JP2024010273A - Surface treatment agent for cyanoacrylate adhesive composition, and adhesion method using that surface treatment agent - Google Patents
Surface treatment agent for cyanoacrylate adhesive composition, and adhesion method using that surface treatment agent Download PDFInfo
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- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 52
- 239000004830 Super Glue Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229920000768 polyamine Polymers 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 229920001971 elastomer Polymers 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 20
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- -1 polypropylene Polymers 0.000 description 13
- 229920002397 thermoplastic olefin Polymers 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 229920003244 diene elastomer Polymers 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001887 crystalline plastic Polymers 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical compound CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SKCNNQDRNPQEFU-UHFFFAOYSA-N n'-[3-(dimethylamino)propyl]-n,n,n'-trimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)CCCN(C)C SKCNNQDRNPQEFU-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- AIXZBGVLNVRQSS-UHFFFAOYSA-N 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C(C)(C)C)=NC2=C1 AIXZBGVLNVRQSS-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229940007550 benzyl acetate Drugs 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
- 239000000919 ceramic Substances 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
- 238000007796 conventional method Methods 0.000 description 1
- 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 1
- LFJLAWZRNOKTDN-UHFFFAOYSA-N dodecyl 2-cyanoprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(=C)C#N LFJLAWZRNOKTDN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000000945 filler Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- UNEXJVCWJSHFNN-UHFFFAOYSA-N n,n,n',n'-tetraethylmethanediamine Chemical compound CCN(CC)CN(CC)CC UNEXJVCWJSHFNN-UHFFFAOYSA-N 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 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 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、シアノアクリレート接着剤組成物を用いてポリプロピレン、ポリエチレン等のポリオレフィン、ポリアセタール、ふっ素系樹脂および結晶性の高いプラスチック、並びに前記ポリオレフィンとジエン系ゴムからなるＴＰＥやＴＰＯ、ＴＰＶ等の熱可塑性エラストマー等の難接着材料を接着する際の該材料の表面処理に用いられるシアノアクリレート接着剤組成物用表面処理剤に関する。 The present invention uses a cyanoacrylate adhesive composition to bind polyolefins such as polypropylene and polyethylene, polyacetals, fluororesins, highly crystalline plastics, and thermoplastics such as TPE, TPO, and TPV made of the polyolefins and diene rubbers. The present invention relates to a surface treatment agent for cyanoacrylate adhesive compositions used for surface treatment of difficult-to-bond materials such as elastomers.
２－シアノアクリレートモノマーを主成分とするシアノアクリレート接着剤組成物は、一般に極めて高いアニオン重合性を有し、塩基性物質をはじめ求核性の弱い水やアルコールなどにより常温で速やかに重合して強靱なポリマーを与える。この性質を利用して、シアノアクリレート接着剤組成物は、電気機器、輸送機器、精密機器、機械等用の瞬間接着剤として、各種工業産業界および一般家庭におけるゴム、プラスチック、セラミックス等の接着に広く利用されている。 Cyanoacrylate adhesive compositions containing 2-cyanoacrylate monomers as a main component generally have extremely high anionic polymerizability, and can be rapidly polymerized at room temperature with basic substances and weak nucleophilic substances such as water and alcohol. Provides tough polymers. Utilizing this property, cyanoacrylate adhesive compositions can be used as instant adhesives for electrical equipment, transportation equipment, precision equipment, machinery, etc., and for bonding rubber, plastics, ceramics, etc. in various industrial industries and general households. Widely used.
しかしながら、シアノアクリレート接着剤組成物は、被着体の材質によっては接着性が極めて劣る場合がある。特に前述した難接着材料は極性が小さいため、シアノアクリレート接着剤組成物を用いても通常の方法では、十分な接着強度を得られない場合や、接着強度の立ち上がり速度が遅くなるなど接着が困難であることが知られる。 However, cyanoacrylate adhesive compositions may have extremely poor adhesive properties depending on the material of the adherend. In particular, the above-mentioned difficult-to-adhesive materials have low polarity, so even if a cyanoacrylate adhesive composition is used, it may not be possible to obtain sufficient adhesion strength, or the rate of increase in adhesive strength may be slow, making it difficult to adhere. It is known that
そのため、これまでに難接着材料をシアノアクリレート接着剤組成物で接着する方法が種々検討されている。例えば、表面処理剤（プライマー）を予め難接着材料の被着体表面に塗布した後、該被着体表面にシアノアクリレート接着剤組成物を塗布して接着することにより接着強度を向上させる方法が知られており、また、該表面処理剤として、例えば、特定の構造を有するジアミン化合物および脂肪族炭化水素系溶媒（特許文献１）を含む組成物等が知られている。 Therefore, various methods of bonding difficult-to-bond materials with cyanoacrylate adhesive compositions have been studied. For example, there is a method of improving adhesive strength by applying a surface treatment agent (primer) to the surface of an adherend made of a difficult-to-adhesive material in advance, and then applying a cyanoacrylate adhesive composition to the surface of the adherend for adhesion. Furthermore, as the surface treatment agent, for example, a composition containing a diamine compound having a specific structure and an aliphatic hydrocarbon solvent (Patent Document 1) is known.
