトして得たものが好ましい。
また本発明の合せガラスは十分は接着性を有す
るものであるが、中間層が−20℃から40℃の範囲
で下記式を満足する時はさらに大きな接着強
度、低温での耐貫通性を有している。
log Ｅ≦10.0−0.0286T
Ｅ；110Hzで測定した複素弾性率の実数部
（dyne／cm2）
Ｔ；温度（℃）
本発明に用いる中間層に用いる共重合体はその
ままで十分に性能を有しているが、ジブチルフタ
レート、ジエチルヘキシルフタレート、ジオクチ
ルフタレートなどのフタル酸系の可塑剤、セバシ
ン酸ジブチル、アジピン酸ジオクチルなどの脂肪
酸系の可塑剤、トリキシレニルホスフエート、ト
リスクロロエチルホスフエートなどの燐酸系可塑
剤、さらには各種酸化防止剤、紫外線吸収剤、着
色剤などを本発明の目的をそこなわない範囲で添
加する事ができる。
本発明の合せガラスは上記共重合体を公知の加
工法、例えばカレンダーロール法、押出レシート
キヤステイング法、インフレーシヨン法などによ
つて製膜し、この樹脂膜をガラス間に重ね合わせ
て加熱、加圧下で熱溶融、圧着すればよい。この
場合加熱温度は80〜200℃、通常100〜180℃が用
いられる。圧力は中間膜とガラス板間の密着、及
び界面、中間層内の気泡除去に必要な圧力でよ
く、５〜15Kg／cm2が通常用いられる。加熱圧着に
際しては加熱プレス成形機、加熱炉付圧着ロー
ル、油圧又は空気圧式オートクレーブ等の従来の
可塑化ポリビニルブチラール膜に使用される貼り
合せ装置を用いることができる。
以上に説明した如く本発明の合せガラスは中間
層に前記したグラフト共重合体を用いる事によ
り、特に低温での耐貫通性にすぐれるとともに、
接着性、耐湿度性、耐水性、耐熱性にすぐれると
ともに耐光性、透明度が従来の合せガラスとくら
べて何ら劣らないのみならず、その製造工程にお
いて接着加工作業性にすぐれている為に安価に優
秀な合せガラスを得ることができ、工業的にきわ
めて有意なものである。本発明の合せガラスは車
輌用窓材、一般窓材或いは間仕切等に極めて有効
である。
次に本発明を実施例にて具体的に説明するが、
本発明はそれに限定されるものではない。
実施例 １
アクリル酸エチル成分の含有率が25重量％のエ
チレン−アクリル酸エチル共重合体150重量部お
よび無水マレイン酸６重量部を精製したトルエン
1000重量部に溶解し、180℃に保つた。この溶液
にベンゾイルーオキサイド0.5重量部をトルエン
1000重量部に溶解した溶液を撹拌下に180℃で５
時間にわたつて添加し、つづいて20分間撹拌をつ
づけた。冷却後大量のメタノール中に反応液を投
入精製した。得られたものの無水マレイン酸のグ
ラフト付加率は1.1重量％であつた。このグラフ
ト共重合体のＥの温度分散を第１図の曲線１に示
す。得られた共重合体を厚さ0.76mmにプレス成形
し、２枚のガラス板の間にはさみ80℃の雰囲気下
に20分間放置し、80℃のローラー間を通し両圧３
Kg／cmで予備接着を行なつた。つづいて150℃−
13Kg／cm2の空気圧式オートクレーブ中で30分間加
熱し、完全に接着し、合せガラスを得た。合せガ
ラスは下記の方法で評価した。結果を第１表に示
す。比較例にくらべて明かに低温での耐貫通性、
接着性が向上していることがわかる。又樹脂は自
着性が低い為、作業性はすこぶる良好であつた。
落球高さ；合せガラスを300×300mmの支持枠に
保持し、その上から2.26Kgの鋼球を試験
片の中央に落下させる。鋼球の高さを増
しながら一定高さでの繰り返し試験でそ
の試験数の50％が、鋼球によつて貫通し
ないときの、ガラス面への鋼球の落下距
離を求め、その距離をもつて落球高さと
した。従つて落球高さが大であるほど貫
通強度が大である事を示す。
パンメル値；合せガラスを１時間以上−20℃に
保つて恒温にしたのち、ハンマー破砕試
験にかけ、被着ガラスを粉砕する。割れ
たガラス片を振り落し、中間層が露出し
た部分を０〜８のランクにわけて露出度
が大きい程値が小さくなる様に判定す
る。
実施例 ２
酢酸ビニル成分の含有率が32重量％のエチレン
−酢酸ビニル共重合体を出発原料とする以外は実
施例１と同様にして合せガラスを得た。物性値は
第１表にしめす。その中間層樹脂の無水マレイン
酸のグラフト付加率は1.2重量％であり、そのＥ
の温度分散を第１図の曲線２に示す。
比較例 １
重量度1700、ケン化度99.6％のポリビニルアル
コールを用いて常法により得たブチラール化度66
モル％のポリビニルブチラールにトリエチレング
リコール・ジ・２−エチルブチレートを40部添加
