JPH04146982A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPH04146982A JPH04146982A JP2274992A JP27499290A JPH04146982A JP H04146982 A JPH04146982 A JP H04146982A JP 2274992 A JP2274992 A JP 2274992A JP 27499290 A JP27499290 A JP 27499290A JP H04146982 A JPH04146982 A JP H04146982A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- adhesive composition
- cyanoacrylate
- silicone oil
- 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
- 239000000853 adhesive Substances 0.000 title claims description 27
- 230000001070 adhesive effect Effects 0.000 title claims description 27
- 239000000203 mixture Substances 0.000 title claims description 20
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002545 silicone oil Polymers 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims abstract description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- -1 tetrahydrofurfuryl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002148 esters Chemical class 0.000 abstract description 2
- 230000008719 thickening Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract 1
- 239000004830 Super Glue Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920001651 Cyanoacrylate Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QXNIBPDSSDVBQP-UHFFFAOYSA-N acetic acid;2-methylpropanoic acid Chemical compound CC(O)=O.CC(C)C(O)=O QXNIBPDSSDVBQP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003086 colorant Substances 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
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 1
- 229950010048 enbucrilate Drugs 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- ZTYMNUBYYQNBFP-UHFFFAOYSA-N propyl 2-cyanoprop-2-enoate Chemical compound CCCOC(=O)C(=C)C#N ZTYMNUBYYQNBFP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は瞬間接着剤として有用なα−シアノアクリレー
ト系接着剤に関し、さらに詳しくはα−シアノアクリレ
ート系接着剤の弱点の−っである硬化物の脆性を改良し
、耐衝撃性、耐剥離性、耐水性を付与する方法に係わる
。Detailed Description of the Invention <Industrial Application Field> The present invention relates to α-cyanoacrylate adhesives useful as instant adhesives, and more specifically to curing, which is a weak point of α-cyanoacrylate adhesives. It relates to methods for improving the brittleness of objects and imparting them with impact resistance, peeling resistance, and water resistance.
〈従来の技術〉
一般式
％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こし易く固体表面や空
気中の水分、アルカリ物質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
を有するのて、ゴム、プラスチック、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。<Prior art> General formula % formula % (wherein R is alkyl having 16 or less carbon atoms, alkenyl,
α-Cyanoacrylate represented by aralkyl, alkoxyalkyl, haloalkyl, cyclohexyl, phenyl, etc.) is extremely susceptible to anionic polymerization, and it is difficult to polymerize without adding a catalyst or heating due to the solid surface, moisture in the air, and anionic active species of alkaline substances. Because it has the property of polymerizing and curing in a short time, it is widely used as an instant adhesive for bonding rubber, plastics, metals, glass, etc.
しかしなから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
か大きいために、その硬化物は固くて脆く、かつ変形、
剥離等の現象か現われる欠点を有している。それ故、種
々の産業で利用されているものの仮止めの域を脱しきれ
ていない。However, when α-cyanoacrylate adhesive is used alone, due to its high cohesive strength and high volume shrinkage during polymerization, the cured product is hard, brittle, and deformed.
It has the disadvantage of causing phenomena such as peeling. Therefore, although it is used in various industries, it has not gone beyond the level of temporary fixing.
従来このような欠点を解決すべく種々の方法か提案され
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（米国特
許第２７８４１２７号）、■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（米国特許第２８
１６０９３号）、■ゴム状ポリマーを幹としてスチレン
をグラフト共重合させた共重合体を添加する方法（特公
昭４７−５１８０７）、■α−シアノアクリレートにア
クリロニトリル−ブタジェン共重合物を混合したもの（
特公昭５９−５００１３２）か公知である。Various methods have been proposed in the past to solve these drawbacks, such as: (1) Adding a plasticizer such as dialkyl phthalate to give the adhesive film flexibility (U.S. Pat. No. 2,784,127), (2) A method of increasing adhesive strength by using a polymerizable vinyl monomer (U.S. Pat. No. 28
16093), ■ A method of adding a copolymer obtained by graft copolymerizing styrene with a rubbery polymer as a backbone (Japanese Patent Publication No. 47-51807), ■ A method of mixing α-cyanoacrylate with an acrylonitrile-butadiene copolymer (
Japanese Patent Publication No. 59-500132) is well known.