しかしながら、上記した表面処理剤は無色透明であると共に、表面処理剤を塗布した後、シアノアクリレート接着剤組成物を塗布する前に乾燥させる必要がある一方、塗布後、塗布箇所や塗布量の確認が必要であるにも拘わらず、斯かる確認が困難であることから、特に大量の被着体を接着するに際し、塗布漏れや塗布量の不足が生じる場合があった。 However, the above-mentioned surface treatment agent is colorless and transparent, and it is necessary to dry it after applying the surface treatment agent and before applying the cyanoacrylate adhesive composition. Although this is necessary, since such confirmation is difficult, there have been cases where coating leakage or insufficient coating amount occurs, especially when bonding a large number of adherends.
本発明は、塗布した後に塗布箇所や塗布量の確認が可能なシアノアクリレート接着剤組成物用の表面処理剤の提供を目的とする。 An object of the present invention is to provide a surface treatment agent for a cyanoacrylate adhesive composition that allows confirmation of the application location and amount of application after application.
本発明者らは、鋭意検討を重ねた結果、下記する成分（Ａ）～（Ｃ）を特定の割合で含む表面処理剤によれば、前記課題が解決可能であることを見出した。具体的には、本発明は以下の発明を含む。 As a result of extensive studies, the present inventors have found that the above-mentioned problems can be solved by a surface treatment agent containing the following components (A) to (C) in specific proportions. Specifically, the present invention includes the following inventions.
〔１〕
下記（Ａ）、（Ｂ）及び（Ｃ）を含有し、且つ（Ｂ）の含有量が（Ａ）１００重量部に対し０．０５～５．０重量部であり、（Ｃ）の含有量が（Ａ）１００重量部に対し０．０２～０．５５重量部である、シアノアクリレート接着剤組成物用表面処理剤。
（Ａ）分岐を有してもよい炭素数５～１５の脂肪族炭化水素系溶媒を含む有機溶媒。
（Ｂ）下記一般式（１）：
[1]
Contains the following (A), (B) and (C), and the content of (B) is 0.05 to 5.0 parts by weight per 100 parts by weight of (A), and the content of (C) is is 0.02 to 0.55 parts by weight based on 100 parts by weight of (A), a surface treatment agent for a cyanoacrylate adhesive composition.
(A) An organic solvent containing an aliphatic hydrocarbon solvent having 5 to 15 carbon atoms which may have branches.
(B) The following general formula (1):
で表される化合物および下記一般式（２）：
The compound represented by and the following general formula (2):
で表される化合物からなる群から選ばれる少なくとも１種のポリアミン化合物。
（Ｃ）下記一般式（３）：
At least one polyamine compound selected from the group consisting of compounds represented by:
(C) The following general formula (3):
で表される化合物。
A compound represented by
〔２〕
表面処理を行う被着体の内、少なくとも一方がポリオレフィン樹脂またはポリオレフィン樹脂を含有するエラストマーである、〔１〕に記載のシアノアクリレート接着剤組成物用表面処理剤。
[2]
The surface treatment agent for a cyanoacrylate adhesive composition according to [1], wherein at least one of the adherends to be surface treated is a polyolefin resin or an elastomer containing a polyolefin resin.
〔３〕
シアノアクリレート接着剤組成物によって被着体同士を接着する接着方法であって、接着の前工程として下記工程（１）及び（２）をこの順で含む、接着方法。
（１）〔１〕又は〔２〕に記載のシアノアクリレート接着剤組成物用表面処理剤を被着体の少なくとも一方に塗布する工程。
（２）塗布したシアノアクリレート接着剤組成物用表面処理剤を乾燥する工程。
[3]
An adhesion method for adhering adherends together using a cyanoacrylate adhesive composition, the adhesion method comprising the following steps (1) and (2) in this order as a pre-adhesion step.
(1) A step of applying the surface treatment agent for a cyanoacrylate adhesive composition according to [1] or [2] to at least one of the adherends.
(2) Drying the applied surface treatment agent for cyanoacrylate adhesive composition.
〔４〕
被着体の内、少なくとも一方がポリオレフィン樹脂またはポリオレフィン樹脂を含有するエラストマーである、〔３〕に記載の接着方法。
[4]
The adhesion method according to [3], wherein at least one of the adherends is a polyolefin resin or an elastomer containing a polyolefin resin.
〔５〕
更に、下記工程（ａ）を含む〔３〕に記載の接着方法（ただし、工程（ａ）は工程（１）より後に実施する）。
（ａ）シアノアクリレート接着剤組成物用表面処理剤の塗布面に紫外線を照射し、蛍光発光により塗布面を確認する工程。
[5]
Furthermore, the adhesion method according to [3], which further includes the following step (a) (however, step (a) is carried out after step (1)).
(a) A step of irradiating the surface coated with the surface treatment agent for a cyanoacrylate adhesive composition with ultraviolet rays and confirming the coated surface by fluorescence emission.