して得た樹脂を中間層として実施例１の方法に準
じて合せガラスを得た。
結果を表１に記す。尚この樹脂は自着性が強
く、本発明例に比較して作業性がきわめて悪かつ
た。
【表】DETAILED DESCRIPTION OF THE INVENTION A. Technical Field of the Invention The present invention relates to a laminated glass having a graft copolymer as an intermediate layer. More specifically, the present invention provides a laminated glass having excellent penetration resistance and adhesive strength particularly at low temperatures, as well as excellent light resistance, penetration resistance, and water resistance. B. Prior art and its problems Conventionally, laminated glass has been made by thermo-compression bonding of two glass plates via plasticized polyvinyl butyral resin, and is widely used for safety glass for automobiles, aircraft, and construction. . However, polyvinyl butyral has an extremely strong film surface adhesion at room temperature, which causes the films to stick to each other after film formation (hereinafter referred to as self-adhesion), so the film surface is embossed to prevent such adhesion. In addition, an anti-blocking agent such as bicarbonate of soda is sprayed. Therefore, when bonding the polyvinyl butyral layer and glass, the anti-blocking agent must be removed by washing with water or the like.
However, polyvinyl butyral has −
Since it contains OH groups, it tends to absorb moisture easily, which can easily cause foaming during bonding, so a drying process is essential. This drying process causes problems in practical use due to a decrease in adhesiveness and transparency. Furthermore, laminated glass used as safety glass is particularly required to have penetration resistance at low temperatures. When polyvinyl butyral is used as an intermediate layer, it is necessary to add a particularly large amount of plasticizer in order to satisfy penetration resistance at low temperatures. If a large amount of plasticizer is added, the self-adhesiveness of the resin will become too large, resulting in amplification of troubles in the joining process as described above.
