JPS59145271A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPS59145271A JPS59145271A JP1867783A JP1867783A JPS59145271A JP S59145271 A JPS59145271 A JP S59145271A JP 1867783 A JP1867783 A JP 1867783A JP 1867783 A JP1867783 A JP 1867783A JP S59145271 A JPS59145271 A JP S59145271A
- Authority
- JP
- Japan
- Prior art keywords
- cyanoacrylate
- resin
- adhesive
- vinyl acetate
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は接着剤組成物に関する。さらに詳しくは耐衝撃
性が改善されたα−シアノアクリレート接着剤組成物に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesive compositions. More specifically, the present invention relates to an α-cyanoacrylate adhesive composition with improved impact resistance.
一般式
(式中Rは炭素数16以下のアルキル、アルケニル、ア
ラルキル、アルコキシアルキル、ハロアルキル、シクロ
ヘキシル、フェニル等)で示されるα−シアノアクリレ
ートは極めてアニオン重合を起し易く固体表面や空気中
の水分、アルカリ物質等のアニオン活性種により触媒の
添加や加熱を行なう事なく短時間で重合硬化する性質を
有するので、ゴム、プラスチックス、金属、ガラス等の
接着に瞬間接着剤として広く利用されている。α-Cyanoacrylate represented by the general formula (wherein R is alkyl, alkenyl, aralkyl, alkoxyalkyl, haloalkyl, cyclohexyl, phenyl, etc. having 16 or fewer carbon atoms) is extremely susceptible to anionic polymerization, and moisture on the solid surface or in the air It has the property of polymerizing and curing in a short time using anionic active species such as alkaline substances without adding catalysts or heating, so it is widely used as an instant adhesive for bonding rubber, plastics, metals, glass, etc. .
しかしながらα−シアノアクリレート接着剤を単独で用
いる場合その高い凝集力と重合時に於ける体積収縮率が
大きいためにその接着が固くて脆くかつ変形、剥離等の
現象が現われる欠点を有している。従来このような欠点
を解決べく種々の方法が提案されており、例えばジアル
キルフタレートのような可塑剤を添加して接着被膜に可
撓性を持たせる方法、重合性のビニルモノマーを併用し
てその接着力を増大させる方法、ゴム状ポリマーを幹と
してスチレンをグラフト共重合せしめた共重合体を添加
する方法などであるが、これらの方法はいずれもα−シ
アノアクリレート接着剤の耐衝撃性を本質的に改善する
ものではない。However, when an α-cyanoacrylate adhesive is used alone, it has the drawback that its high cohesive force and high volume shrinkage during polymerization make the adhesive hard and brittle, and phenomena such as deformation and peeling occur. Various methods have been proposed to overcome these drawbacks, including adding plasticizers such as dialkyl phthalates to make the adhesive film flexible, and adding polymerizable vinyl monomers to make the adhesive film more flexible. There are methods to increase adhesive strength and methods to add a copolymer made by graft copolymerizing styrene to a rubber-like polymer as a backbone, but all of these methods are based on the impact resistance of α-cyanoacrylate adhesives. It does not improve the situation.
本発明者等はα−シアノアクリレート接着剤の耐衝撃性
等の性質を改善すべく種々研究の結果。The present inventors have conducted various studies to improve properties such as impact resistance of α-cyanoacrylate adhesives.
α−シアノアクリレートにエチレン−酢酸ビニル共重合
体を添加併用することによって耐衝撃性を著るしく改善
できることを見出し本発明に到達した。The present inventors have discovered that impact resistance can be significantly improved by adding and using an ethylene-vinyl acetate copolymer to α-cyanoacrylate.
本発明で用いられるα−シアノアクリレートとしては例
えばメチル−α−シアノアクリレート、エチル−α−シ
アノアクリレート、プロピル−α−シアノアクリレート
、ブチル−α−シアノアクリレート、アリル−α−シア
ノアクリレート、メトキシエチル−α−シアノアクリレ
ート、エトキシエチル−α−シアノアクリレート、2−
クロロエチル−α−シアノアクリレート、シクロへキシ
ル−α−シアノアクリレート等である。Examples of the α-cyanoacrylate used in the present invention include methyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, propyl-α-cyanoacrylate, butyl-α-cyanoacrylate, allyl-α-cyanoacrylate, and methoxyethyl- α-cyanoacrylate, ethoxyethyl-α-cyanoacrylate, 2-
These include chloroethyl-α-cyanoacrylate, cyclohexyl-α-cyanoacrylate, and the like.