本発明によれば、塗布した後に塗布箇所や塗布量の確認が可能な表面処理剤の提供が可能となる。また、本発明の表面処理剤は、塗布してから３時間経過後であっても、照明の点いた明るい室内環境中において視認可能であることから、その後の工程における作業時間を長く確保することができ、取り扱い性に優れる。また、本発明の表面処理剤は、通常無色透明であり、且つ紫外線を照射することで蛍光発光が生じ視認可能となる物であるところ、塗布してから一定時間経過後には照明の点いた明るい室内環境下では視認できない程度に蛍光発光が減衰することから、完成品の外観に影響を与えない。また、後述する実施例の項で示す通り、本発明の表面処理剤によれば、前述した難接着材料の接着において、充分な硬化速度が得られるとともに、上記特許文献１に記載の表面処理剤を使用した場合と同程度かそれ以上の接着強度を得ることができる。 According to the present invention, it is possible to provide a surface treatment agent that allows confirmation of the application location and application amount after application. In addition, the surface treatment agent of the present invention is visible in a brightly lit indoor environment even after 3 hours have passed after application, so it is possible to secure a longer working time in subsequent steps. It is easy to handle. In addition, the surface treatment agent of the present invention is usually colorless and transparent, and when irradiated with ultraviolet light, it emits fluorescence and becomes visible, but after a certain period of time after application, it becomes bright and illuminated. Since the fluorescent light emission is attenuated to the extent that it cannot be seen in an indoor environment, it does not affect the appearance of the finished product. Furthermore, as shown in the Examples section below, the surface treatment agent of the present invention can achieve a sufficient curing speed in bonding the difficult-to-bond materials described above, and the surface treatment agent described in Patent Document 1 It is possible to obtain adhesive strength comparable to or greater than when using .
以下、本発明のシアノアクリレート接着剤組成物用表面処理剤について、詳細に説明する。 Hereinafter, the surface treating agent for cyanoacrylate adhesive compositions of the present invention will be explained in detail.
［成分（Ａ）］
成分（Ａ）は、少なくとも分岐を有してもよい炭素数５～１５の脂肪族炭化水素系溶媒を含む。前記分岐を有してもよい炭素数５～１５の脂肪族炭化水素系溶媒の具体例としては、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、リグロイン等が挙げられる。中でも、分岐を有してもよい炭素数５～１０の脂肪族炭化水素系溶媒が好ましく、ヘプタン、オクタン、ノナン、リグロインがより好ましい。これらの脂肪族炭化水素系溶媒は、単独で用いてもよく、２種以上を併用してもよい。
[Component (A)]
Component (A) contains at least an aliphatic hydrocarbon solvent having 5 to 15 carbon atoms which may have a branch. Specific examples of the aliphatic hydrocarbon solvent having 5 to 15 carbon atoms which may have branches include pentane, hexane, heptane, octane, nonane, decane, ligroin, and the like. Among these, aliphatic hydrocarbon solvents having 5 to 10 carbon atoms which may have branches are preferred, and heptane, octane, nonane, and ligroin are more preferred. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.
また、成分（Ａ）に含まれていてもよい、分岐を有してもよい炭素数５～１５の脂肪族炭化水素系溶媒以外の他の有機溶媒としては、例えば、低級アルコール系溶媒、低級脂肪酸のエステル系溶媒、ケトン系溶媒、芳香族炭化水素系溶媒、ハロゲン化炭化水素系溶媒等が挙げられる。具体的には、例えば、低級アルコール系溶媒としてメタノール、エタノール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール等が挙げられ、低級脂肪酸のエステル系溶媒として酢酸メチル、酢酸エチル、酢酸－ｉ－プロピル、酢酸－ｎ－プロピル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸ベンンジル、酢酸シクロヘキシル等が挙げられ、ケトン系溶媒としてアセトン、メチルエチルケトン、メチルイソブチルケトン等が挙げられ、芳香族炭化水素系溶媒としてベンゼン、トルエン、キシレン等が挙げられ、ハロゲン化炭化水素系溶媒として塩化メチレン、１，１，１－トリクロルエタン、二塩化エタン、トリクロルトリフルオロエタン、パークロルエタン等が挙げられる。これらの他の有機溶媒は１種又は２種以上含まれていてもよいが、分岐を有してもよい炭素数５～１５の脂肪族炭化水素系溶媒を単独で使用する方が好ましい。 In addition, other organic solvents other than the optionally branched aliphatic hydrocarbon solvent having 5 to 15 carbon atoms that may be included in component (A) include, for example, lower alcohol solvents, lower Examples include fatty acid ester solvents, ketone solvents, aromatic hydrocarbon solvents, and halogenated hydrocarbon solvents. Specifically, for example, lower alcohol solvents include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, etc., and lower fatty acid ester solvents include methyl acetate, ethyl acetate, i-propyl acetate, Examples include n-propyl acetate, n-butyl acetate, isobutyl acetate, benzyl acetate, cyclohexyl acetate, etc. Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and aromatic hydrocarbon solvents include benzene, Examples of the halogenated hydrocarbon solvent include toluene and xylene, and examples of the halogenated hydrocarbon solvent include methylene chloride, 1,1,1-trichloroethane, dichlorethane, trichlorotrifluoroethane, and perchloroethane. One or more of these other organic solvents may be included, but it is preferable to use a branched aliphatic hydrocarbon solvent having 5 to 15 carbon atoms alone.
［成分（Ｂ）］
成分（Ｂ）は、上記一般式（１）で表される化合物および上記一般式（２）で表される化合物からなる群から選ばれる少なくとも１種のポリアミン化合物である。
[Component (B)]
Component (B) is at least one polyamine compound selected from the group consisting of the compound represented by the above general formula (1) and the compound represented by the above general formula (2).