There was a limitation in that the various performances required for laminated glass were actually deteriorated. In view of the above conventional problems, the present inventors have completed the present invention as a result of intensive studies in order to solve the problems. C Structure, purpose, and effects of the present invention That is, the present invention comprises a plurality of glass plates by grafting an ethylenically unsaturated carboxylic acid or carboxylic acid anhydride component onto a copolymer of an ethylene component and an acrylic ester or a vinyl acetate component. The content of the unsaturated carboxylic acid or carboxylic acid anhydride obtained by
This is a laminated glass bonded with 5% by weight of a graft copolymer as an intermediate layer, and the resulting laminated glass has excellent penetration resistance, especially at low temperatures, and also has excellent moisture resistance, water resistance, and heat resistance. Not only is the light resistance and transparency comparable to that of conventional laminated glass, but it also has excellent adhesion workability in the manufacturing process. The graft copolymer used in the intermediate layer contains an acrylic ester or vinyl acetate component. The content varies depending on its structure, but is more preferably 20 to 40% by weight than 10 to 45% by weight. As the same component, acrylic acid esters such as acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, and acrylic acid 2-ethylhexyl ester are preferably used, but acrylic acid ethyl ester is more preferably used. The graft copolymer used in the present invention can be obtained by randomly copolymerizing these acrylic esters or vinyl acetate with ethylene, and then grafting an ethylenically unsaturated carboxylic acid or anhydride to this copolymer. . The content of ethylenically unsaturated carboxylic acid or carboxylic acid anhydride component in the graft copolymer is
The content is 0.1 to 5% by weight, more preferably 0.5 to 4% by weight. The same components include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, crotonic acid, and itaconic anhydride. Furthermore, when grafting, it may be preferable to co-graft styrene. There are no particular limitations on the method for producing the random copolymer or the graft copolymer. Among graft copolymers, ethylene-
Preferably, it is obtained by grafting maleic anhydride alone onto an acrylic acid ethyl ester copolymer, or by co-grafting it with styrene. Furthermore, although the laminated glass of the present invention has sufficient adhesive properties, it has even greater adhesive strength and penetration resistance at low temperatures when the intermediate layer satisfies the following formula in the range of -20°C to 40°C. are doing. log E≦10.0−0.0286T E: Real part of complex modulus measured at 110Hz (dyne/cm 2 ) T: Temperature (°C) The copolymer used for the intermediate layer used in the present invention has sufficient performance as it is. However, phthalic acid plasticizers such as dibutyl phthalate, diethylhexyl phthalate, and dioctyl phthalate, fatty acid plasticizers such as dibutyl sebacate and dioctyl adipate, tricylenyl phosphate, trischloroethyl phosphate, etc. A phosphoric acid plasticizer, various antioxidants, ultraviolet absorbers, colorants, etc. can be added within the range that does not impair the purpose of the present invention. The laminated glass of the present invention is produced by forming the above-mentioned copolymer into a film by a known processing method, such as a calender roll method, an extrusion receipt casting method, an inflation method, etc., and then stacking the resin film between glasses and heating it. , heat melting and pressure bonding under pressure. In this case, the heating temperature is 80 to 200°C, usually 100 to 180°C. The pressure may be any pressure necessary to maintain close contact between the interlayer film and the glass plate and to remove air bubbles at the interface and within the interlayer, and a pressure of 5 to 15 kg/cm 2 is usually used. For heat-compression bonding, conventional bonding devices used for plasticized polyvinyl butyral films, such as a hot press molding machine, a pressure roll with a heating furnace, and a hydraulic or pneumatic autoclave, can be used. As explained above, by using the above-mentioned graft copolymer in the intermediate layer, the laminated glass of the present invention has excellent penetration resistance especially at low temperatures, and
Not only does it have excellent adhesion, humidity resistance, water resistance, and heat resistance, and is no inferior to conventional laminated glass in terms of light resistance and transparency, but it is also inexpensive because it has excellent adhesion workability in the manufacturing process. It is possible to obtain excellent laminated glass, which is extremely significant industrially. The laminated glass of the present invention is extremely effective for vehicle window materials, general window materials, partitions, etc. Next, the present invention will be specifically explained with examples.
The invention is not limited thereto. Example 1 Toluene purified from 150 parts by weight of ethylene-ethyl acrylate copolymer containing 25% by weight of ethyl acrylate component and 6 parts by weight of maleic anhydride
It was dissolved in 1000 parts by weight and kept at 180°C. Add 0.5 parts by weight of benzoyl oxide to this solution and add toluene.
A solution of 1000 parts by weight was heated at 180°C with stirring for 5 minutes.
