JP5253315B2 - Solvent type epoxy adhesive and bonding method - Google Patents
Solvent type epoxy adhesive and bonding method Download PDFInfo
- Publication number
- JP5253315B2 JP5253315B2 JP2009173880A JP2009173880A JP5253315B2 JP 5253315 B2 JP5253315 B2 JP 5253315B2 JP 2009173880 A JP2009173880 A JP 2009173880A JP 2009173880 A JP2009173880 A JP 2009173880A JP 5253315 B2 JP5253315 B2 JP 5253315B2
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- JP
- Japan
- Prior art keywords
- adhesive
- solvent
- epoxy resin
- mass
- parts
- 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.)
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- 229920006332 epoxy adhesive Polymers 0.000 title claims description 124
- 239000002904 solvent Substances 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 49
- 229920000647 polyepoxide Polymers 0.000 claims description 128
- 239000003822 epoxy resin Substances 0.000 claims description 118
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 102
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 91
- 239000000843 powder Substances 0.000 claims description 79
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 229910000838 Al alloy Inorganic materials 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 33
- 239000011256 inorganic filler Substances 0.000 claims description 31
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 31
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 24
- 238000004381 surface treatment Methods 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 19
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 16
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 15
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 14
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 150000002576 ketones Chemical class 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 245
- 230000001070 adhesive effect Effects 0.000 description 242
- 239000007864 aqueous solution Substances 0.000 description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 79
- 239000004695 Polyether sulfone Substances 0.000 description 60
- 229920006393 polyether sulfone Polymers 0.000 description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 57
- 239000000203 mixture Substances 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 238000005530 etching Methods 0.000 description 36
- 238000002474 experimental method Methods 0.000 description 35
- 238000012360 testing method Methods 0.000 description 27
- 239000000126 substance Substances 0.000 description 25
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- 239000004576 sand Substances 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- -1 aliphatic amines Chemical class 0.000 description 20
- 238000000227 grinding Methods 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 19
- 238000010298 pulverizing process Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 229920001971 elastomer Polymers 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000000523 sample Substances 0.000 description 16
- 229910002012 Aerosil® Inorganic materials 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 229920005992 thermoplastic resin Polymers 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000003486 chemical etching Methods 0.000 description 14
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 14
- 229920000573 polyethylene Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000012790 adhesive layer Substances 0.000 description 13
- 239000013527 degreasing agent Substances 0.000 description 13
- 238000005237 degreasing agent Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 101001139130 Homo sapiens Krueppel-like factor 5 Proteins 0.000 description 12
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910021485 fumed silica Inorganic materials 0.000 description 10
- 238000001879 gelation Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000454 talc Substances 0.000 description 10
- 229910052623 talc Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000004984 aromatic diamines Chemical class 0.000 description 8
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- 239000010949 copper Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 8
- 229960002218 sodium chlorite Drugs 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- 239000012971 dimethylpiperazine Substances 0.000 description 6
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- 238000000576 coating method Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 238000001556 precipitation Methods 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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Description
本発明は、移動機械、電気機器、医療機器、及び一般機械等の製造分野において使用されるエポキシ接着剤に関する。特に、無溶剤型と同等の接着力を有し、かつ接着対象に噴霧させることが可能な溶剤型エポキシ接着剤と、その溶剤型エポキシ接着剤を使用した接着方法に関する。 The present invention relates to an epoxy adhesive used in the manufacturing field of mobile machines, electrical equipment, medical equipment, general machines, and the like. In particular, the present invention relates to a solvent-type epoxy adhesive having an adhesive force equivalent to that of a solventless type and capable of being sprayed on an object to be bonded, and a bonding method using the solvent-type epoxy adhesive.
本発明者らは、金属合金同士、又は金属合金とＣＦＲＰ（Carbon Fiber Reinforced Plasticsの略）をエポキシ接着剤により強固に接着する技術を開発した。特許文献１には、アルミニウム合金同士、又はアルミニウム合金とＣＦＲＰとを１液性エポキシ接着剤を使用して強固に接着する技術を開示している。同様に、特許文献２、３、４、５、及び６には、マグネシウム合金、銅合金、チタン合金、ステンレス鋼、及び一般鋼材を、それぞれ金属合金又はＣＦＲＰ部材と１液性エポキシ接着剤を使用して強固に接着する技術を開示している。 The present inventors have developed a technique for firmly bonding metal alloys or metal alloys and CFRP (abbreviation of Carbon Fiber Reinforced Plastics) with an epoxy adhesive. Patent Document 1 discloses a technique for firmly bonding aluminum alloys or between an aluminum alloy and CFRP using a one-component epoxy adhesive. Similarly, in Patent Documents 2, 3, 4, 5, and 6, magnesium alloy, copper alloy, titanium alloy, stainless steel, and general steel material are respectively used as a metal alloy or a CFRP member and a one-component epoxy adhesive. Thus, a technique for firmly bonding is disclosed.