前記一般式（１）において、Ｒ１～Ｒ４はそれぞれ独立してメチル基又はエチル基を表す。Ｒ５は分岐を有してもよい炭素数１～１０のアルキレン基を表し、好ましくは直鎖状の炭素数１～１０のアルキレン基であり、より好ましくは直鎖状の炭素数１～６のアルキレン基である。なお、Ｒ１～Ｒ４は同一であることが好ましい。 In the general formula (1), R 1 to R 4 each independently represent a methyl group or an ethyl group. R 5 represents an optionally branched alkylene group having 1 to 10 carbon atoms, preferably a linear alkylene group having 1 to 10 carbon atoms, and more preferably a linear alkylene group having 1 to 6 carbon atoms. is an alkylene group. Note that R 1 to R 4 are preferably the same.
前記一般式（１）で表される化合物の具体例としては、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノメタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノエタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノブタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノヘプタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノオクタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノデカン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラエチルジアミノメタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラエチルジアミノエタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラエチルジアミノプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラエチルジアミノブタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラエチルジアミノヘキサン等が挙げられる。これら具体例の中でも、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノエタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノプロパン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラエチルジアミノエタンが好ましい。 Specific examples of the compound represented by the general formula (1) include N,N,N',N'-tetramethyldiaminomethane, N,N,N',N'-tetramethyldiaminoethane, N,N ,N',N'-tetramethyldiaminopropane, N,N,N',N'-tetramethyldiaminobutane, N,N,N',N'-tetramethyldiaminohexane, N,N,N',N '-tetramethyldiaminoheptane, N,N,N',N'-tetramethyldiaminooctane, N,N,N',N'-tetramethyldiaminodecane, N,N,N',N'-tetraethyldiaminomethane , N,N,N',N'-tetraethyldiaminoethane, N,N,N',N'-tetraethyldiaminopropane, N,N,N',N'-tetraethyldiaminobutane, N,N,N', Examples include N'-tetraethyldiaminohexane. Among these specific examples, N,N,N',N'-tetramethyldiaminoethane, N,N,N',N'-tetramethyldiaminopropane, N,N,N',N'-tetramethyldiaminohexane , N,N,N',N'-tetraethyldiaminoethane is preferred.
前記一般式（２）において、Ｒ６～Ｒ９はそれぞれ独立してメチル基又はエチル基を表す。Ｒ１０は分岐を有してもよい炭素数１～１０のアルキレン基を表し、好ましくは直鎖状の炭素数１～１０のアルキレン基であり、より好ましくは直鎖状の炭素数１～６のアルキレン基であり、更に好ましくは直鎖状の炭素数２～３のアルキレン基である。ｎは２～１０の整数を表し、好ましくは２～４である。なお、Ｒ６～Ｒ９は同一であることが好ましい。また、複数存在するＲ１０は互いに同一であっても、異なっていてもよいが、同一であることが好ましい。 In the general formula (2), R 6 to R 9 each independently represent a methyl group or an ethyl group. R 10 represents an optionally branched alkylene group having 1 to 10 carbon atoms, preferably a linear alkylene group having 1 to 10 carbon atoms, and more preferably a linear alkylene group having 1 to 6 carbon atoms. is an alkylene group, more preferably a linear alkylene group having 2 to 3 carbon atoms. n represents an integer of 2 to 10, preferably 2 to 4. Note that R 6 to R 9 are preferably the same. Further, a plurality of R 10s may be the same or different, but it is preferable that they are the same.
前記一般式（２）で表される化合物の具体例としては、Ｎ－メチル－Ｎ，Ｎ－ビス［３－（ジメチルアミノ）プロピル］アミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチル－（３－アミノプロピル）エチレンジアミン等が挙げられる。これら具体例の中でも、Ｎ－メチル－Ｎ，Ｎ－ビス［３－（ジメチルアミノ）プロピル］アミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチルジエチレントリアミンが好ましい。 Specific examples of the compound represented by the general formula (2) include N-methyl-N,N-bis[3-(dimethylamino)propyl]amine, N,N,N', N'',N' '-pentamethyldiethylenetriamine, N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine, and the like. Among these specific examples, N-methyl-N,N-bis[3-(dimethylamino)propyl]amine and N,N,N',N'',N''-pentamethyldiethylenetriamine are preferred.
成分（Ｂ）の含有量は、成分（Ａ）１００重量部に対し、通常０．０５～５．０重量部、好ましくは０．１～５．０重量部、より好ましくは０．３～４．０重量部である。０．０５重量部より少ない場合、表面処理剤としての効果が小さくシアノアクリレート接着剤組成物で接着した際に十分な接着力が発現せず、また、５重量部より多い場合、塗布面に成分（Ｂ）の層ができ、シアノアクリレート接着剤組成物を被着体に塗布後すぐに硬化して接着できなかったり、前記成分（Ｂ）の層ごと剥がれが生じて接着力が低下する虞がある。 The content of component (B) is usually 0.05 to 5.0 parts by weight, preferably 0.1 to 5.0 parts by weight, more preferably 0.3 to 4 parts by weight, per 100 parts by weight of component (A). .0 parts by weight. If it is less than 0.05 parts by weight, the effect as a surface treatment agent is small and sufficient adhesive strength will not be developed when bonded with the cyanoacrylate adhesive composition, and if it is more than 5 parts by weight, the component There is a risk that a layer of component (B) will form and the cyanoacrylate adhesive composition will harden immediately after being applied to the adherend, making it impossible to bond, or that the entire layer of component (B) will peel off, resulting in a decrease in adhesive strength. be.