The mixture was added over a period of time followed by continued stirring for 20 minutes. After cooling, the reaction solution was poured into a large amount of methanol for purification. The graft addition rate of maleic anhydride in the obtained product was 1.1% by weight. The temperature distribution of E of this graft copolymer is shown in curve 1 of FIG. The obtained copolymer was press-molded to a thickness of 0.76 mm, sandwiched between two glass plates, left in an atmosphere at 80°C for 20 minutes, passed between rollers at 80°C, and heated at both pressures of 3.
Pre-bonding was carried out at Kg/cm. Next, 150℃−
It was heated in a pneumatic autoclave at 13 kg/cm 2 for 30 minutes to completely adhere and obtain a laminated glass. The laminated glass was evaluated by the following method. The results are shown in Table 1. Penetration resistance at low temperatures is clearly higher than that of the comparative example.
It can be seen that the adhesiveness is improved. Also, since the resin has low self-adhesion, workability was very good. Falling ball height: The laminated glass is held in a 300 x 300 mm support frame, and a 2.26 kg steel ball is dropped from above onto the center of the test piece. Determine the falling distance of the steel ball on the glass surface when the steel ball does not penetrate 50% of the times in repeated tests at a constant height while increasing the height of the steel ball, and obtain that distance. The height of the ball was determined by the height of the ball. Therefore, the greater the falling ball height, the greater the penetration strength. Pummel value: After the laminated glass is kept at -20°C for more than 1 hour to reach a constant temperature, it is subjected to a hammer crushing test to crush the adhered glass. The broken glass piece is shaken off, and the exposed portion of the intermediate layer is ranked from 0 to 8, and the higher the degree of exposure, the lower the value. Example 2 A laminated glass was obtained in the same manner as in Example 1 except that an ethylene-vinyl acetate copolymer having a vinyl acetate content of 32% by weight was used as the starting material. Physical property values are shown in Table 1. The graft addition rate of maleic anhydride in the intermediate layer resin was 1.2% by weight, and the E
The temperature distribution is shown in curve 2 of FIG. Comparative Example 1 Butyralization degree 66 obtained by a conventional method using polyvinyl alcohol with a weight of 1700 and a saponification degree of 99.6%.
A laminated glass was obtained according to the method of Example 1 using a resin obtained by adding 40 parts of triethylene glycol di-2-ethyl butyrate to mol % polyvinyl butyral as an intermediate layer. The results are shown in Table 1. This resin had strong self-adhesive properties and had extremely poor workability compared to the examples of the present invention. 【table】
第１図は中間層に用いたグラフト共重合体の複
素弾性率の実数部Ｅと温度Ｔとの関係を示すグラ
フであり、縦軸はlogE、横軸は温度Ｔ（℃）を示
す。
１……実施例１の曲線、２……実施例２の曲
線。
FIG. 1 is a graph showing the relationship between the real part E of the complex modulus of elasticity of the graft copolymer used for the intermediate layer and the temperature T, where the vertical axis shows logE and the horizontal axis shows the temperature T (° C.). 1...Curve of Example 1, 2...Curve of Example 2.
Claims (1)
エステルもしくは酢酸ビニル成分との共重合体に
エチレン性不飽和カルボン酸もしくは該カルボン
酸無水物成分をグラフトして得た、前記不飽和カ
ルボン酸もしくは該カルボン酸無水物の含有量が
グラフト共重合体に対し0.1〜５重量％であるグ
ラフト共重合体を中間層として接合した合せガラ
ス。 ２ 中間層が温度−20°から40℃の間で下記式
を満足する特許請求の範囲１に記載の合せガラ
ス。 log Ｅ≦10.0−0.0286T…… Ｅ；110Hzで測定した複素弾性率の実数部 （dyne／cm2） Ｔ；温度（℃） ３ 中間層がエチレン成分とアクリル酸エステル
成分との共重合体にエチレン性不飽和カルボン酸
もしくは該カルボン酸無水物成分をグラフトして
得たグラフト共重合体である特許請求の範囲第１
または第２項に記載の合せガラス。[Scope of Claims] 1 A plurality of glass plates are prepared by grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component onto a copolymer of an ethylene component and an acrylic ester or a vinyl acetate component. A laminated glass bonded with a graft copolymer having a content of saturated carboxylic acid or carboxylic acid anhydride of 0.1 to 5% by weight based on the graft copolymer as an intermediate layer. 2. The laminated glass according to claim 1, wherein the intermediate layer satisfies the following formula at a temperature between -20°C and 40°C. log E≦10.0−0.0286T... E: Real part of complex modulus measured at 110Hz (dyne/cm 2 ) T: Temperature (℃) 3 The intermediate layer is a copolymer of ethylene component and acrylic ester component. Claim 1, which is a graft copolymer obtained by grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component.
