JPS636074A - Aqueous dispersion adhesive - Google Patents
Aqueous dispersion adhesiveInfo
- Publication number
- JPS636074A JPS636074A JP14897686A JP14897686A JPS636074A JP S636074 A JPS636074 A JP S636074A JP 14897686 A JP14897686 A JP 14897686A JP 14897686 A JP14897686 A JP 14897686A JP S636074 A JPS636074 A JP S636074A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- phosphate
- powder
- aqueous dispersion
- ester
- 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
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 37
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 37
- 239000006185 dispersion Substances 0.000 title claims description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 9
- -1 phosphate ester Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000011888 foil Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 229920003002 synthetic resin Polymers 0.000 abstract description 7
- 239000000057 synthetic resin Substances 0.000 abstract description 7
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004254 Ammonium phosphate Substances 0.000 abstract description 2
- 229920012753 Ethylene Ionomers Polymers 0.000 abstract description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract description 2
- 235000019289 ammonium phosphates Nutrition 0.000 abstract description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229920000554 ionomer Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- 235000011008 sodium phosphates Nutrition 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-L ethyl phosphate(2-) Chemical compound CCOP([O-])([O-])=O ZJXZSIYSNXKHEA-UHFFFAOYSA-L 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、水中に熱可塑性接着剤粉末を分散させたディ
スパージョン型の接着剤に関し、特に金Ｎ箔と親水性合
成樹脂製フィルムとの接着力の向上に寄与するディスパ
ージョン型の接着剤に関するものである。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a dispersion type adhesive in which thermoplastic adhesive powder is dispersed in water, and in particular to a dispersion type adhesive in which thermoplastic adhesive powder is dispersed in water. This invention relates to a dispersion-type adhesive that contributes to improving the adhesive strength of.
（ロ）従来の技術及び発明が解決しようとする問題点
従来より、包装資材として金属箔と合成樹脂製フィルム
とを貼合したものが用いられている。この貼合に当たっ
ては、種々の接着剤が適宜採用されている。ところで、
金属箔と親水性合成樹脂製フィルムとの貼合には、主に
水性ディスパージョン型の接着剤が多くの場合採用され
ている。(B) Problems to be Solved by the Prior Art and the Invention Conventionally, packaging materials made by laminating metal foil and synthetic resin film have been used. Various adhesives are appropriately used for this bonding. by the way,
Aqueous dispersion type adhesives are mainly used in many cases to bond metal foils and hydrophilic synthetic resin films.
しかし、水性ディスパージョン型の接着剤の場合には、
接着力が弱いという憾みがあった。接着力が不足する場
合には、包装資材を成型若しくは加工して包装容器とす
る際に、金属箔と合成樹脂製フィルムとの貼合が剥離す
るという欠点があり、包装容器としての商品価値を低下
させてしまうということがあった。However, in the case of water-based dispersion type adhesives,
I was disappointed that the adhesive strength was weak. If the adhesive strength is insufficient, the bond between the metal foil and the synthetic resin film will peel off when the packaging material is molded or processed into a packaging container, which may reduce the commercial value of the packaging container. There was a possibility that it would be lowered.
そこで、本発明は水性ディスパージョン型の接着剤の接
着力を向上させることを目的としてなされたものである
。Therefore, the present invention was made with the object of improving the adhesive strength of aqueous dispersion type adhesives.
（ハ）問題点を解決するための手段及び作用即ち本発明
は、水中に熱可塑性接着剤粉末を分散させた懸濁液に、
リン酸塩又はリン酸エステルを添加させてなることを特
徴とする水性ディスパージョン接着剤に係るものである
。(c) Means and operation for solving the problem, that is, the present invention provides a suspension of thermoplastic adhesive powder dispersed in water.
This invention relates to an aqueous dispersion adhesive characterized by adding a phosphate or a phosphate ester.
本発明に用いる熱可塑性接着剤粉末としては、ポリエチ
レン、ポリプロピレン、ポリメタクリル酸エチル、ポリ
アクリル酸エチル、ポリ酢酸ビニル、ポリビニルブチラ
ール等の粉末が用いられる。The thermoplastic adhesive powder used in the present invention includes powders of polyethylene, polypropylene, polyethyl methacrylate, polyethyl acrylate, polyvinyl acetate, polyvinyl butyral, and the like.
また、エチレン系アイオノマー樹脂粉末、プロピレン系
アイオノマー樹脂粉末等のアイオノマー樹脂粉末も好適
に用いることができる。粉末の粒子系は、１０〜１００
０μ程度が好ましい。この熱可塑性接着剤粉末を水中に
分散し、懸濁液が調整される。Ionomer resin powders such as ethylene ionomer resin powder and propylene ionomer resin powder can also be suitably used. Powder particle system is 10-100
Approximately 0μ is preferable. This thermoplastic adhesive powder is dispersed in water to prepare a suspension.
この懸濁液において、熱可塑性接着剤粉末の濃度は１０
〜８０重量％程度が好適である。In this suspension, the concentration of thermoplastic adhesive powder is 10
About 80% by weight is suitable.