ここで、上記技術においては金属合金表面を所定の形状、構造とすることで、アンカー効果によって接着力を獲得していた。本発明者らは、この理論を「ＮＡＴ（Nano Adhesion Technologyの略）」と称している。ＮＡＴでは、金属合金表面が以下に示す３条件を具備することで、被着材との強固な接着を達成することとしている。 Here, in the said technique, the adhesive force was acquired by the anchor effect by making the metal alloy surface into a predetermined shape and structure. The inventors refer to this theory as “NAT (Nano Adhesion Technology)”. In NAT, the metal alloy surface satisfies the following three conditions to achieve strong adhesion to the adherend.
（１）第１の条件は、最新型のダイナミックモード型の走査型プローブ顕微鏡で金属合金表面を走査したときに、ＲＳｍが０．８〜１０μｍであり、Ｒｚが０．２〜５μｍである粗度面となっていることである。ここでＲＳｍは、日本工業規格（JIS B 0601:2001, ISO 4287:1997）に規定される輪郭曲線要素の平均長さであり、Ｒｚは、日本工業規格（JIS B 0601:2001, ISO 4287:1997）に規定される最大高さである。この粗度面を「ミクロンオーダーの粗度を有する表面」と称す。
（２）第２の条件は、上記ミクロンオーダーの粗度を有する金属合金表面に、さらに５ｎｍ周期以上の超微細凹凸が形成されていることである。当該条件を具備するために、上記金属合金表面に微細エッチングを行い、前述のミクロンオーダーの粗度をなす凹部内壁面に５〜５００ｎｍ、好ましくは１０〜３００ｎｍ、より好ましくは３０〜１００ｎｍ（最適値は５０〜７０ｎｍ）周期の超微細凹凸を形成する。
（３）第３の条件は、上記金属合金の表層がセラミック質であることである。具体的には、元来耐食性のある金属合金種に関しては、その表層が自然酸化層レベルかそれ以上の厚さの金属酸化物層であることを要し、耐食性が比較的低い金属合金種（例えばマグネシウム合金や一般鋼材等）では、その表層が化成処理等によって生成した金属酸化物又は金属リン酸化物の薄層であることが第３の条件となる。
(1) The first condition is that when the metal alloy surface is scanned with the latest dynamic mode scanning probe microscope, RSm is 0.8 to 10 μm and Rz is 0.2 to 5 μm. It is a measure. Here, RSm is the average length of contour curve elements defined in Japanese Industrial Standard (JIS B 0601: 2001, ISO 4287: 1997), and Rz is Japanese Industrial Standard (JIS B 0601: 2001, ISO 4287: 1997). This roughness surface is referred to as a “surface having a roughness on the order of microns”.
(2) The second condition is that ultrafine irregularities having a period of 5 nm or more are further formed on the surface of the metal alloy having a roughness on the order of microns. In order to satisfy the conditions, fine etching is performed on the surface of the metal alloy, and the inner wall surface of the concave portion having a roughness on the order of micron is 5 to 500 nm, preferably 10 to 300 nm, more preferably 30 to 100 nm (optimum value). Form ultra-fine irregularities with a period of 50 to 70 nm.
(3) The third condition is that the surface layer of the metal alloy is ceramic. Specifically, with respect to the metal alloy type that originally has corrosion resistance, the surface layer needs to be a metal oxide layer having a thickness equal to or greater than that of the natural oxide layer, and the metal alloy type having relatively low corrosion resistance ( For example, in the case of a magnesium alloy or a general steel material, the third condition is that the surface layer is a thin layer of metal oxide or metal phosphorous oxide generated by chemical conversion treatment or the like.
これらを模式的に図にすると図１４のようになる。金属合金４０の表面にはミクロンオーダーの粗度を成している凹部（Ｃ）が形成され、さらにその凹部内壁には超微細凹凸（Ａ）が形成され、表層はセラミック質層４１となっており、この超微細凹凸に接着剤硬化物層４２の一部が浸入している。このようにした金属合金表面に液状の接着剤が侵入し、侵入後に硬化すると、金属合金と硬化した接着剤は非常に強固に接合するという簡潔な考え方である。 These are schematically illustrated as shown in FIG. Concave portions (C) having a roughness on the order of microns are formed on the surface of the metal alloy 40, and ultra fine irregularities (A) are formed on the inner walls of the concave portions, and the surface layer is a ceramic layer 41. In addition, a part of the cured adhesive layer 42 penetrates into the ultra-fine irregularities. It is a simple idea that when a liquid adhesive enters the surface of the metal alloy thus formed and hardens after the penetration, the metal alloy and the hardened adhesive are bonded very firmly.
上述した技術においては、金属合金と被着材である金属合金又はＣＦＲＰ部材を接着する際に、市販の１液性エポキシ接着剤（主に「ＥＰ１０６ＮＬ」（セメダイン株式会社製））を使用していた。このような市販の１液性エポキシ接着剤であっても、ＮＡＴの条件に適合する金属合金が接着対象となることで常温下において極めて高い接着力を発揮した。 In the above-described technology, a commercially available one-component epoxy adhesive (mainly “EP106NL” (manufactured by Cemedine Co., Ltd.)) is used to bond the metal alloy and the metal alloy or CFRP member as the adherend. It was. Even such a commercially available one-part epoxy adhesive exhibits a very high adhesive force at room temperature because a metal alloy that meets the conditions of NAT is to be bonded.