本発明に用いられるエチレン−酢酸ビニル共重合体樹脂
としては酢酸ビニル含量が約50〜90重量%のものが
好ましい。酢酸ビニル含量が50重景%以下ではα−シ
アノアクリレートに溶解、懸濁がむつかしく二層分離し
てしまうので安定した性能が得られず、又、90重量%
以上では共重体樹脂の軟化点が高く衝撃エネルギーを吸
収しなくなるので良好な耐衝撃性が得られない。The ethylene-vinyl acetate copolymer resin used in the present invention preferably has a vinyl acetate content of about 50 to 90% by weight. If the vinyl acetate content is less than 50% by weight, it is difficult to dissolve and suspend it in α-cyanoacrylate, resulting in two-layer separation, making it impossible to obtain stable performance.
If the copolymer resin has a high softening point and cannot absorb impact energy, good impact resistance cannot be obtained.
エチレン−酢酸ビニル共重合樹脂の添加割合は得られる
接着剤組成物の用途や添加する樹脂の種類に応じて適宜
に決められるが、α−シアノアクリレートに対して1〜
15重量%の添加が好ましい。The ratio of the ethylene-vinyl acetate copolymer resin to be added is determined as appropriate depending on the intended use of the resulting adhesive composition and the type of resin to be added, but it is 1 to 1 to α-cyanoacrylate.
An addition of 15% by weight is preferred.
1重量%以下では耐衝撃性付与の効果がなく、15重量
%以上ではα−シアノアクリレートの特徴である瞬間接
着性が損なわれてしまう。If it is less than 1% by weight, there is no effect of imparting impact resistance, and if it is more than 15% by weight, the instant adhesive property, which is a characteristic of α-cyanoacrylate, will be impaired.
これらのエチレン−酢酸ビニル共重合体樹脂を添加混合
するに当ってはこれを直接α−シアノアクリレートに混
合してもよく、又適当な溶媒に溶解してから添加混合し
てもよい。When adding and mixing these ethylene-vinyl acetate copolymer resins, they may be directly mixed with α-cyanoacrylate, or may be added and mixed after being dissolved in a suitable solvent.
又必要に応じて充填剤、軟化剤、安定剤等を添加混合す
ることも可能であり例えばカーボンブラック、ベンガラ
、ケイ酸カルシウム、酸化チタン等の充填剤、DBP、
、DOP、TICP、トリブトキシエチルホスフェート
、その他各種エステル類等の軟化剤、亜硫酸ガス、ハイ
ドロキノン、トリメチルジヒドロキノン等の安定剤、更
にメチルメタアクリレート等のα−シアノアクリレート
と相溶性のある他のポリマー等を添加併用することがで
きる。It is also possible to add and mix fillers, softeners, stabilizers, etc. as necessary, such as fillers such as carbon black, red iron, calcium silicate, titanium oxide, DBP,
Softeners such as , DOP, TICP, tributoxyethyl phosphate, and various other esters; stabilizers such as sulfur dioxide gas, hydroquinone, and trimethyldihydroquinone; and other polymers that are compatible with α-cyanoacrylates such as methyl methacrylate. etc. can be added and used in combination.
本発明のエチレン−酢酸ビニル共重合樹脂を添加併用し
て得られるα−シアノアクリレート接着剤は耐衝撃性が
著るしく改善されると同時に著るしく増粘され、その結
果α−シアノアクリレート単独では接着できなかったよ
うな多孔質の材料の接着も可能になり、又重合時の体積
収縮率も低下するので被接着体の変形あるいは剥離等の
現象を防止することが可能である。The α-cyanoacrylate adhesive obtained by the combined use of the ethylene-vinyl acetate copolymer resin of the present invention has significantly improved impact resistance and is also significantly thickened, and as a result, α-cyanoacrylate alone It is now possible to bond porous materials that could not be bonded with other methods, and since the volumetric shrinkage rate during polymerization is also reduced, it is possible to prevent phenomena such as deformation or peeling of the bonded object.
次に本発明を実施例で説明する。Next, the present invention will be explained with examples.
実施例1〜4
攪拌器付きの容量300m1の四つ目フラスコに500
ppmのハイドロキノン、20ppmの亜硫酸ガスを含
むエチル−α−シアノアクリレートを200g仕込み、
攪拌下に表1に示す微小片のエチレン−酢酸ビニル共重
合体樹脂を添加した。Examples 1-4 500 ml in a four-eye flask with a capacity of 300 m1 equipped with a stirrer
Prepare 200g of ethyl-α-cyanoacrylate containing ppm of hydroquinone and 20ppm of sulfur dioxide gas,
While stirring, small pieces of ethylene-vinyl acetate copolymer resin shown in Table 1 were added.