［成分（Ｃ）］
成分（Ｃ）は上記一般式（３）で表される、蛍光性を有する化合物である。上記一般式（３）中、Ｒ１１及びＲ１２はそれぞれ独立して水素原子または分岐を有してもよい炭素数１～８のアルキル基を表し、好ましくは水素原子または炭素数１～４の分岐を有してもよいアルキル基である。
[Component (C)]
Component (C) is a fluorescent compound represented by the above general formula (3). In the above general formula (3), R 11 and R 12 each independently represent a hydrogen atom or an optionally branched alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is an alkyl group that may have a branch.
上記一般式（３）で表される化合物としては、例えば、２，５－ビス（５－ｔｅｒｔ－ブチル－２－ベンゾオキサゾリル）チオフェン等が挙げられる。 Examples of the compound represented by the above general formula (3) include 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene.
成分（Ｃ）の含有量は、成分（Ａ）１００重量部に対し、通常０．０２～０．５５重量部であり、好ましくは０．０５～０．３０重量部である。０．０２重量部より少ないと、塗布範囲確認の際に充分な蛍光発光が得られない場合がある。また、０．５５重量部より多いとポリオレフィンとジエン系ゴムからなるＴＰＥやＴＰＯ、ＴＰＶ等の熱可塑性エラストマー等の難接着材料を接着する際に、充分な接着力が得られない場合がある。 The content of component (C) is usually 0.02 to 0.55 parts by weight, preferably 0.05 to 0.30 parts by weight, per 100 parts by weight of component (A). If it is less than 0.02 part by weight, sufficient fluorescence may not be obtained when checking the coating area. If the amount is more than 0.55 parts by weight, sufficient adhesive strength may not be obtained when bonding difficult-to-bond materials such as TPE made of polyolefin and diene rubber, and thermoplastic elastomers such as TPO and TPV.
本発明のシアノアクリレート接着剤組成物用表面処理剤は、例えば、上記した成分（Ａ）～（Ｃ）を混合することで製造することが可能である。また、必要に応じ、本願発明の目的及び効果を損なわない範囲で公知の無機化合物、樹脂、着色剤、脱臭剤、香料、可塑剤等を適宜、添加配合することもできる。 The surface treatment agent for a cyanoacrylate adhesive composition of the present invention can be produced, for example, by mixing the above-mentioned components (A) to (C). Further, if necessary, known inorganic compounds, resins, colorants, deodorizers, fragrances, plasticizers, etc. may be added and blended as appropriate within a range that does not impair the purpose and effects of the present invention.
本発明におけるシアノアクリレート接着剤組成物としては、従来公知の２－シアノアクリレートを主成分として含むものであれば特に限定されない。主成分として含まれる２－シアノアクリレートとしては、例えば、２－シアノアクリル酸のメチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｓｅｃ－ブチル、オクチル、ネオペンチル、シクロヘキシル、エチルヘキシル、ドデシル、アリル、メトキシエチル、エトキシエチル、メトキシプロピル、ベンジル、フェニル、クロロエチル、テトラヒドロフルフリル等のエステル類が挙げられる。これらの２－シアノアクリレートは単独で用いてもよく、２種以上を併用してもよい。 The cyanoacrylate adhesive composition in the present invention is not particularly limited as long as it contains a conventionally known 2-cyanoacrylate as a main component. Examples of the 2-cyanoacrylate contained as a main component include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, octyl, neopentyl, cyclohexyl, ethylhexyl, dodecyl 2-cyanoacrylate, Examples include esters such as allyl, methoxyethyl, ethoxyethyl, methoxypropyl, benzyl, phenyl, chloroethyl, and tetrahydrofurfuryl. These 2-cyanoacrylates may be used alone or in combination of two or more.
また、本発明で用いられるシアノアクリレート接着剤組成物には、必要に応じて、従来、シアノアクリレート接着剤組成物に用いられている各種充填剤、可塑剤、増粘剤、強度向上剤、揺変剤、耐熱性付与剤、耐水性付与剤、速硬化添加剤、軟化剤、可撓性付与剤、安定剤、香料、溶剤等が、２－シアノアクリレートモノマーの硬化速度および安定性を阻害しない範囲で含まれていてもよい。 In addition, the cyanoacrylate adhesive composition used in the present invention may optionally contain various fillers, plasticizers, thickeners, strength improvers, and additives conventionally used in cyanoacrylate adhesive compositions. Modifiers, heat resistance imparting agents, water resistance imparting agents, fast curing additives, softeners, flexibility imparting agents, stabilizers, fragrances, solvents, etc. do not inhibit the curing speed and stability of the 2-cyanoacrylate monomer. May be included within the range.
続いて、本発明のシアノアクリレート接着剤組成物用表面処理剤（以下、本発明の表面処理剤と称することもある。）を用いた、シアノアクリレート接着剤組成物による被着体の接着方法（以下、本発明の接着方法と称することもある。）について詳述する。 Next, a method for bonding an adherend with a cyanoacrylate adhesive composition using the surface treatment agent for a cyanoacrylate adhesive composition of the present invention (hereinafter sometimes referred to as the surface treatment agent of the present invention). Hereinafter, the bonding method of the present invention (also referred to as the bonding method of the present invention) will be described in detail.