しかしながら、上記接着実験において使用した１液性エポキシ接着剤は無溶剤型であって粘度が高いという性質を有する。高粘度の接着剤を接着対象の所定の範囲に過不足無く塗布することは容易ではない。特に接着剤層が厚くなりすぎると、結果として安定して高い接着力を得ることが困難であることから、接着対象の所定の範囲に均一の厚さの接着剤層を形成するという困難な作業が必要になる。さらに、低コストで大量生産が要求される用途には、このような接着剤の塗布方法は適さない。このような問題を解消する方法として、接着剤をヘラ等によって金属合金表面に塗布するのではなく、噴霧器によって接着対象部分に噴霧させることが考えられる。しかし、これを行うためには１液性エポキシ接着剤の粘度を大幅に低下させて、噴霧が可能な低粘度のものとしなければならない。 However, the one-component epoxy adhesive used in the above-described adhesion experiment is a solvent-free type and has a high viscosity. It is not easy to apply a high-viscosity adhesive within a predetermined range to be bonded without excess or deficiency. In particular, if the adhesive layer becomes too thick, it is difficult to stably obtain a high adhesive force. As a result, it is difficult to form an adhesive layer having a uniform thickness in a predetermined range to be bonded. Is required. Furthermore, such an adhesive application method is not suitable for applications that require mass production at low cost. As a method for solving such a problem, it is conceivable that the adhesive is not applied to the surface of the metal alloy with a spatula or the like, but is sprayed onto the bonding target portion by a sprayer. However, in order to do this, the viscosity of the one-part epoxy adhesive must be greatly reduced to a low viscosity that can be sprayed.
また、耐熱性のあるエポキシ樹脂硬化物を作成するために、１液性エポキシ接着剤には硬化剤として芳香族ジアミン類が使用されているものも多い。しかし芳香族ジアミンの多くは固体であって、エポキシ当量に基づく添加量は、エポキシ樹脂１００質量部に対して通常２５〜３５質量部と多い。その結果、得られる１液性エポキシ接着剤は粘度が高くならざるを得ない。ＣＦＲＰプリプレグのマトリックス樹脂としては、常温で固体となるエポキシ樹脂組成物を採用している例も多い。しかし、このような高粘度のエポキシ樹脂組成物を接着剤として使用するには接着剤自体又は接着対象を加熱しなければならない等の制限が多く、実用面で大きな問題が残る。 Moreover, in order to create a cured epoxy resin having heat resistance, many one-component epoxy adhesives use aromatic diamines as curing agents. However, most of the aromatic diamine is solid, and the amount added based on the epoxy equivalent is usually 25 to 35 parts by mass with respect to 100 parts by mass of the epoxy resin. As a result, the resulting one-component epoxy adhesive must be highly viscous. As the matrix resin for CFRP prepreg, there are many examples in which an epoxy resin composition that is solid at room temperature is employed. However, in order to use such a high-viscosity epoxy resin composition as an adhesive, there are many limitations such as the need to heat the adhesive itself or the object to be bonded, and a great problem remains in practical use.
このような点から、１液性エポキシ接着剤を低粘度とすることは技術的に極めて重要である。ここで、単に粘度を低下させるだけであれば、接着剤組成物に溶剤を加えるだけで良いが、１液性エポキシ接着剤を溶剤型とすることは通常は推奨されていない。本発明者らも、市販の１液性エポキシ接着剤を溶剤型として、ＮＡＴの条件に適合する表面とした金属合金と被着材を接着させたが、その全てで接着力が大幅に低下した。 From such a point, it is technically very important to make the one-component epoxy adhesive have a low viscosity. Here, if the viscosity is simply lowered, it is sufficient to add a solvent to the adhesive composition, but it is not usually recommended to use a one-component epoxy adhesive as a solvent type. The present inventors also used a commercially available one-part epoxy adhesive as a solvent type, and adhered the metal alloy and the adherend with a surface that conformed to the conditions of NAT, but all of them significantly reduced the adhesive strength. .