次いで密栓下に70℃の油浴中で加熱溶解し均一に混合
し攪拌しながら放冷した。このようにして得られた接着
剤組成物の粘度およびこれを用いて鋼−鋼接者した場合
の固着時間、引張剪断強度及び衝撃強度を測定した。そ
の結果を表1に示す。Next, the mixture was heated and dissolved in an oil bath at 70° C. under a tightly closed stopper, mixed uniformly, and allowed to cool while stirring. The viscosity of the adhesive composition thus obtained, the fixing time, tensile shear strength, and impact strength when the adhesive composition was used to join steel to steel were measured. The results are shown in Table 1.
尚上記固着時間は研磨、脱脂した接着面積1entを有
する鋼鉄製バットピースに、温度20℃、湿度50±5
%R2(の条件下で接着剤を塗布後、2枚のピースを重
ね合わせて放置し、 8kg/cnffの抗張力が得ら
れるまでの時間を測定したものである。引張剪断強度は
研磨、脱脂した25 X 100 X 1.6mmの軟
鋼板を用い、接着面積12.5 X 25mmで重ね合
わせ、24時間養生した後引張試験機(島津製作所製l
S−5000)で50mm/minの引張速度で引張っ
て測定したものである。The above adhesion time is based on a polished and degreased steel butt piece with an adhesion area of 1 ent, at a temperature of 20°C and a humidity of 50±5.
After applying the adhesive under the conditions of %R2, the two pieces were placed on top of each other and left to stand, and the time required to obtain a tensile strength of 8 kg/cnff was measured.The tensile shear strength was determined by polishing and degreasing. Using mild steel plates measuring 25 x 100 x 1.6 mm, they were overlapped with an adhesive area of 12.5 x 25 mm, cured for 24 hours, and then tested using a tensile tester (Shimadzu Corporation).
S-5000) at a tensile speed of 50 mm/min.
衝撃強度はASTM−D950−54規格に準じて鋼製
試験片(25X 25 X 6mm)を接着、24時間
養生後アイゾツト衝撃強度試験機(東洋精機製作新製)
を使用して衝撃強度を測定した。環境条件は20℃、6
0%RHである。Impact strength was determined by gluing steel test pieces (25 x 25 x 6 mm) according to the ASTM-D950-54 standard, and after curing for 24 hours using an Izotsu impact strength tester (newly manufactured by Toyo Seiki).
The impact strength was measured using Environmental conditions are 20℃, 6
It is 0%RH.
実施例5
実施例1〜4と同様にして10gのジクロルメタンと1
80gのエチル−α−シアノアクリレートを仕込んだ後
、攪拌下にソアレックスDH(日本合成化学工業(株)
製エチレンー酢酸ビニル共重合体樹脂、酢ビ含量70%
)10gを溶解混合して組成物を得た。物性試験結果を
表1に示す。Example 5 In the same manner as in Examples 1 to 4, 10 g of dichloromethane and 1
After charging 80 g of ethyl-α-cyanoacrylate, Solex DH (Nippon Gosei Kagaku Kogyo Co., Ltd.) was added while stirring.
Made of ethylene-vinyl acetate copolymer resin, vinyl acetate content 70%
) was dissolved and mixed to obtain a composition. Table 1 shows the physical property test results.
比較例1〜2
実施例と同様にして粒状のゴーセニールPV−500(
日本合成化学工業(株)製酢酸ビニル樹脂)を溶解混合
して組成物を得た。物性試験結果を表1に示す。Comparative Examples 1-2 Granular Gosenil PV-500 (
A composition was obtained by dissolving and mixing vinyl acetate resin (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.). Table 1 shows the physical property test results.
また他樹脂無添加のエチル−α−シアノアクリレートの
粘度および接着試験結果を比較例2として表1に示した
。In addition, the viscosity and adhesion test results of ethyl-α-cyanoacrylate without the addition of other resins are shown in Table 1 as Comparative Example 2.
表1の結果から、本発明接着剤は従来のシアノアクリレ
ート接着剤に比し、瞬間接着性を一失なうことなく接着
強度、特に耐衝撃性が著しく改善されていることが明ら
かである。From the results in Table 1, it is clear that the adhesive strength of the present invention, especially the impact resistance, is significantly improved compared to the conventional cyanoacrylate adhesive without any loss in instant adhesive properties.
特許出願人 田岡化学工業株式会社Patent applicant: Taoka Chemical Industry Co., Ltd.