本発明において、この懸濁液にリン酸塩若しくはリン酸
エステルを添加する０本発明に言うリン酸とは、最も広
義の意味において使用されており、オルトリン酸は勿論
、ポリリン酸、メタリン酸。In the present invention, phosphoric acid or phosphoric acid ester is added to this suspension.The phosphoric acid referred to in the present invention is used in the broadest sense, and includes not only orthophosphoric acid but also polyphosphoric acid and metaphosphoric acid.
次亜リン酸、亜すン酸、ピロ亜すン酸、ピロリン酸、三
すン酸、ベルオクソリン酸等をも包含するものである。It also includes hypophosphorous acid, sulfurous acid, pyrophosphorous acid, pyrophosphoric acid, trisonic acid, peroxolinic acid, and the like.
従って、リン酸塩としては、リン酸アンモニウム、リン
酸ナトリウム、リン酸カリウム、次亜リン酸ナトリウム
、ビロリン酸ナトリウム、酸性メタリン酸ナトリウム、
トリポリリン酸ナトリウム等が用いられ、リン酸エステ
ルとしては、リン酸トリメチル、リン酸トリエチル、リ
ン酸トリブチル、リン酸モノエチル、リン酸ジエチル、
メタリン酸エチル、ビロリン酸エチル等が用いられる。Therefore, as phosphates, ammonium phosphate, sodium phosphate, potassium phosphate, sodium hypophosphite, sodium birophosphate, sodium acid metaphosphate,
Sodium tripolyphosphate etc. are used, and the phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monoethyl phosphate, diethyl phosphate,
Ethyl metaphosphate, ethyl birophosphate, etc. are used.
リン酸塩若しくはリン酸エステルの添加量は、￥！、′
／！ｉＡ液中の接着剤（固形分）１００重量部に対して
０．０１〜３重量部程置部好ましい。リン酸塩若しくは
リン酸エステルの添加量が０．０１未満の場合又は３重
量部を超えた場合には接着剤の接着力が低下する傾向と
なる。The amount of phosphate or phosphate ester added is ¥! ,′
/! The amount is preferably 0.01 to 3 parts by weight per 100 parts by weight of the adhesive (solid content) in the iA liquid. If the amount of phosphate or phosphoric acid ester added is less than 0.01 or exceeds 3 parts by weight, the adhesive strength of the adhesive tends to decrease.
（ニ）実施例
実施例１
工、チレン系アイオノマー樹脂ディスパージョン（三井
石油化学工業ｆｉｎ！！Ｊ、ケミバールＳ−３００）
中に、該ディスパージョン固形分１００重量部に対して
０．５重量部のリン酸ナトリウムを添加して、水性ディ
スパージョン接着剤を得た。この水性ディスパージョン
接着剤を１５０μのアルミニウム箔に＃６のバーコータ
ーを用いて塗布し、次いで塗布された水性ディスパージ
ョン接着剤を乾燥した。(D) Examples Example 1 Polyethylene ionomer resin dispersion (Mitsui Petrochemical Industries fin!!J, Chemivar S-300)
0.5 parts by weight of sodium phosphate was added to 100 parts by weight of the solid content of the dispersion to obtain an aqueous dispersion adhesive. This aqueous dispersion adhesive was applied to a 150μ aluminum foil using a #6 bar coater, and then the applied aqueous dispersion adhesive was dried.
その後、エチレン系アイオノマー樹脂フィルム（三井石
油化学工業■製、ハイミラン１６５２）を重ね合わせて
８０℃で加熱、加圧して仮接着し、更に１７０℃に加熱
されたドラムを用いて１０秒間加熱、加圧してアルミニ
ウム箔とフィルムとの貼合物を得た。After that, ethylene-based ionomer resin films (manufactured by Mitsui Petrochemical Industries, Ltd., Himilan 1652) were overlapped and temporarily bonded by heating and pressing at 80°C, and then heating and pressing for 10 seconds using a drum heated to 170°C. Pressing was performed to obtain a bonded product of aluminum foil and film.
この貼合物の接着力を評価するため、１８０°剥離強度
を測定したところ、剥離速度２００Ｍ／分の条件下で１
５００ ｇ ／ １５ｆｉ巾であった。In order to evaluate the adhesive strength of this laminated product, the 180° peel strength was measured and the results were as follows:
It was 500g/15fi width.
実施例２
実施例１で用いたエチレン系アイオノマー樹脂フィルム
に代えてポリエステルフィルムを用いる以外は、全て実
施例１と同一の条件でアルミニウム箔とフィルムとの貼
合物を得た。Example 2 A bonded product of aluminum foil and film was obtained under the same conditions as in Example 1 except that a polyester film was used in place of the ethylene-based ionomer resin film used in Example 1.
この貼合物の１８０°剥離強度は、剥離速度２００ｆｌ
／分の条件下で１２００ｇ／１５ｍ巾であった。The 180° peel strength of this bond was determined at a peel rate of 200 fl.
It was 1200g/15m width under the condition of /min.