〈発明か解決しようとする課題〉
しかしなから従来の技術においては接着剤が高粘度とな
り、低粘度て可撓性をもたすことかできなかった。その
上、貯蔵中にα−シアノアクリレートモノマーと添加物
か分離し保存性に乏しく諸性質ともに満足しうるもので
なく、商品価値の極めて低い接着剤しか得られない。<Problem to be Solved by the Invention> However, in the conventional technology, the adhesive has a high viscosity, and it has been impossible to provide the adhesive with low viscosity and flexibility. Moreover, the α-cyanoacrylate monomer and additives separate during storage, resulting in poor storage stability and unsatisfactory properties, resulting in an adhesive with extremely low commercial value.
本発明の目的は、かかる課題を解決することてあり、十
分満足し得る耐衝撃性、耐剥離性、耐水性を保有し、か
つ貯蔵中の保存性かよく、増粘および曳糸性も有せず、
瞬間接着剤としてのイメージを損なうことのないα−シ
アノアクリレート系接着剤を提供することである。The purpose of the present invention is to solve the above problems, and has a structure that has sufficiently satisfactory impact resistance, peeling resistance, and water resistance, has good preservability during storage, and has thickening and stringing properties. Without,
An object of the present invention is to provide an α-cyanoacrylate adhesive that does not spoil its image as an instant adhesive.
これにより、従来のα−シアノアクリレート系接着剤の
非構造用分野だけの利用でなく、苛酷な環境に耐えなけ
れはならないような重構造用分野にも拡大てきる。This will expand the use of conventional α-cyanoacrylate adhesives not only in non-structural applications, but also into heavy structural applications that must withstand harsh environments.
〈課題を解決するための手段〉
本発明者らは上記α−シアノアクリレート系接着剤にお
ける課題を改良すべく鋭意検討し、本発明に到達したも
のである。<Means for Solving the Problems> The present inventors have made extensive studies to improve the problems with the above α-cyanoacrylate adhesives, and have arrived at the present invention.
即ち、本発明はα−シアノアクリレートに下記式［Ｉ］
〔ここてＲ１−Ｒ８は水素原子、置換若しくは非置換の
アルキル基、フェニル基、ハロゲン原子、アルコキシ基
、フエ７ノキシ基、カルボキシル基、エステル基であり
、又、ｍ、ｎは１以上の整数である。〕
て示されるシリコーンオイルを含有してなることを特徴
とする接着剤組成物である。That is, the present invention provides α-cyanoacrylate with the following formula [I] [where R1-R8 are hydrogen atoms, substituted or unsubstituted alkyl groups, phenyl groups, halogen atoms, alkoxy groups, Fe7noxy groups, carboxyl groups, It is an ester group, and m and n are integers of 1 or more. ] An adhesive composition characterized by containing a silicone oil shown in the following.
本発明にいうα−シアノアクリレートとしては、具体的
には、例えばメチル−α−シアノアクリレート、エチル
シアノ−α−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、メトキンエチル−α−シアノ
アクリレート、エトキシエチル−α−ノアノアクリレー
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−１・等か挙げられる。Specifically, the α-cyanoacrylate referred to in the present invention includes, for example, methyl-α-cyanoacrylate, ethylcyano-α-acrylate, propyl-α-cyanoacrylate, butyl-α-cyanoacrylate, and allyl-α-cyanoacrylate.
Examples thereof include α-cyanoacrylate, metquinethyl-α-cyanoacrylate, ethoxyethyl-α-noanoacrylate, 2chloroethyl-α-cyanoacrylate, and cyclohexyl-α-cyanoacrylate-1.
