JPH0147505B2 - - Google Patents
Info
- Publication number
- JPH0147505B2 JPH0147505B2 JP55185498A JP18549880A JPH0147505B2 JP H0147505 B2 JPH0147505 B2 JP H0147505B2 JP 55185498 A JP55185498 A JP 55185498A JP 18549880 A JP18549880 A JP 18549880A JP H0147505 B2 JPH0147505 B2 JP H0147505B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- months
- adhesive
- cyano
- acid 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.)
- Expired
Links
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 14
- -1 2-cyanoacrylic acid ester Chemical class 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- WLVPRARCUSRDNI-UHFFFAOYSA-N 2-hydroxy-1-phenyl-1-propanone Chemical compound CC(O)C(=O)C1=CC=CC=C1 WLVPRARCUSRDNI-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000004830 Super Glue Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- XOVJAYNMQDTIJD-UHFFFAOYSA-N cyclopentobarbital Chemical group C1CC=CC1C1(CC=C)C(=O)NC(=O)NC1=O XOVJAYNMQDTIJD-UHFFFAOYSA-N 0.000 description 1
- 229950000178 cyclopentobarbital Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は新規な接着剤組成物、特に剥離性、耐
衝撃性等の接着性が改良されたシアノアクリル酸
エステル系接着剤組成物に係るものである。
２−シアノアクリル酸エステル系接着剤（以下
シアノ系接着剤と記す）は、アニオン重合性が大
きく被着体表面の微量の水分でも常温で速やかな
重合を行い強固な接着を行うので瞬間接着剤とし
て金属、プラスチツク、ゴム、ガラスや木材をは
じめ各種の材質の接着に利用されている事は周知
の通りである。
各種の材質を常温で短時間に強固に接着するシ
アノ系接着剤は優れた組成物であるが耐衝撃性、
耐剥離性の点では不十分であり、この様な応力負
荷がされる場所の接着には供し難いものであつ
た。これらの性質は実用上重要な特性である為、
従来はゴム等を緩衝材として介して接着する方法
や組成物の中に各種添加剤を用いる方法が試みら
れているが瞬間接着剤としてのシアノ系接着剤本
来の特性を著しく減退させる事が多く満足できる
ものでなく、その改良が要請されていた。
従来提案されているカルボン酸やその無水物類
を用いる方法は、耐衝撃性の改良には有効である
が硬化速度が遅くなるとか、或いは性能品質の経
時的劣化が激しく実用には供し得ないものであり
ヒドロキシカルボン酸エステルを用いる方法は効
果の点で尚満足し難いものであつた。
本発明者は２−シアノアクリレートの本来の重
合性を害う事なく接着性能が改良されたシアノ系
接着剤組成物を得るべく研究した結果、２−シア
ノアクリレートにα−ヒドロキシケトン化合物を
１種又は２種以上混合して配合した組成物は通常
のシアノ系組成物に比較して例えば剥離強度、衝
撃強度が10倍又はそれ以上も大きくて改良でき、
かつ本来のシアノ系接着剤の特性を有している事
を見い出して本発明に至つた。
本発明に用いられる２−シアノアクリル酸エス
テルは通常瞬間接着剤として使用されているエス
テルが全て使用できる。これらは例えば、メチ
ル、エチル、プロピル、ブチル、アシル、ヘキシ
ル、シクロヘキシル、ベンジル、フエニル、オク
チル、ドデシル、アリル、プロパギル、メトキシ
エチル、エトキシエチル、フルフリル、テトラヒ
ドロフルフリル、クロロエチル、フロロエチル、
ヘキサクロロエチル等の２−シアノアクリル酸エ
ステルである。
これらの２−シアノアクリル酸エステルに添加
して効果のある化合物は
式で示されるα−ヒドロキシケトン（式中R1、
R2はメチル、エチル、ブチル、オクチル、フエ
ニル、ベンジル、シクロヘキシル、シクロペンタ
ル、エトキシエチル、ブトキシエチル、フラン、
テトラヒドロフラン、テトラヒドロフルフリル、
アリル、プロパギルの様な互に同一又は別異の炭
化水素基又はそれから誘導される基或いはこれら
の炭化水素基又は誘導される基のクロロ、又はフ
ロロ置換基である）化合物である。