Claims (1)
体樹脂を添加したことを特徴とする接着剤組成物。An adhesive composition characterized in that an ethylene-vinyl acetate copolymer resin is added to α-cyanoacrylate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1867783A JPS59145271A (en) | 1983-02-05 | 1983-02-05 | Adhesive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1867783A JPS59145271A (en) | 1983-02-05 | 1983-02-05 | Adhesive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59145271A true JPS59145271A (en) | 1984-08-20 |
Family
ID=11978234
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1867783A Pending JPS59145271A (en) | 1983-02-05 | 1983-02-05 | Adhesive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59145271A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6225185A (en) * | 1985-07-25 | 1987-02-03 | Alpha Giken:Kk | Alpha-cyanoacrylate adhesive composition |
JPS633072A (en) * | 1986-06-24 | 1988-01-08 | Toagosei Chem Ind Co Ltd | Adhesive composition |
WO2010029134A1 (en) * | 2008-09-10 | 2010-03-18 | Loctite (R&D) Limited | Toughened cyanoacrylate compositions |
WO2010074095A1 (en) * | 2008-12-25 | 2010-07-01 | 東亞合成株式会社 | Adhesive composition |
KR20150040793A (en) * | 2012-05-23 | 2015-04-15 | 헨켈 아게 운트 코. 카게아아 | A curable composition comprising cyanoacrylate monomers |
JP2015525145A (en) * | 2012-05-23 | 2015-09-03 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Article comprising a film on a support or release substrate |
-
1983
- 1983-02-05 JP JP1867783A patent/JPS59145271A/en active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6225185A (en) * | 1985-07-25 | 1987-02-03 | Alpha Giken:Kk | Alpha-cyanoacrylate adhesive composition |
JPH058951B2 (en) * | 1985-07-25 | 1993-02-03 | Alpha Techno Co | |
JPS633072A (en) * | 1986-06-24 | 1988-01-08 | Toagosei Chem Ind Co Ltd | Adhesive composition |
WO2010029134A1 (en) * | 2008-09-10 | 2010-03-18 | Loctite (R&D) Limited | Toughened cyanoacrylate compositions |
WO2010074095A1 (en) * | 2008-12-25 | 2010-07-01 | 東亞合成株式会社 | Adhesive composition |
JP5267571B2 (en) * | 2008-12-25 | 2013-08-21 | 東亞合成株式会社 | Adhesive composition |
US8541495B2 (en) | 2008-12-25 | 2013-09-24 | Toagosei Co., Ltd. | Adhesive composition |
KR20150040793A (en) * | 2012-05-23 | 2015-04-15 | 헨켈 아게 운트 코. 카게아아 | A curable composition comprising cyanoacrylate monomers |
JP2015523426A (en) * | 2012-05-23 | 2015-08-13 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co.KGaA | Curable composition containing cyanoacrylate monomer |
JP2015525145A (en) * | 2012-05-23 | 2015-09-03 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Article comprising a film on a support or release substrate |
TWI577768B (en) * | 2012-05-23 | 2017-04-11 | 漢高股份有限及兩合公司 | A curable composition comprising cyanoacrylate monomers |
TWI582194B (en) * | 2012-05-23 | 2017-05-11 | 漢高股份有限及兩合公司 | An article comprising a film on a carrier or release substrate |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3832274A (en) | Fast curing adhesives | |
KR102050259B1 (en) | Structural acrylic adhesive | |
CA2078476C (en) | High performance solvent-free contact adhesive | |
US3725504A (en) | Fast curing polychloroprene acrylic adhesive | |
EP0096500B1 (en) | Two-part self-indicating adhesive composition | |
KR102543292B1 (en) | (meth)acrylic adhesive composition, manufacturing method thereof and use thereof | |
JPS6141946B2 (en) | ||
CA2243573A1 (en) | Free radical polymerizable compositions including para-halogenated aniline derivatives | |
JPH09511264A (en) | Moisture-Curable Modified Acrylic Polymer Sealant Composition | |
JPS6019789B2 (en) | two-component adhesive | |
US6632908B1 (en) | Bonding system having adherence to low energy surfaces | |
TR27653A (en) | Process for the preparation of thermoplastic resin compositions with excellent hcfc resistance. | |
GB924451A (en) | Composition and method for making panel for printed circuits | |
JPS59145271A (en) | Adhesive composition | |
JPS58160379A (en) | Adhesive blend | |
IE921368A1 (en) | Multicomponent adhesive composition | |
US3637615A (en) | Pressure-sensitive adhesive | |
CN106519995A (en) | Toughened alpha-cyanoacrylate adhesive | |
JPS5974176A (en) | Adhesive composition | |
JPS58103504A (en) | Emulsion polymerization and product | |
JPH0524953B2 (en) | ||
JPH0586347A (en) | Adhesive | |
JPS58185666A (en) | Novel cyanoacrylate adhesive | |
US3446874A (en) | Polymerizable solvent adhesive composition containing mixed cobalt/zinc catalyst promoter | |
EP0218365A1 (en) | Acrylic adhesives and sealants with improved hot strength |