本来、エポキシ接着剤の利点の一つは、無溶剤型であるということにある。即ちエポキシ樹脂と硬化剤との反応によって、全組成物が固化成分に繋がり、取り込まれることで高い接着力が得られているのである。これに対して、溶剤型とした１液性エポキシ接着剤は、低沸点の溶剤を混合した場合には、ゲル化時に揮発発砲が生じ、密度の低い接着剤硬化物層が形成されると考えられる。一方、高沸点の溶剤を混合した場合には、加熱時に徐々に揮発するので脆弱な接着剤硬化物層が形成されると考えられる。さらに、溶剤自体も、その分子形状によっては高温下でエポキシ樹脂と化学反応する可能性がある。高温下においてエポキシ樹脂の硬化反応が生じつつある中で、揮発性を有することにより共存量が不安定となる異種化合物の存在は好ましくない。このように、１液性エポキシ接着剤を溶剤型とすることは、安定して高い接着力を得ることが困難であるとして推奨されていなかった。 Originally, one of the advantages of epoxy adhesives is that they are solventless. That is, by the reaction between the epoxy resin and the curing agent, the entire composition is connected to the solidifying component, and a high adhesive force is obtained by being taken in. On the other hand, in the case of a one-part epoxy adhesive made into a solvent type, when a solvent having a low boiling point is mixed, volatile firing occurs at the time of gelation, and a cured adhesive layer having a low density is formed. It is done. On the other hand, when a solvent having a high boiling point is mixed, it is considered that a fragile cured adhesive layer is formed because it gradually evaporates during heating. Furthermore, the solvent itself may chemically react with the epoxy resin at a high temperature depending on its molecular shape. While the curing reaction of the epoxy resin is occurring at a high temperature, the presence of a different compound in which the coexistence amount becomes unstable due to volatility is not preferable. Thus, it was not recommended that the one-component epoxy adhesive be of a solvent type because it is difficult to stably obtain a high adhesive force.
一方で、前述したように噴霧塗装が可能な溶剤型の１液性エポキシ接着剤であれば、様々な接着対象に接着剤を塗装することが極めて容易となる。ヘラ等によって塗布する場合と異なり、接着対象の形状が単純形状ではない場合にも噴霧器によって容易に接着剤の塗装をなし得る。また、接着剤を塗布すべき範囲の周囲を遮蔽物により覆って、当該範囲にのみ接着剤を噴霧させることが可能なので、接着剤の正確な塗装が可能であり、接着剤層の厚さの制御も容易になる。本発明はこのような観点からなされたものであり、その目的は、溶剤型の１液性エポキシ接着剤であって、無溶剤型に近い接着力を発揮するものを提供することにある。また、このような接着剤を使用した接着方法を提供することにある。 On the other hand, as described above, a solvent-type one-component epoxy adhesive capable of spray coating makes it very easy to apply an adhesive to various objects to be bonded. Unlike the case of applying with a spatula or the like, even when the shape to be bonded is not a simple shape, the adhesive can be easily applied with a sprayer. In addition, since the periphery of the area where the adhesive is to be applied is covered with a shield and the adhesive can be sprayed only on the area, the adhesive can be accurately applied, and the thickness of the adhesive layer can be reduced. Control is also easy. The present invention has been made from such a viewpoint, and an object of the present invention is to provide a solvent-type one-component epoxy adhesive that exhibits an adhesive force close to that of a solventless type. Moreover, it is providing the adhesion | attachment method using such an adhesive agent.
前述した事情から、１液性エポキシ接着剤を溶剤型としつつ、無溶剤型と同等の接着性能を発揮させることは困難であるといえる。本発明者らは、以下に示すようにして、この課題を解決した。まず、硬化剤としてジシアンジアミド粉体を採用した。ジシアンジアミド粉体は常温近辺ではエポキシ樹脂に溶解しない。ジシアンジアミド粉体をエポキシ樹脂に添加して混練して得た混練物は、ジシアンジアミド粉体とエポキシ樹脂が溶け合わずに単に混ざり合っている状態であれば、常温付近でゲル化及び硬化を開始しない。結果として、１液性エポキシ接着剤としての安定性を保ち得る。一方で、適当な溶剤が介在してジシアンジアミドがエポキシ樹脂中に一定量溶かされると、エポキシ樹脂との反応が開始し、１日〜数日で硬化するという例がある（非特許文献１）。即ち、ジシアンジアミドを硬化剤として使用したエポキシ接着剤においては、無溶剤型の場合には１液性接着剤といえるが、溶剤型とした場合には２液性接着剤の如く機能する。 From the circumstances described above, it can be said that it is difficult to exhibit the same adhesive performance as the solventless type while using the one-component epoxy adhesive as the solvent type. The present inventors solved this problem as follows. First, dicyandiamide powder was employed as a curing agent. Dicyandiamide powder does not dissolve in epoxy resin near room temperature. If the dicyandiamide powder is added to the epoxy resin and kneaded, the kneaded product will not start to gel and cure near room temperature if the dicyandiamide powder and the epoxy resin are not mixed but simply mixed. . As a result, the stability as a one-component epoxy adhesive can be maintained. On the other hand, there is an example in which when a certain amount of dicyandiamide is dissolved in an epoxy resin through the presence of an appropriate solvent, the reaction with the epoxy resin starts and cures in one to several days (Non-patent Document 1). That is, an epoxy adhesive using dicyandiamide as a curing agent can be said to be a one-component adhesive in the case of a solventless type, but functions as a two-component adhesive in the case of a solvent type.