これらの１例を示せばベンゾイン、２−ヒドロ
キシプロピオフエノン、１，１，１−トリフロロ
２−ヒドロキシプロピオフエノンで代表されるα
−ヒドロキシケトンを挙げる事ができる。
これらのα−ヒドロキシケトンは１種又は２種
以上を混合0.01％以下では効果が少なく、２％以
上加えてもそれ以上の効果は対応せず、経済的価
値が減少するので0.01〜２％を２−シアノアクリ
ル酸エステルに加えて更に通常使用されている安
定剤、増粘剤、可塑剤、着色剤、架橋剤を必要に
応じて添加して本発明の組成物を調製する事がで
きる。
この様にして得られる本発明の組成物はカルボ
ン酸やその無水物を用いる組成物で認められる様
な保存中で性能の経時劣化や硬化速度の遅延がな
く、保存安定性が良好で鉄、銅、アルミニウム、
錫、亜鉛やこれらの合金類、フエライト等の金属
の他、ガラス、セラミツク、陶磁器等の無機材や
プラスチツク、ゴム等に対しても極めて大きな剥
離強度や耐衝撃強度を示している。この様な効果
が顕われる理由は、金属等の固体表面にα−ヒド
ロキシケトンがキレート結合、又は配位結合を形
成し接着の界面状態を変えている事も想定される
が明らかでない。何れの機序に基づくものである
にせよシアノ系接着剤の特性を失う事なく剥離強
度や耐衝撃強度が著しく改良されるので実用上有
用である。
以下に実施例及び比較例を示す。文中部はいず
れも重量部を表わす。
実施例 １
安定剤として20ppmのSO2と100ppmのハイド
ロキノンを含む２−シアノエチルアクリレート96
部にトリメリツト酸トリオクチル2.5部と、２−
ヒドロキシプロピオフエノン0.05部、トリフロロ
アセチルアセトン0.05部を加え室温で撹拌して溶
解させて無色透明な組成物を得た。
この組成物をJIS−Ｋ−6861に基づいて試験し
た結果、70℃５日間の所定条件で粘度の変化率は
0.1％、着色等の外観の変化も無く貯蔵安定性は
良好であつた。
各種接着性能はセツトタイム軟鋼40秒、引張剪
断強さ250Kg／cm2、150℃１時間加熱後の室温での
引張剪断強さは240Kg／cm2JIS−Ｋ−6855に基づく
衝撃剥離強度は150Kgｆ／in2以上であり、又200μ
のアルミニウム箔をトリクロロエチレンで超音波
洗浄後23℃59％RHの雰囲気下で接着24時間同条
件で養生した試片のＴ字剥離強さ（剥離速度50
mm／min）は5.9Kg／25mmであり、後に示す比較
例に示した通常の製品に比べて剥離強さ、衝撃強
さが特に優れていた。
製品を20ｇポリエチレン容器に入れ23℃、59〜
60％RHの雰囲気下で放置した後の性能の経時変
化は引張剪断強さは３ケ月、６ケ月、９ケ月で共
に変化はなく、剥離強度は３ケ月6.2Kg／25mm、
９ケ月6.2Kg／２mm衝撃強さは、３ケ月、６ケ月、
９ケ月共に150Kgｆ／in2以上であり性能の経時変
化が無く良好であつた。
実施例 ２
安定剤として20ppmのSO2と100ppmのハイド
ロキノンと３％のトリメリツト酸トリオクチルを
含む各種２−シアノククリレートに表１に示すよ
うに各種α−ヒドロキシケトンを加えて組成物を
調製し同様に試験した。
この結果は表−２、表−３に示す通りであり、
通常配合である比較例に比べ接着性能が優れてい
た。
The present invention relates to a novel adhesive composition, particularly a cyanoacrylate adhesive composition with improved adhesive properties such as peelability and impact resistance. 2-Cyanoacrylic acid ester adhesives (hereinafter referred to as cyano adhesives) are highly anionic polymerizable and quickly polymerize at room temperature even with a small amount of moisture on the surface of the adherend, resulting in strong adhesion, so they are considered instant adhesives. As is well known, it is used to bond various materials including metal, plastic, rubber, glass, and wood. Cyano adhesive has an excellent composition that can firmly bond various materials in a short time at room temperature, but it has poor impact resistance,
It has insufficient peeling resistance and is difficult to be used for adhesion in places where such stress is applied. These properties are important in practical terms, so