本発明に用いられる上記式［ＩＩで示されるシリコーン
オイルとは、一般に無機骨格であるシロキサン結合（−
Ｓｉ−０−３ｉ−）を主鎖に、側鎖にメチル基、ビニル
基、フェニル基なとの有機基を含むオルガノシロキサン
ポリマーてあってオイル状のものであり、具体的には、
上記式［ＩＩにおいて、ｍが１〜１００、好ましくは２
〜５０の整数であり、ｎか１〜５０の整数でありものか
好ましく用いられる。これらは、東芝シリコーン■製の
ＴＳＦシリズ（４３１，４３３，４３４等）、日本ユニ
カー■製のＦＺ、信越シリコーン■製のＫＦシリーズ（
５０，５４等）等として市販されているものか適用され
る。The silicone oil represented by the above formula [II used in the present invention generally refers to the siloxane bond (-
It is an oil-like organosiloxane polymer containing Si-0-3i-) as the main chain and organic groups such as methyl groups, vinyl groups, and phenyl groups in the side chains. Specifically,
In the above formula [II, m is 1 to 100, preferably 2
It is an integer from 1 to 50, preferably n or an integer from 1 to 50. These are the TSF series (431, 433, 434, etc.) made by Toshiba Silicone ■, the FZ made by Nippon Unicar ■, and the KF series (made by Shin-Etsu Silicone ■).
Commercially available products such as 50, 54, etc.) are applicable.
本発明の接着剤組成物を得るには、α−ノアノアクリレ
ートに上記式［ＩＩで示されるノリコーンオイルを添加
混合すれば容易に得られる。The adhesive composition of the present invention can be easily obtained by adding and mixing the noricone oil represented by the above formula [II] with α-noanoacrylate.
添加方法としては上記シリコーンオイルをそのままα−
シアノアクリレ−１・に添加混合するか、又はＩ、 Ｉ
、 １− ）ジクロルエタン、ジクロルメタン、アセト
ン、トルエン、酢酸エチル等の溶媒に溶解してから添加
混合する方法かある。The method of addition is to add the above silicone oil directly to α-
Add and mix to cyanoacrylate-1 or I, I
1-) There is a method of dissolving in a solvent such as dichloroethane, dichloromethane, acetone, toluene, ethyl acetate, etc. and then adding and mixing.
その使用に際しては、溶剤含有の接着剤組成物そのまま
使用しても良いし、又、溶剤を蒸発させた接着剤組成物
として使用してもよい。When using it, the adhesive composition containing a solvent may be used as it is, or the adhesive composition may be used as an adhesive composition in which the solvent has been evaporated.
α−シアノアクリレートに対する上記式 ［ＩＩで示さ
れるシリコーンオイルの添加量は、α−ンアノアクリレ
ート１００重量部に対し、０．１〜５０重量部、好まし
くは１〜４０重量部の範囲であり、これ以上多く添加す
ると硬化速度、接着強度、保存安定性、共に低下する傾
向を示す。The amount of the silicone oil represented by the above formula [II for α-cyanoacrylate is in the range of 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of α-cyanoacrylate. If more than this amount is added, the curing speed, adhesive strength, and storage stability tend to decrease.
本発明の課題を解決し、さらに効果的に目的を達成する
方法として、前述の接着剤組成物に対して更に下記式［
ＩＩ］
（式中、ｎは２〜３の整数であり、少なくとも２個の水
酸基は隣接位にあるものとし、またＸは水素原子、ハロ
ゲン原子、アルキル基、アルコキシル基、アリール基又
はベンゾイル基を示す。）て示される化合物及び／又は
下記式［ＩＩ０＝Ｃ−ＯＲ
（式中、Ｒは水素原子、アルキル基、アルコキンアルキ
ル基、了り九基、プロパルギル基、ソクロヘキシル基ま
たはテトラヒドロフルフリル基を示し、ｍは２以上の整
数である。）
て示される化合物を更に添加混合することが好ましい。As a method for solving the problems of the present invention and achieving the objects more effectively, the following formula [
II] (where n is an integer of 2 to 3, at least two hydroxyl groups are in adjacent positions, and X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, or a benzoyl group) ) and/or the compound represented by the following formula [II0=C-OR (wherein, R is a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkyl group, a propargyl group, a soclohexyl group, or a tetrahydrofurfuryl group) , and m is an integer of 2 or more.) It is preferable to further add and mix the compound shown.