本発明の接着方法は、接着の前工程として以下工程（１）及び（２）をこの順で含む。
（１）本発明の表面処理剤を被着体の少なくとも一方に塗布する工程。
（２）塗布した本発明の表面処理剤を乾燥する工程。
The adhesion method of the present invention includes the following steps (1) and (2) in this order as a pre-adhesion step.
(1) A step of applying the surface treatment agent of the present invention to at least one of the adherends.
(2) Drying the applied surface treatment agent of the present invention.
工程（１）において、被着体は常法により予め清浄化されていてもよい。また、本発明の表面処理剤の塗布方法としては、従来公知のシアノアクリレート接着剤組成物用表面処理剤と同様の方法が使用でき、例えば、容器やスポイトからの滴下、刷毛やペン等での塗布、スプレーによる噴霧、被着体を表面処理剤に浸漬させる方法等が挙げられる。また、本発明における被着体としては特に限定されないが、本発明のシアノアクリレート接着剤組成物用表面処理剤を使用することで、シアノアクリレート接着剤組成物単独で接着することが困難であるポリプロピレン、ポリエチレン等のポリオレフィン、ポリアセタール、ふっ素系樹脂および結晶性の高いプラスチック、並びにポリオレフィンとジエン系ゴム等からなるＴＰＥやＴＰＯ、ＴＰＶ等の熱可塑性エラストマー等の難接着材料の接着においても、充分な硬化速度および高い接着強度を得ることができることから、被着体の少なくとも一方はこれらの難接着材料であることが好ましい。 In step (1), the adherend may be cleaned in advance by a conventional method. Furthermore, as a method for applying the surface treatment agent of the present invention, the same method as that for conventionally known surface treatment agents for cyanoacrylate adhesive compositions can be used, such as dripping from a container or dropper, or applying with a brush or pen. Examples include methods such as coating, spraying, and immersing the adherend in a surface treatment agent. In addition, the adherend in the present invention is not particularly limited, but by using the surface treatment agent for the cyanoacrylate adhesive composition of the present invention, polypropylene which is difficult to adhere with the cyanoacrylate adhesive composition alone can be used. Sufficient curing for adhesion of difficult-to-bond materials such as polyolefins such as polyethylene, polyacetals, fluororesins, highly crystalline plastics, and thermoplastic elastomers such as TPE, TPO, and TPV made of polyolefins and diene rubbers. At least one of the adherends is preferably made of these difficult-to-bond materials, since speed and high adhesive strength can be obtained.
工程（２）において、本発明の表面処理剤を乾燥する方法としては、例えば、本発明の表面処理剤を塗布した後、室温にて静置し表面処理剤に含まれる溶媒を乾燥させる方法等が挙げられる。 In step (2), the method of drying the surface treatment agent of the present invention includes, for example, a method of applying the surface treatment agent of the present invention and then allowing it to stand at room temperature to dry the solvent contained in the surface treatment agent. can be mentioned.
本発明の接着方法は、接着の前工程として更に以下工程（ａ）を含んでいてもよい。
（ａ）シアノアクリレート接着剤組成物用表面処理剤の塗布面に紫外線を照射し、蛍光発光により塗布面を確認する工程（ただし、工程（ａ）は工程（１）より後に実施する）。
The adhesion method of the present invention may further include the following step (a) as a pre-adhesion step.
(a) A step of irradiating the coated surface of the surface treatment agent for a cyanoacrylate adhesive composition with ultraviolet rays and confirming the coated surface by fluorescence emission (however, step (a) is carried out after step (1)).
工程（ａ）において、紫外線を照射し、蛍光発光により塗布面を確認する方法は特に限定されないが、例えば、発光波長領域が４００ｎｍ未満である公知または市販の紫外線照射装置を用いて塗布面に紫外線を照射し、蛍光発光を目視で確認する方法等が挙げられる。シアノアクリレート接着剤組成物塗布する前に、シアノアクリレート接着剤組成物用表面処理剤の塗布面を確認することで、塗布漏れ等を起こす可能性を低減することができ、充分な硬化速度および高い接着強度で接着することができる。 In step (a), the method of irradiating ultraviolet rays and checking the coated surface by fluorescence emission is not particularly limited, but for example, the method of irradiating the coated surface with ultraviolet rays using a known or commercially available ultraviolet irradiation device with an emission wavelength range of less than 400 nm is used. For example, a method of irradiating the fluorescent light and visually confirming the fluorescence emission can be mentioned. Before applying the cyanoacrylate adhesive composition, by checking the surface to be coated with the surface treatment agent for the cyanoacrylate adhesive composition, you can reduce the possibility of coating leakage, etc., and ensure a sufficient curing speed and high Can be bonded with adhesive strength.
上記した接着の前工程を行った後、例えば、被着体の一方または両方の接着面にシアノアクリレート接着剤組成物を塗布して貼り合わせ、圧締して養生する方法等により、被着体同士を接着することができる。 After performing the above-mentioned pre-adhesion process, the adherend is bonded by, for example, applying a cyanoacrylate adhesive composition to one or both bonding surfaces of the adherend, bonding, pressing, and curing. They can be glued together.