In the past, attempts have been made to bond using rubber or other materials as a cushioning material, or to use various additives in the composition, but these often significantly reduce the inherent properties of cyano adhesives as instant adhesives. This was not satisfactory and improvements were requested. Conventionally proposed methods using carboxylic acids and their anhydrides are effective in improving impact resistance, but they slow down the curing speed or cause severe deterioration of performance quality over time, making them impractical. However, the method using hydroxycarboxylic acid ester was still unsatisfactory in terms of effectiveness. As a result of research to obtain a cyano-based adhesive composition with improved adhesive performance without impairing the original polymerizability of 2-cyanoacrylate, the present inventors discovered that one type of α-hydroxyketone compound was added to 2-cyanoacrylate. Or, a composition prepared by mixing two or more types can be improved by having peel strength and impact strength that are 10 times or more greater than those of ordinary cyano-based compositions.
They also discovered that it has the characteristics of a cyano adhesive, leading to the present invention. As the 2-cyanoacrylic acid ester used in the present invention, all esters commonly used as instant adhesives can be used. These include, for example, methyl, ethyl, propyl, butyl, acyl, hexyl, cyclohexyl, benzyl, phenyl, octyl, dodecyl, allyl, propargyl, methoxyethyl, ethoxyethyl, furfuryl, tetrahydrofurfuryl, chloroethyl, fluoroethyl,
2-cyanoacrylic acid ester such as hexachloroethyl. Compounds that are effective when added to these 2-cyanoacrylic acid esters are α-Hydroxyketone represented by the formula (wherein R 1 ,
R2 is methyl, ethyl, butyl, octyl, phenyl, benzyl, cyclohexyl, cyclopental, ethoxyethyl, butoxyethyl, furan,
Tetrahydrofuran, Tetrahydrofurfuryl,
They are compounds which are mutually the same or different hydrocarbon groups such as allyl and propargyl, or groups derived therefrom, or chloro or fluoro substituents of these hydrocarbon groups or groups derived therefrom. Examples of these include benzoin, 2-hydroxypropiophenone, and 1,1,1-trifluoro-2-hydroxypropiophenone.