これら式［ＩＩ］及び／又は式［ＩＩで示される化合物
の好ましい添加混合量は前述の接着剤組成物（１００重
量部）に対し、式［］Ｉ］及び／又は式［ＩＩ［］で示
される化合物を羊独又は混合した状態で０．００１〜０
．５重量部の範囲か好ましい。The preferable amount of the compound represented by formula [II] and/or formula [II] to be added to the above-mentioned adhesive composition (100 parts by weight) is represented by formula [I] and/or formula [II [] 0.001 to 0 in a mixed or mixed state
．． A range of 5 parts by weight is preferred.
式［ＩＩ］で示される化合物としては、具体的にはカテ
コール、ピロガロール、１．２．４−ベンゼントリオー
ルをあげることかできる。Specific examples of the compound represented by formula [II] include catechol, pyrogallol, and 1,2,4-benzenetriol.
また、式［ＩＩ［］で示される化合物としては、具体的
には２，４−ジヒドロキノ安息香酸、２，５−ジヒドロ
キシ安息香酸、２．６−ジヒドロキノ安息香酸、３゜４
−ジヒドロキシ安息香酸、３，５−シヒ１−ロキシ安息
香酸、３．４．５− ）ジヒドロキノ安息香酸、および
これらの安息香酸のエステル類、例えば、メチル、エチ
ル、プロピル、ラウリル、ステアリル、メトキシエチル
、エトキシエチル、ブトキシエチル、アリル、プロパル
ギル、ベンジル、シクロヘキシル、テトラヒドロフルフ
リルエステル等かあげられる。Further, as the compound represented by the formula [II[], specifically, 2,4-dihydroquinobenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroquinobenzoic acid, 3゜4
-dihydroxybenzoic acid, 3,5-schhy-1-roxybenzoic acid, 3.4.5-)dihydroquinobenzoic acid, and esters of these benzoic acids, such as methyl, ethyl, propyl, lauryl, stearyl, methoxyethyl , ethoxyethyl, butoxyethyl, allyl, propargyl, benzyl, cyclohexyl, tetrahydrofurfuryl ester, etc.
また、本発明で得られる接着剤には従来からα−シアノ
アクリレート系接着剤に添加して用いられている安定剤
（例えば、二酸化イオウ、ｐ−）ルエンスルホン酸、メ
タンスルホン酸、三弗化硼素ジエチルエーテル、ＨＢＦ
、等のアニオン重合防止剤や、ハイドロキノン、ハイド
ロキノンモノメチルエーテル、ｔ−ブチルカテコール等
のラジカル重合防止剤等）、増粘剤（例えば、ポリメチ
ルメタクリレート、ポリビニルアセテート、セルロース
アセテートイソブチレート、アクリルゴム、ポリウレタ
ン等）、可塑剤、着色剤、香料、溶剤等も目的に応して
適宜モノマーの安定性を阻害しない範囲で添加配合して
使用することができる。The adhesive obtained in the present invention also contains stabilizers (e.g., sulfur dioxide, p-)luenesulfonic acid, methanesulfonic acid, trifluoride, etc., which have been conventionally added to α-cyanoacrylate adhesives. Boron diethyl ether, HBF
, radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, etc.), thickeners (e.g., polymethyl methacrylate, polyvinyl acetate, cellulose acetate isobutyrate, acrylic rubber, Polyurethane, etc.), plasticizers, colorants, fragrances, solvents, etc. can also be added and blended as appropriate depending on the purpose within a range that does not impede the stability of the monomer.