以下、実施例等を挙げて本発明をより詳細に説明するが、本発明はこれらに何ら限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
＜実施例１～１１、比較例１～１０＞
撹拌機を備えたガラス製容器に、表１及び表２に示す割合で各成分を仕込み、攪拌溶解することで、各実施例および比較例に係るシアノアクリレート接着剤用表面処理剤を調製した。得られたシアノアクリレート接着剤用表面処理剤を用いて、表１及び表２に示す各項目について、下記する方法により測定・評価を行った。なお、表１及び表２における「オープンタイム」とはシアノアクリレート接着剤用表面処理剤を塗布した後、シアノアクリレート接着剤組成物を滴下するまでの乾燥工程の時間のことを表す。また、表１及び表２における記号、略号の意味は次の通りである。
・ＴＰＯ：オレフィン系熱可塑性エラストマー
・ＥＰＤＭ：エチレンプロピレンジエンゴム
・ＰＰ：ポリプロピレン
・ＰＥ：高密度ポリエチレン（ＨＤＰＥ）
<Examples 1 to 11, Comparative Examples 1 to 10>
A surface treatment agent for cyanoacrylate adhesives according to each example and comparative example was prepared by charging each component in the proportions shown in Tables 1 and 2 into a glass container equipped with a stirrer, and stirring and dissolving the components. Using the obtained surface treatment agent for cyanoacrylate adhesive, each item shown in Tables 1 and 2 was measured and evaluated by the method described below. In addition, "open time" in Tables 1 and 2 represents the time of the drying process after applying the cyanoacrylate adhesive surface treatment agent until dropping the cyanoacrylate adhesive composition. Furthermore, the meanings of the symbols and abbreviations in Tables 1 and 2 are as follows.
・TPO: Olefin thermoplastic elastomer ・EPDM: Ethylene propylene diene rubber ・PP: Polypropylene ・PE: High density polyethylene (HDPE)
＜表面処理剤の外観及び溶液の均一性の評価＞
前記の通り調製したシアノアクリレート接着剤組成物用表面処理剤を２５℃で２４時間保管した後、表面処理剤の「外観」及び「溶液の均一性」について目視で確認した。
<Evaluation of appearance of surface treatment agent and uniformity of solution>
After storing the surface treatment agent for a cyanoacrylate adhesive composition prepared as described above at 25° C. for 24 hours, the “appearance” and “uniformity of the solution” of the surface treatment agent were visually confirmed.
＜手感度による接着強度および接着状態の評価＞
ＴＰＯ板（２５×５０×３ｍｍ、エンジニアリングテストサービス社製）の接着面に前記の通り調製したシアノアクリレート接着剤組成物用表面処理剤を綿棒で塗布し、２０℃の室内に３０分間静置して塗布面を乾燥した後、シアノアクリレート接着剤組成物（シアノボンドＲＰ－Ｘ：田岡化学工業株式会社製（主成分：エチル－α－シアノアクリレート））をＥＰＤＭ板（２５×５０×２ｍｍ、スタンダードテストピース社製）上に１滴滴下し、１／２インチオーバーラップで被着体同士を接着後、そのまま２秒間手で押さえて固定した後、すみやかに１８０度剥離方向に両被着体を手で引っ張り、手感度で接着強度および接着状態を評価した。なお、評価基準は下記の通りである。
〇：材破
×：材破以外（界面破壊等）
<Evaluation of adhesive strength and adhesive condition by hand sensitivity>
The surface treatment agent for the cyanoacrylate adhesive composition prepared as described above was applied with a cotton swab to the adhesive surface of a TPO board (25 x 50 x 3 mm, manufactured by Engineering Test Service Co., Ltd.), and the mixture was left standing in a room at 20°C for 30 minutes. After drying the coated surface, a cyanoacrylate adhesive composition (Cyanobond RP-X: manufactured by Taoka Chemical Co., Ltd. (main component: ethyl-α-cyanoacrylate)) was applied to an EPDM board (25 x 50 x 2 mm, standard test). After adhering the adherends to each other with a 1/2 inch overlap (manufactured by Peace Inc.), after adhering the adherends to each other with a 1/2 inch overlap, hold the adherends together by hand for 2 seconds to fix them. The adhesive strength and condition were evaluated using hand sensitivity. The evaluation criteria are as follows.
〇: Material damage ×: Other than material damage (interface failure, etc.)
＜引張剪断接着強さの測定および接着状態の評価＞
両方の被着体の接着面に前記の通り調製したシアノアクリレート接着剤組成物用表面処理剤を綿棒で塗布し、２０℃の室内に１５分間静置して塗布面を乾燥した後、一方の被着体の接着面にシアノアクリレート接着剤組成物（シアノボンドＲＰ－Ｘ：田岡化学工業株式会社製（主成分：エチル－α－シアノアクリレート））を２滴滴下し、１／２インチオーバーラップで被着体同士を接着、圧締し１時間養生後、ＪＩＳ Ｋ ６８６１に準拠して引張剪断接着強さ（単位（Ｎ／ｍｍ２）を測定し、また、接着状態を評価した。なお、評価基準は下記の通りである。また、被着体としては、ポリプロピレン（ＰＰ）及びポリエチレン（ＰＥ）板（どちらも２５×１００×２ｍｍ、エンジニアリングテストサービス社製）を準備し、ＰＰ板とＰＰ板同士、ＰＥ板とＰＥ板同士を接着させた。
〇：材破
×：材破以外（界面破壊等）
<Measurement of tensile shear adhesive strength and evaluation of adhesive state>
The surface treatment agent for the cyanoacrylate adhesive composition prepared as described above was applied to the adhesive surfaces of both adherends using a cotton swab, and the applied surface was dried by leaving it in a room at 20°C for 15 minutes. Two drops of a cyanoacrylate adhesive composition (Cyanobond RP-X: manufactured by Taoka Chemical Industry Co., Ltd. (main component: ethyl-α-cyanoacrylate)) were dropped onto the adhesive surface of the adherend, and the adhesive was applied with a 1/2 inch overlap. After adhering and pressing the adherends together and curing for 1 hour, the tensile shear adhesive strength (unit: N/mm 2 ) was measured in accordance with JIS K 6861, and the adhesion state was evaluated. The standards are as follows.In addition, polypropylene (PP) and polyethylene (PE) plates (both 25 x 100 x 2 mm, manufactured by Engineering Test Service Co., Ltd.) were prepared as adherends, and PP plates and PP plates were prepared. PE boards were bonded together.