従って、仮にエポキシ樹脂は溶解するがジシアンジアミドは溶解しない溶剤があれば、この溶剤を介在させることで接着剤を低粘度のものとし、かつ、ジシアンジアミドはこの溶剤に影響を受けないので、この混合物は１液性接着剤として維持できることになる。このような条件に合致する溶剤として、本発明者らはアセトン等のケトン系溶剤を選択した。本発明者らは、エポキシ樹脂に少量のジシアンジアミド粉体を加え、更にエポキシ樹脂と同量のアセトンを加えてよく混合した。その結果、エポキシ樹脂がアセトンに溶けて全体は白濁した低粘度の液体になった。その液体をさらに１時間撹拌しても白濁した状態のままであった。その後、撹拌を止めて静置したところ、１分も経たず白色成分が沈降し、液体上部は透明になった。 Therefore, if there is a solvent that dissolves epoxy resin but not dicyandiamide, the adhesive is made to have a low viscosity by interposing this solvent, and dicyandiamide is not affected by this solvent. It can be maintained as a one-component adhesive. The present inventors selected a ketone solvent such as acetone as a solvent meeting such conditions. The inventors added a small amount of dicyandiamide powder to the epoxy resin, and further added the same amount of acetone as the epoxy resin and mixed well. As a result, the epoxy resin was dissolved in acetone, and the whole became a cloudy, low-viscosity liquid. The liquid remained cloudy even after stirring for another hour. Then, when stirring was stopped and left still, the white component settled in less than 1 minute, and the upper part of the liquid became transparent.
前述した撹拌中における白濁した低粘度の液体は、１液性エポキシ接着剤であるといえる。アセトンのみならず、メチルエチルケトン（以下「ＭＥＫ」という）やメチルイソブチルケトン（以下「ＭＩＢＫ」という）を溶剤として使用しても同様の１液性エポキシ接着剤を作成することができた。従って、これらの液体を接着対象に噴霧して、一定時間放置することによって溶剤を揮発させ、さらに５０〜７０℃にセットした温風乾燥機内に置くことにより溶剤の大部分が揮発する。その結果、接着対象に無溶剤型の接着剤を薄く塗りつけた場合と同様の結果になる。 It can be said that the cloudy low-viscosity liquid during stirring described above is a one-component epoxy adhesive. A similar one-part epoxy adhesive could be prepared by using not only acetone but also methyl ethyl ketone (hereinafter referred to as “MEK”) or methyl isobutyl ketone (hereinafter referred to as “MIBK”) as a solvent. Therefore, these liquids are sprayed on the object to be bonded and left for a certain period of time to evaporate the solvent, and when placed in a hot air dryer set at 50 to 70 ° C., most of the solvent evaporates. As a result, the same result is obtained as when a solventless adhesive is thinly applied to the object to be bonded.
しかし、この場合の問題点は、白濁した低粘度の液体である１液性エポキシ接着剤の撹拌を止めると直ちにジシアンジアミド粉体の沈降が始まることにある。撹拌を止めて数十秒経過してしまうと、もはや噴霧も円滑に行うことができず、噴霧しても硬化剤の濃度が異なるので接着力が低下する。撹拌をしつつ噴霧可能な噴霧器を使用しなければならないとすると、制御が煩雑となり、塗装コストに影響する。従って、撹拌を止めて少なくとも数分は硬化剤が沈降分離しないようにし、実用性の高い１液性エポキシ接着剤を作成することを目標とした。 However, the problem in this case is that the precipitation of the dicyandiamide powder starts as soon as the stirring of the one-component epoxy adhesive, which is a cloudy, low-viscosity liquid, is stopped. When stirring is stopped and several tens of seconds have passed, spraying can no longer be performed smoothly, and even if sprayed, the concentration of the curing agent is different, so that the adhesive strength is reduced. If it is necessary to use a sprayer that can be sprayed while stirring, the control becomes complicated and the coating cost is affected. Accordingly, the aim was to create a highly practical one-component epoxy adhesive by stopping stirring and preventing the curing agent from settling and separating for at least several minutes.
この課題を解決する手段として、本発明者らはジシアンジアミド粉体の粉砕及び分散に湿式粉砕機を使用した。最新型サンドグラインドミル等の湿式粉砕機は、液中で粉体を更に粉砕する能力があると共に、数ミクロンレベルの微粒子が凝集した状態の集合物を破壊し、分散させる能力がある。また、サンドグラインドミル等の湿式粉砕機を使用すると、単に被砕物（ここではジシアンジアミド粉体）の粉砕が進むだけでなく、粉砕で被砕物にできた新たな表面に液体（ここでは溶剤やエポキシ樹脂）が即触れることで、被砕物表面に化学反応性などの物理化学的変化が生ずる場合がある。これは所謂メカノケミカル効果と言われるものである。サンドグラインドミル等の湿式粉砕機を使用することでメカノケミカル効果が得られると、ジシアンジアミド粉体の表面は親ケトン型に近づく可能性があり、その結果、溶剤中の分散性が著しく向上し撹拌を止めてから沈下分離するまでの時間が格段に長くなることが期待される。 As means for solving this problem, the present inventors used a wet pulverizer for pulverizing and dispersing dicyandiamide powder. A wet grinding machine such as the latest sand grind mill has the ability to further pulverize powder in a liquid, and also has the ability to break and disperse aggregates in a state where fine particles of several micron level are aggregated. When a wet grinder such as a sand grind mill is used, not only the crushed material (here, dicyandiamide powder) is pulverized but also liquid (here, solvent or epoxy) is formed on the crushed material. When the resin is immediately touched, physicochemical changes such as chemical reactivity may occur on the surface of the material to be crushed. This is the so-called mechanochemical effect. When a mechanochemical effect is obtained by using a wet grinder such as a sand grind mill, the surface of the dicyandiamide powder may approach the parent ketone type, resulting in significantly improved dispersibility in the solvent and stirring. It is expected that the time from the stoppage to the subsidence separation will be much longer.