〈発明の効果〉
本発明の接着剤組成物は、接着剤の硬化時の体積収縮率
を緩和させ、硬化物の弾性率を低下させる。その結果、
α−シアノアクリレート系接着剤としてすぐれた耐衝撃
性、耐剥離性、耐水性を有し、又、接着剤の高粘度化、
曳糸性、層分離もおこらない。<Effects of the Invention> The adhesive composition of the present invention moderates the volume shrinkage rate of the adhesive upon curing, and lowers the elastic modulus of the cured product. the result,
It has excellent impact resistance, peel resistance, and water resistance as an α-cyanoacrylate adhesive, and also has high viscosity and
Neither stringiness nor layer separation occurs.
さらに式［ＩＩ］及び／又は式［ＩＩ［］で示される化
合物を添加する事により、これらの化合物を添加しない
接着剤組成物よりも更に優れた耐衝撃性、耐剥離性、耐
水性を示す。Furthermore, by adding a compound represented by formula [II] and/or formula [II[], it exhibits even better impact resistance, peel resistance, and water resistance than an adhesive composition that does not contain these compounds. .
〈実施例〉 以下、実施例によって本発明を更に詳細に説明する。<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１〜７
１ 試料の調整
ハイドロキノン０．０５重量部、ＳＯ□ガス０．００３
重量部を含むエチル又はメチル−α−シアノアクリレー
ト１００重量部にそれぞれ表−１に示す量のシリコーン
オイルを添加してその性能試験を行った。Examples 1 to 7 1 Sample preparation Hydroquinone 0.05 parts by weight, SO□ gas 0.003
A performance test was conducted by adding silicone oil in the amount shown in Table 1 to 100 parts by weight of ethyl or methyl-α-cyanoacrylate.
なお、各実施例に用いた［Ｉ］て示されるシリコーンオ
イルは次のとおりである。The silicone oil indicated by [I] used in each example is as follows.
実施例１〜４て用いたシリコーンオイル式［１］におい
て、Ｒ，〜Ｒ８かメチル基、ｍ＝３７、ｎ＝８であるフ
ェニル基含有率２０ｍｏｌ％のメチルフェニルシリコー
ンオイル、実施例５て用いたシリコーンオイル
式［Ｉ］において、Ｒ３−Ｒ１かメチル基、ｍ＝３５、
ｎ＝２であるフェニル基含有率５ｍｏｌ％のメチルフェ
ニルシリコーンオイル、
実施例６で用いたシリコーンオイル
式［Ｉ］において、Ｒ３〜Ｒ，かメチル基、ｍ＝１０、
ｎ＝７であるフェニル基含有率３５ｍｏｌ％のメチルフ
ェニルシリコーンオイル、実施例７て用いたシリコーン
オイル
東芝シリコーン■製のＴＳＦ−４３３
ｉ 試験方法
■粘度、 ＪＩＳ Ｋ６８３８に準じて測定した。In the silicone oil formula [1] used in Examples 1 to 4, methyl phenyl silicone oil with a phenyl group content of 20 mol% where R, ~ R8 is a methyl group, m = 37, n = 8, a methylphenyl silicone oil used in Example 5 In the silicone oil formula [I], R3-R1 or methyl group, m = 35,
Methylphenyl silicone oil with a phenyl group content of 5 mol% where n = 2, in the silicone oil formula [I] used in Example 6, R3 to R, or a methyl group, m = 10,
Methylphenyl silicone oil with phenyl group content of 35 mol % where n=7, silicone oil used in Example 7 TSF-433 manufactured by Toshiba Silicone Test method ■ Viscosity, measured according to JIS K6838.
■セットタイム； ＪＩＳ Ｋ６８６１−８に準じて測
定した。■Set time; Measured according to JIS K6861-8.
被着材は鋼−鋼を用いた。Steel-steel was used as the adherend.
■剥離強度はＪＩＳ Ｋ６８５４に準じて測定した。(2) Peel strength was measured according to JIS K6854.
被着材は鋼−鋼て、Ｔ形剥離強度を測定した。The adherend was steel-steel, and the T-peel strength was measured.
■衝撃強度はＪＩＳ Ｋ６８５５に準じて測定した。■Impact strength was measured according to JIS K6855.
被着材は鋼−鋼を用いた。Steel-steel was used as the adherend.