-Hydroxyketones may be mentioned. These α-hydroxyketones have little effect if one or more of them are mixed at 0.01% or less, and even if 2% or more is added, no further effect will be obtained and the economic value will decrease, so 0.01 to 2% should be used. In addition to the 2-cyanoacrylic acid ester, the composition of the present invention can be prepared by adding, if necessary, commonly used stabilizers, thickeners, plasticizers, colorants, and crosslinking agents. The composition of the present invention obtained in this manner does not deteriorate over time or slow down the curing speed during storage, unlike compositions using carboxylic acids or their anhydrides, and has good storage stability. copper, aluminum,
It exhibits extremely high peel strength and impact resistance against metals such as tin, zinc, their alloys, and ferrite, as well as inorganic materials such as glass, ceramics, and ceramics, as well as plastics and rubber. The reason why such an effect appears is not clear, although it is assumed that α-hydroxyketone forms a chelate bond or coordinate bond on the surface of a solid such as a metal, thereby changing the interfacial state of adhesion. Regardless of the mechanism, it is practically useful because the peel strength and impact strength are significantly improved without losing the properties of the cyano adhesive. Examples and comparative examples are shown below. All parts in the middle of the sentence represent parts by weight. Example 1 2-cyanoethyl acrylate 96 with 20 ppm SO 2 and 100 ppm hydroquinone as stabilizers
2.5 parts of trioctyl trimellitate and 2-
0.05 part of hydroxypropiophenone and 0.05 part of trifluoroacetylacetone were added and dissolved by stirring at room temperature to obtain a colorless and transparent composition. As a result of testing this composition based on JIS-K-6861, the rate of change in viscosity under the specified conditions of 70℃ for 5 days was
0.1%, the storage stability was good with no change in appearance such as coloring. Various adhesion properties are set time: 40 seconds for mild steel, tensile shear strength: 250 Kg/cm 2 , tensile shear strength at room temperature after heating at 150°C for 1 hour: 240 Kg/cm 2 Impact peel strength based on JIS-K-6855: 150 Kgf /in 2 or more and 200μ
T-peel strength of a specimen made of aluminum foil ultrasonically cleaned with trichlorethylene, bonded in an atmosphere of 23°C, 59% RH, and cured under the same conditions for 24 hours (peel speed 50
mm/min) was 5.9 Kg/25 mm, and the peel strength and impact strength were particularly excellent compared to the normal products shown in the comparative examples shown later. Place the product in a 20g polyethylene container at 23℃, 59~
Changes in performance over time after being left in an atmosphere of 60% RH show that the tensile shear strength remains the same after 3 months, 6 months, and 9 months, and the peel strength is 6.2 kg/25 mm after 3 months.
9 months 6.2Kg/2mm impact strength is 3 months, 6 months,
It was 150Kgf/in 2 or more for 9 months, and the performance was good with no change over time. Example 2 Compositions were prepared by adding various α-hydroxyketones as shown in Table 1 to various 2-cyanoccrylates containing 20 ppm SO 2 , 100 ppm hydroquinone, and 3% trioctyl trimellistate as stabilizers, and the same compositions were prepared. was tested. The results are shown in Table-2 and Table-3,
Adhesive performance was superior to that of the comparative example, which had a normal formulation.
【表】【table】
【表】【table】
【表】
各実施例の貯蔵安定性試験の結果、粘度、外観
セツトタイムに著しい変化は何れも認められず良
好であつた。[Table] The results of the storage stability test for each example were good, with no significant changes observed in viscosity or appearance setting time.
Claims (1)
キシケトン化合物を１種又は２種以上混合して配
合した剥離性や他の接着性能の改良された接着剤
組成物。1. An adhesive composition with improved peelability and other adhesive properties, which is prepared by mixing one or more α-hydroxyketone compounds with 2-cyanoacrylic acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18549880A JPS57109876A (en) | 1980-12-27 | 1980-12-27 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18549880A JPS57109876A (en) | 1980-12-27 | 1980-12-27 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57109876A JPS57109876A (en) | 1982-07-08 |
| JPH0147505B2 true JPH0147505B2 (en) | 1989-10-13 |
Family
ID=16171814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18549880A Granted JPS57109876A (en) | 1980-12-27 | 1980-12-27 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57109876A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53100170A (en) * | 1977-02-15 | 1978-09-01 | Hitachi Ltd | Removing method for nitrogen monoxide |
| JPS5770170A (en) * | 1980-10-21 | 1982-04-30 | Suriibondo:Kk | Adhesive composition |
-
1980
- 1980-12-27 JP JP18549880A patent/JPS57109876A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53100170A (en) * | 1977-02-15 | 1978-09-01 | Hitachi Ltd | Removing method for nitrogen monoxide |
| JPS5770170A (en) * | 1980-10-21 | 1982-04-30 | Suriibondo:Kk | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57109876A (en) | 1982-07-08 |
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