このような効果が得られた１液性エポキシ接着剤は噴霧に適したものとなる。一方で、ジシンジアミド粉体の表面が親エポキシ型にもなりうるので、２液性接着剤のように常温近くでゲル化及び硬化を開始してしまう可能性も生じる。本発明者らは、後述する実験においてケトン系溶剤を使用して接着実験を行った。その結果、低粘度で且つ硬化剤が沈降し難く噴霧に適しており、さらに常温近くでゲル化及び硬化を開始することのない安定した１液性エポキシ接着剤が得られることを確認した。 The one-component epoxy adhesive having such an effect is suitable for spraying. On the other hand, since the surface of the dicindiamide powder can also be a parent epoxy type, there is a possibility that gelation and curing start near normal temperature like a two-component adhesive. The inventors conducted an adhesion experiment using a ketone solvent in an experiment described later. As a result, it was confirmed that a stable one-part epoxy adhesive having a low viscosity and hard to settle was suitable for spraying and further, which did not start gelation and curing near normal temperature.
［１液性エポキシ接着剤］
本発明の１液性エポキシ接着剤に関して、以下詳述する。標準的なエポキシ接着剤は、エポキシ樹脂、硬化剤、及び無機充填材の３成分を少なくとも含んでいる。本発明の１液性エポキシ接着剤では、この他に硬化助剤、超微細無機充填材、熱可塑性樹脂粉体、及びケトン系溶剤を含む。
[One-part epoxy adhesive]
The one-component epoxy adhesive of the present invention will be described in detail below. Standard epoxy adhesives include at least three components: an epoxy resin, a curing agent, and an inorganic filler. In addition to this, the one-component epoxy adhesive of the present invention contains a curing aid, an ultrafine inorganic filler, a thermoplastic resin powder, and a ketone solvent.
（エポキシ樹脂）
多種のエポキシ接着剤が市販されているが、エポキシ接着剤の原料は容易に市中から入手できるので自作も可能である。例えば接着剤の原料となるエポキシ樹脂として、ビスフェノール型エポキシ樹脂、多官能ポリフェノール型エポキシ樹脂、脂環型エポキシ樹脂等が市販されている。また、エポキシ基が多官能の化合物（例えば複数の水酸基やアミノ基を有する多官能化合物やオリゴマー等）と結合した多官能エポキシ樹脂も多種市販されている。通常、これらを適当に混ぜ合わせて使用する。
(Epoxy resin)
Although various types of epoxy adhesives are commercially available, the raw materials for epoxy adhesives can be easily obtained from the city, so that they can be made by themselves. For example, bisphenol-type epoxy resins, polyfunctional polyphenol-type epoxy resins, alicyclic epoxy resins, and the like are commercially available as epoxy resins that serve as raw materials for adhesives. In addition, various polyfunctional epoxy resins in which an epoxy group is bonded to a polyfunctional compound (for example, a polyfunctional compound or oligomer having a plurality of hydroxyl groups or amino groups) are commercially available. Usually, these are used by mixing them appropriately.
通常の市販接着剤では、全エポキシ樹脂中の大部分（概ね９０質量％以上）を占めるのは液状で粘度の低いビスフェノールＡ型エポキシ樹脂単量体である。それ故、このような接着剤は液状物に近いペースト状となっている。この粘度の低いビスフェノールＡ型エポキシ樹脂単量体に添加するエポキシ樹脂としては、迅性を与える可能性がある分子量の大きいビスフェノールＡ型エポキシ樹脂オリゴマー、耐熱性を向上させる可能性があるフェノール樹脂型エポキシ樹脂、更には、強度及び硬度を向上させる為にエポキシ基が多官能型となっている芳香族型化合物等が考えられる。 In a normal commercially available adhesive, the liquid epoxy resin monomer having a low viscosity is a major component (approximately 90% by mass or more) in the total epoxy resin. Therefore, such an adhesive is in a paste shape close to a liquid material. The epoxy resin added to the low viscosity bisphenol A type epoxy resin monomer includes a bisphenol A type epoxy resin oligomer having a large molecular weight that may give quickness, and a phenol resin type that may improve heat resistance. An epoxy resin, and an aromatic type compound in which an epoxy group is a polyfunctional type in order to improve strength and hardness can be considered.