実施例３
実施例１でディスパージランに添加するために用いたリ
ン酸ナトリウムに代えてリン酸トリメチルを用いる以外
は、全て実施例１と同一の条件でアルミニウム箔とフィ
ルムとの貼合物を得た。Example 3 A laminate of aluminum foil and film was obtained under the same conditions as in Example 1, except that trimethyl phosphate was used in place of the sodium phosphate used to add dispergylan in Example 1. Ta.
この貼合物の１８０°剥離強度は、剥離速度２００鶴／
分の条件下で１３００ｇ／１５ｍ巾であった。The 180° peel strength of this laminated material is as follows:
It was 1300g/15m width under the conditions of 15 minutes.
比較例
実施例１で用いたエチレン系アイオノマー樹脂ディスパ
ージョンにリン酸ナトリウムを添加しないで、そのまま
アルミニウム箔に塗布する以外は、全て実施例１と同一
の条件でアルミニウム箔とフィルムとの貼合物を得た。Comparative Example A laminate of aluminum foil and film was prepared under the same conditions as in Example 1 except that sodium phosphate was not added to the ethylene-based ionomer resin dispersion used in Example 1 and the dispersion was applied directly to the aluminum foil. I got it.
この貼合物の１８０°剥離強度は、剥離速度２００、／
分の条件下で６００ｇ／１５ｍ巾であった。The 180° peel strength of this laminated material is as follows:
It was 600g/15m width under the conditions of 15 minutes.
（ホ）発明の詳細
な説明したように、リン酸塩又はリン酸エステルが添加
されている本発明に係る水性ディスパージョン接着剤を
用いれば、リン酸塩又はリン酸エステルが添加されてい
ない従来のディスパージラン型接着剤を用いた場合に比
べて、金属箔と合成樹脂製フィルムとの接着力が向上す
る。従って、金属箔と合成樹脂製フィルムとの貼合物を
包装資材として用い、各種の成型又は加工を施しても金
属箔と合成樹脂製フィルムとが剥離することが少なく、
商品価値の高い包装容器を得ることができる。(E) As described in detail of the invention, if the aqueous dispersion adhesive according to the present invention to which phosphate or phosphate ester is added is used, it will be possible to use the aqueous dispersion adhesive according to the present invention, The adhesive strength between the metal foil and the synthetic resin film is improved compared to when a dispargy run adhesive is used. Therefore, even when a laminate of metal foil and synthetic resin film is used as a packaging material and subjected to various molding or processing, the metal foil and synthetic resin film are unlikely to peel off.
A packaging container with high commercial value can be obtained.
Claims (1)
酸塩又はリン酸エステルを添加させてなることを特徴と
する水性ディスパージョン接着剤。An aqueous dispersion adhesive characterized by adding a phosphate or a phosphate ester to a suspension of thermoplastic adhesive powder dispersed in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14897686A JPS636074A (en) | 1986-06-25 | 1986-06-25 | Aqueous dispersion adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14897686A JPS636074A (en) | 1986-06-25 | 1986-06-25 | Aqueous dispersion adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS636074A true JPS636074A (en) | 1988-01-12 |
| JPH0220674B2 JPH0220674B2 (en) | 1990-05-10 |
Family
ID=15464890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14897686A Granted JPS636074A (en) | 1986-06-25 | 1986-06-25 | Aqueous dispersion adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS636074A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4502815A (en) * | 1982-09-27 | 1985-03-05 | Nicolon Corporation | Revetment panel methods |
| US4592675A (en) * | 1982-09-27 | 1986-06-03 | Nicolon Corporation | Revetment panel with staggered compartments |
| US5352514A (en) * | 1990-04-25 | 1994-10-04 | Nitta Gelatin Inc. | Metal surface adhered to a second metal surface |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4996054A (en) * | 1972-12-16 | 1974-09-11 | ||
| JPS59120647A (en) * | 1982-12-27 | 1984-07-12 | Japan Synthetic Rubber Co Ltd | Method for producing carboxy-modified latex |
| JPS59191780A (en) * | 1983-04-13 | 1984-10-30 | Hoechst Gosei Kk | Macromolecular adhesive and preparation thereof |
-
1986
- 1986-06-25 JP JP14897686A patent/JPS636074A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4996054A (en) * | 1972-12-16 | 1974-09-11 | ||
| JPS59120647A (en) * | 1982-12-27 | 1984-07-12 | Japan Synthetic Rubber Co Ltd | Method for producing carboxy-modified latex |
| JPS59191780A (en) * | 1983-04-13 | 1984-10-30 | Hoechst Gosei Kk | Macromolecular adhesive and preparation thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4502815A (en) * | 1982-09-27 | 1985-03-05 | Nicolon Corporation | Revetment panel methods |
| US4592675A (en) * | 1982-09-27 | 1986-06-03 | Nicolon Corporation | Revetment panel with staggered compartments |
| US5352514A (en) * | 1990-04-25 | 1994-10-04 | Nitta Gelatin Inc. | Metal surface adhered to a second metal surface |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0220674B2 (en) | 1990-05-10 |
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