〇: Material damage ×: Other than material damage (interface failure, etc.)
＜表面処理剤塗布部の視認性評価＞
前記の通り調製したシアノアクリレート接着剤組成物用表面処理剤を、綿棒を用いてオレフィン系熱可塑性エラストマー（ＴＰＯ）板（２５×５０×３ｍｍ、エンジニアリングテストサービス社製）に塗布した後、塗布部に１０ｃｍの距離から３６５ｎｍのハンディ紫外線ライト（マナスル化学工業社製）で紫外線を照射し、塗布部の蛍光発光を目視で観察し、視認性を評価した。また、所定時間経過毎に同様の方法で塗布部の蛍光発光を目視で観察し、所定時間経過後の視認性についても同様に評価した。なお、評価基準は下記の通りである。
〇：通常の照明の点いた明るい室内環境中において塗布部の確認可
△：暗室内において塗布部の確認可
×：塗布部の確認が不可
<Visibility evaluation of surface treatment agent applied area>
After applying the surface treatment agent for the cyanoacrylate adhesive composition prepared as described above to a thermoplastic olefin elastomer (TPO) plate (25 x 50 x 3 mm, manufactured by Engineering Test Service Co., Ltd.) using a cotton swab, Ultraviolet light was irradiated from a distance of 10 cm using a 365 nm handy ultraviolet light (manufactured by Manaslu Chemical Industry Co., Ltd.), and fluorescence emission from the coated area was visually observed to evaluate visibility. In addition, the fluorescent light emission of the coated area was visually observed every predetermined time period using the same method, and the visibility after the predetermined time period was also evaluated in the same manner. The evaluation criteria are as follows.
〇: The coated area can be confirmed in a bright indoor environment with normal lighting △: The coated area can be confirmed in a dark room ×: The coated area cannot be confirmed
＜表面処理剤の被着体外観への影響＞
前記の通り調製したシアノアクリレート接着剤組成物用表面処理剤を、綿棒を用いてオレフィン系熱可塑性エラストマー（ＴＰＯ）板（２５×５０×３ｍｍ、エンジニアリングテストサービス社製）に塗布した後、通常の照明の点いた明るい室内環境中において、被着体外観への影響を目視で確認した。
<Effect of surface treatment agent on the appearance of the adherend>
The surface treatment agent for the cyanoacrylate adhesive composition prepared as described above was applied to a thermoplastic olefin elastomer (TPO) board (25 x 50 x 3 mm, manufactured by Engineering Test Service Co., Ltd.) using a cotton swab. The effect on the appearance of the adherend was visually confirmed in a bright indoor environment with lights on.
Claims (5)
（Ａ）分岐を有してもよい炭素数５～１５の脂肪族炭化水素系溶媒を含む有機溶媒。
（Ｂ）下記一般式（１）：
で表される化合物および下記一般式（２）：
で表される化合物からなる群から選ばれる少なくとも１種のポリアミン化合物。
（Ｃ）下記一般式（３）：
で表される化合物。 Contains the following (A), (B) and (C), and the content of (B) is 0.05 to 5.0 parts by weight per 100 parts by weight of (A), and the content of (C) is is 0.02 to 0.55 parts by weight based on 100 parts by weight of (A), a surface treatment agent for a cyanoacrylate adhesive composition.
(A) An organic solvent containing an aliphatic hydrocarbon solvent having 5 to 15 carbon atoms which may have branches.
(B) The following general formula (1):
The compound represented by and the following general formula (2):
At least one polyamine compound selected from the group consisting of compounds represented by:
(C) The following general formula (3):
A compound represented by
（１）請求項１又は２に記載のシアノアクリレート接着剤組成物用表面処理剤を被着体の少なくとも一方に塗布する工程。
（２）塗布したシアノアクリレート接着剤組成物用表面処理剤を乾燥する工程。 An adhesion method for adhering adherends together using a cyanoacrylate adhesive composition, the adhesion method comprising the following steps (1) and (2) in this order as a pre-adhesion step.
(1) A step of applying the surface treatment agent for a cyanoacrylate adhesive composition according to claim 1 or 2 to at least one of the adherends.
(2) Drying the applied surface treatment agent for cyanoacrylate adhesive composition.
（ａ）シアノアクリレート接着剤組成物用表面処理剤の塗布面に紫外線を照射し、蛍光発光により塗布面を確認する工程。 The adhesion method according to claim 3, further comprising the following step (a) (provided that step (a) is carried out after step (1)).
(a) A step of irradiating the coated surface of the surface treatment agent for the cyanoacrylate adhesive composition with ultraviolet light and confirming the coated surface by fluorescence emission.
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