（エポキシ樹脂の組成）
エポキシ樹脂の用途は接着剤用としてはむしろ少なく、ＣＦＲＰやガラエポのマトリックス樹脂として多く使用される。その他に、半導体の封止用樹脂としても多用されており、また、電子部品を湿気や水分から守るための注型材としても使用されている。それ故、数十種類のエポキシ樹脂が専門メーカーから市販されている。本発明者らは以下に示す代表的なエポキシ樹脂を購入した。
(Epoxy resin composition)
The use of epoxy resin is rather small for adhesives, and is often used as a matrix resin for CFRP and glass epoxy. In addition, it is frequently used as a resin for sealing semiconductors, and is also used as a casting material for protecting electronic components from moisture and moisture. Therefore, dozens of types of epoxy resins are commercially available from specialized manufacturers. The present inventors purchased the following representative epoxy resins.
（１）ビスフェノールＡ型エポキシ樹脂単量体「ＪＥＲ８２８（ジャパンエポキシレジン株式会社製）」
これの粘度は２５℃で１２０〜１５０Ｐである。
（２）ビスフェノールＡ型エポキシ樹脂オリゴマーであって分子量が１０００以上の「ＪＥＲ１００４（ジャパンエポキシレジン株式会社製）」
これの粘度は２５℃でＱ〜Ｕ（ガードナーホルト粘度）である。
（３）３個以上のエポキシ基を有する多官能型のフェノール樹脂型エポキシ樹脂「ＪＥＲ１５４（ジャパンエポキシレジン株式会社製）」
これの粘度は５２℃で３５０〜６５０Ｐである。
（４）３個以上のエポキシ基を有する多官能型であり、芳香環を有するがフェノール樹脂型でなく、且つ常温で液状のエポキシ樹脂「ＪＥＲ６３０（ジャパンエポキシレジン株式会社製）」
これの粘度は２５℃で５〜１０Ｐである。
(1) Bisphenol A type epoxy resin monomer “JER828 (made by Japan Epoxy Resin Co., Ltd.)”
The viscosity thereof is 120 to 150 P at 25 ° C.
(2) “JER1004 (manufactured by Japan Epoxy Resin Co., Ltd.)” which is a bisphenol A type epoxy resin oligomer and has a molecular weight of 1000 or more.
Its viscosity is Q to U (Gardner-Holt viscosity) at 25 ° C.
(3) Multifunctional phenolic resin type epoxy resin “JER154 (manufactured by Japan Epoxy Resin Co., Ltd.)” having three or more epoxy groups
The viscosity thereof is 350 to 650 P at 52 ° C.
(4) An epoxy resin “JER630 (manufactured by Japan Epoxy Resin Co., Ltd.)”, which is a polyfunctional type having three or more epoxy groups and has an aromatic ring but is not a phenol resin type and is liquid at room temperature.
Its viscosity is 5-10P at 25 ° C.
ここで常温下における接着力を確保することのみを目的とするのであれば、本発明の１液性エポキシ接着剤を構成するエポキシ樹脂分として（１）のみを使用すれば十分である。本発明に係る溶剤型エポキシ接着剤においても、表１に示す接着剤３〜６は（１）のみを使用している。しかしながら、接着剤の耐熱性を向上させるという観点から、（１）〜（４）を所定の比率で混合することが好ましい。以下、（１）〜（４）の好ましい比率に関して説明する。まず最初に、これら（１）〜（４）に示した４種のエポキシ樹脂の粘度に関して説明する。低粘度であるのは（１）「ＪＥＲ８２８」及び（４）「ＪＥＲ６３０」である。一方、固体であるのが（２）「ＪＥＲ１００４」である。３０〜４０℃では高粘度の液状物であるが、２０℃以下の室温下では固体に近いのが（３）「ＪＥＲ１５４」である。要するに低粘度であるのが（１）（４）であり、高粘度であるのが（２）（３）である。これらを大型ビーカーに取り、高温にして溶融し、よく混合して均一化する。そして、その混合物を放冷して２５℃程度まで下げた状態とする。この混合物を１液性エポキシ接着剤の主液とするためには、この状態で少なくとも液状物となっていることが必要である。 Here, if only the purpose is to secure the adhesive force at room temperature, it is sufficient to use only (1) as the epoxy resin component constituting the one-component epoxy adhesive of the present invention. Also in the solvent-type epoxy adhesive according to the present invention, the adhesives 3 to 6 shown in Table 1 use only (1). However, from the viewpoint of improving the heat resistance of the adhesive, it is preferable to mix (1) to (4) at a predetermined ratio. Hereinafter, preferred ratios (1) to (4) will be described. First, the viscosity of the four types of epoxy resins shown in (1) to (4) will be described. Low viscosity is (1) “JER828” and (4) “JER630”. On the other hand, the solid is (2) “JER1004”. Although it is a highly viscous liquid at 30 to 40 ° C., (3) “JER154” is close to a solid at room temperature of 20 ° C. or less. In short, (1) and (4) have low viscosity, and (2) and (3) have high viscosity. Take these in a large beaker, melt at high temperature, mix well and homogenize. Then, the mixture is left to cool to about 25 ° C. In order to use this mixture as the main liquid of the one-part epoxy adhesive, it is necessary to be at least a liquid in this state.