■引張剪断強度はＪＩＳ Ｋ６８６１−６に準じて測定
した。(2) Tensile shear strength was measured according to JIS K6861-6.
被着材は鋼−鋼を用いた。Steel-steel was used as the adherend.
■耐水性は接着硬化後４０°Ｃの水に５日間浸漬したの
ち引張剪断強度を測定した。(2) Water resistance was determined by immersing the adhesive in water at 40°C for 5 days after curing, and then measuring the tensile shear strength.
ｉ 測定結果 表−１，２に示す。i Measurement results Shown in Tables 1 and 2.
（以下余白）
〔表−２〕
〔表−１〕の結果かられかるようにシリコーンオイルを
添加することにより、耐衝撃性、耐剥離性、耐水性等が
著しく向上し、保存安定性においても良好であった。(Left below) [Table 2] As shown in Table 1, by adding silicone oil, impact resistance, peeling resistance, water resistance, etc. are significantly improved, and storage stability is also improved. It was good.
〔表−２〕の結果では、従来知られているエラストマー
（ＳＢＳ、アクリルゴム）との比較を行なった。耐衝撃
性、耐剥離性の向上と共に保存性耐水性共大巾に改善さ
れた。The results in Table 2 are compared with conventionally known elastomers (SBS, acrylic rubber). In addition to improving impact resistance and peeling resistance, both storage and water resistance have been greatly improved.
実施例８〜１３
１ 試料調整
実施例Ｉ及び実施例７の組成物にピロガロール及び３．
４．５−トリヒドロキシ安息香酸エチルを添加混合し、
均一な接着剤組成物を得た。添加量は〔表−３〕に示す
。Examples 8-13 1 Sample Preparation The compositions of Example I and Example 7 were added with pyrogallol and 3.
4. Add and mix ethyl 5-trihydroxybenzoate,
A uniform adhesive composition was obtained. The amount added is shown in [Table 3].
ｉ 試験方法 実施例１〜７に同じ。i Test method Same as Examples 1-7.
ｉ 測定結果 表−３に示す。i Measurement results It is shown in Table-3.
〔表−３〕の結果から衝撃強度、引張剪断強度、耐水性
等共に、実施例１．７の添加しない場合に比較して向上
した。From the results in [Table 3], impact strength, tensile shear strength, water resistance, etc. were all improved compared to Example 1.7 where no addition was made.
（以下余白）(Margin below)
Claims (6)
、化学式、表等があります▼［ I ］ 〔ここでＲ＿１〜Ｒ＿３は水素原子、置換若しくは非置
換のアルキル基、フェニル基、ハロゲン原子、アルコキ
シ基、フェノキシ基、カルボキシル基、エステル基であ
り、又、ｍ、ｎは１以上の整数である。〕 で示されるシリコーンオイルを含有してなることを特徴
とする接着剤組成物。(1) α-cyanoacrylate has the following formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [Here, R_1 to R_3 are hydrogen atoms, substituted or unsubstituted alkyl groups, phenyl groups, halogen atoms, They are an alkoxy group, a phenoxy group, a carboxyl group, and an ester group, and m and n are integers of 1 or more. ] An adhesive composition characterized by containing a silicone oil represented by the following.
［ I ］で示されるシリコーンオイル０．１〜５０重量
部含有する請求項（１）に記載の接着剤組成物。(2) The adhesive composition according to claim 1, which contains 0.1 to 50 parts by weight of silicone oil represented by formula [I] per 100 parts by weight of α-cyanoacrylate.
ニル基含有率が５〜３５ｍｏｌ％である請求項（１）に
記載の接着剤組成物。(3) The adhesive composition according to claim 1, wherein the silicone oil represented by formula [I] has a phenyl group content of 5 to 35 mol%.
酸基は隣接位にあるものとし、またＸは水素原子、ハロ
ゲン原子、アルキル基、アルコキシル基、アリール基又
はベンゾイル基を示す。）で示される化合物を更に含有
してなる請求項（１）〜（３）のいずれかに記載の接着
剤組成物。(4) The following formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, n is an integer of 2 to 3, at least two hydroxyl groups are in adjacent positions, and represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, or a benzoyl group. The adhesive composition according to any one of claims (1) to (3), further comprising a compound represented by thing.