Or the laminated glass according to item 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11876984A JPS60264348A (en) | 1984-06-08 | 1984-06-08 | Laminated glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11876984A JPS60264348A (en) | 1984-06-08 | 1984-06-08 | Laminated glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60264348A JPS60264348A (en) | 1985-12-27 |
| JPH0433750B2 true JPH0433750B2 (en) | 1992-06-03 |
Family
ID=14744610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11876984A Granted JPS60264348A (en) | 1984-06-08 | 1984-06-08 | Laminated glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60264348A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63151649A (en) * | 1986-12-15 | 1988-06-24 | Showa Denko Kk | Interlayer for laminated glass |
| JPH0930844A (en) * | 1995-05-17 | 1997-02-04 | Bridgestone Corp | Laminated glass |
| JPH0930845A (en) * | 1995-05-17 | 1997-02-04 | Bridgestone Corp | Laminated glass |
| KR100761177B1 (en) * | 2005-11-22 | 2007-10-04 | 한수일 | Process for preparing pairglass have color coating layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879817A (en) * | 1972-01-18 | 1973-10-26 |
-
1984
- 1984-06-08 JP JP11876984A patent/JPS60264348A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879817A (en) * | 1972-01-18 | 1973-10-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60264348A (en) | 1985-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6337050B2 (en) | ||
| JPH05310449A (en) | Intermediate film for safety glass and safety glass using the same | |
| RU2325408C9 (en) | Film applied as intermediate layer for triplexes, triplex containing this film and method of transportation and/or storage of rolled film | |
| US3262836A (en) | Laminated safety glass | |
| US3952135A (en) | Laminated glass windows for vehicles | |
| JPH0433750B2 (en) | ||
| JPH11323056A (en) | Interlayer for glass laminate and laminated glass | |
| JP2001226152A (en) | Intermediate film for sandwich glass and sandwich glass | |
| JPH07172878A (en) | Intermediate film for laminated glass | |
| JP6574907B2 (en) | Resin foam, resin foam sheet, adhesive tape, vehicle member and building member | |
| JP4339485B2 (en) | Laminated glass interlayer film and laminated glass | |
| JP2017021527A (en) | Interlayer filling material kit for touch panel, laminate, and method for manufacturing laminate | |
| JPH10338556A (en) | Different kind laminated glass | |
| JP2000247690A (en) | Adhesive intermediate film for laminated glass and laminated glass | |
| JP4404396B2 (en) | Laminated glass interlayer film and laminated glass | |
| WO2014188544A1 (en) | Laminate having excellent sound-insulating properties | |
| JP2000319044A (en) | Intermediate film for sandwich glass and sandwich glass | |
| JPH08109048A (en) | Intermediate film for safety glass and safety glass | |
| JPS6215497B2 (en) | ||
| JPS6337051B2 (en) | ||
| JPH04317443A (en) | Laminated glass | |
| JPS6151339A (en) | Glass laminate | |
| JPS6337052B2 (en) | ||
| JPH101335A (en) | Laminated glass | |
| JPH0372588B2 (en) |