ル基、アリル基、プロパルギル基、シクロヘキシル基ま
たはテトラヒドロフルフリル基を示し、ｍは２以上の整
数である。） で示される化合物を更に含有してなる請求項（１）〜（
３）のいずれかに記載の接着剤組成物。(5) The following formula [III] ▲ Numerical formula, chemical formula, table, etc. ▼ [III] (In the formula, R is a hydrogen atom, an alkyl group, an alkoxyalkyl group, an allyl group, a propargyl group, a cyclohexyl group, or a tetrahydrofurfuryl group. and m is an integer of 2 or more.) Claims (1)-(
The adhesive composition according to any one of 3).
酸基は隣接位にあるものとし、またＸは水素原子、ハロ
ゲン原子、アルキル基、アルコキシル基、アリール基又
はベンゾイル基を示す。）で示される化合物及び下記式
［III］ ▲数式、化学式、表等があります▼［III］ （式中、Ｒは水素原子、アルキル基、アルコキシアルキ
ル基、アリル基、プロパルギル基、シクロヘキシル基ま
たはテトラヒドロフルフリル基を示し、ｍは２以上の整
数である。） で示される化合物を更に含有してなる請求項（１）〜（
３）のいずれかに記載の接着剤組成物。(6) The following formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In the formula, n is an integer of 2 to 3, at least two hydroxyl groups are in adjacent positions, and represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, an aryl group, or a benzoyl group) and the following formula [III] represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, an allyl group, a propargyl group, a cyclohexyl group, or a tetrahydrofurfuryl group, and m is an integer of 2 or more. 1)～(
The adhesive composition according to any one of 3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2274992A JPH04146982A (en) | 1990-10-11 | 1990-10-11 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2274992A JPH04146982A (en) | 1990-10-11 | 1990-10-11 | Adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04146982A true JPH04146982A (en) | 1992-05-20 |
Family
ID=17549396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2274992A Pending JPH04146982A (en) | 1990-10-11 | 1990-10-11 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04146982A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6183593B1 (en) | 1999-12-23 | 2001-02-06 | Closure Medical Corporation | 1,1-disubstituted ethylene adhesive compositions containing polydimethylsiloxane |
| US6607631B1 (en) | 2000-09-08 | 2003-08-19 | Closure Medical Corporation | Adhesive compositions with reduced coefficient of friction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5770171A (en) * | 1980-10-21 | 1982-04-30 | Suriibondo:Kk | Adhesive composition |
| JPH03126782A (en) * | 1989-10-12 | 1991-05-29 | Matsumoto Seiyaku Kogyo Kk | Cyanoacrylate adhesive composition |
| JPH03296581A (en) * | 1990-04-13 | 1991-12-27 | Toagosei Chem Ind Co Ltd | Adhesive composition |
-
1990
- 1990-10-11 JP JP2274992A patent/JPH04146982A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5770171A (en) * | 1980-10-21 | 1982-04-30 | Suriibondo:Kk | Adhesive composition |
| JPH03126782A (en) * | 1989-10-12 | 1991-05-29 | Matsumoto Seiyaku Kogyo Kk | Cyanoacrylate adhesive composition |
| JPH03296581A (en) * | 1990-04-13 | 1991-12-27 | Toagosei Chem Ind Co Ltd | Adhesive composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6183593B1 (en) | 1999-12-23 | 2001-02-06 | Closure Medical Corporation | 1,1-disubstituted ethylene adhesive compositions containing polydimethylsiloxane |
| US6488944B2 (en) | 1999-12-23 | 2002-12-03 | Closure Medical Corporation | 1, 1-disubstituted ethylene adhesive compositions containing polydimethylsiloxane |
| US6607631B1 (en) | 2000-09-08 | 2003-08-19 | Closure Medical Corporation | Adhesive compositions with reduced coefficient of friction |
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