各エポキシ樹脂の組成比について詳述する。１液性エポキシ接着剤をなす全エポキシ樹脂１００質量部のうち、（１）がａ質量部、（２）がｂ質量部、（３）がｃ質量部、（４）がｄ質量部とする。即ち、ａ＋ｂ＋ｃ＋ｄ＝１００とする。 The composition ratio of each epoxy resin will be described in detail. Of 100 parts by mass of the total epoxy resin constituting a one-component epoxy adhesive, (1) is a part by mass, (2) is b part by mass, (3) is c part by mass, and (4) is d part by mass. . That is, a + b + c + d = 100.
高粘度性の（２）及び（３）の量が３２質量部を越えると、混合物は常温で扱いが困難な高粘度物又は固体になる。但し（２）及び（３）も必ず加えたいので下限条件も加えた。即ち、３２≧ｂ＋ｃ≧５（又は９５≧ａ＋ｄ≧６８）とした。また、高温下でも硬度を保ち全体を強化する役割を果たすと考えられる多官能エポキシ樹脂である（３）及び（４）の成分も多く加えたい。但し、これらを加えすぎると常温下では脆くなり却って接着力が低下した。このことから、３２≧ｃ＋ｄ≧１５とした。さらに、硬度を下げて迅性を高める（２）の成分は常温での接着力維持に必要であるが、多すぎると高温下での接着力を下げる。このことから、２２≧ｂ≧５とした。 When the amount of the high viscosity (2) and (3) exceeds 32 parts by mass, the mixture becomes a high viscosity product or solid that is difficult to handle at room temperature. However, since (2) and (3) must be added, the lower limit condition was also added. That is, 32 ≧ b + c ≧ 5 (or 95 ≧ a + d ≧ 68). In addition, it is also desirable to add many components (3) and (4), which are polyfunctional epoxy resins that are considered to play a role of maintaining hardness even at high temperatures and strengthening the whole. However, if these were added too much, they became brittle at room temperature, and the adhesive strength was reduced. From this, 32 ≧ c + d ≧ 15. Furthermore, the component (2) that lowers the hardness and increases the quickness is necessary for maintaining the adhesive strength at room temperature, but if it is too much, the adhesive strength at high temperature is reduced. Therefore, 22 ≧ b ≧ 5.
ここで、多官能エポキシ樹脂である（３）及び（４）に関しては、通常は耐熱性のあるフェノール樹脂組成を有する（３）を多く使用するところであるが、（３）は高粘度であるため、その代替として（４）を採用することとした。本発明者らが実験を行った結果、単純形状である（４）を使用しても、十分な耐熱性を得ることができた。少なくとも実験結果から、（４）は耐熱性という点で何ら問題ないことを確認したので、低粘度の（４）を一定量以上使用すべきとして、ｄ≧７とした。結論として、ａ＋ｂ＋ｃ＋ｄ＝１００としたときのａ、ｂ、ｃ、及びｄの関係は以下のようになる。 Here, regarding (3) and (4) which are polyfunctional epoxy resins, (3) having a phenolic resin composition having heat resistance is usually used, but (3) is highly viscous. As an alternative, (4) was adopted. As a result of experiments conducted by the present inventors, sufficient heat resistance could be obtained even when (4) having a simple shape was used. At least from the experimental results, it was confirmed that (4) had no problem in terms of heat resistance. Therefore, d ≧ 7 was set assuming that (4) having a low viscosity should be used in a certain amount or more. In conclusion, the relationship between a, b, c, and d when a + b + c + d = 100 is as follows.
９５≧ａ＋ｄ≧６８ −式（i）
３２≧ｃ＋ｄ≧１５ −式（ii）
２２≧ｂ≧５ −式（iii）
ｄ≧７ −式（iv）
95 ≧ a + d ≧ 68 −Formula (i)
32 ≧ c + d ≧ 15 −formula (ii)
22 ≧ b ≧ 5-Formula (iii)
d ≧ 7 formula (iv)
式（i）〜式（iv）は、硬化剤がジシアンジアミド粉体であり、硬化助剤が２−フェニルイミダゾール又は３−（３，４−ジクロルフェニル）−１，１−ジメチルウレアの場合に適用する。硬化助剤が２−メチルイミダゾール又はＮ，Ｎ’−ジメチルピペラジンである場合には、以下の式（v）〜式（viii）を適用する。
９５≧ａ＋ｄ≧６８ −式（v）
３０≧ｃ＋ｄ≧１８ −式（vi）
２２≧ｂ≧５ −式（vii）
ｄ≧１０ −式（viii）
Formulas (i) to (iv) are obtained when the curing agent is dicyandiamide powder and the curing aid is 2-phenylimidazole or 3- (3,4-dichlorophenyl) -1,1-dimethylurea. Apply. When the curing aid is 2-methylimidazole or N, N′-dimethylpiperazine, the following formulas (v) to (viii) are applied.
95 ≧ a + d ≧ 68 −Formula (v)
30 ≧ c + d ≧ 18 −formula (vi)
22 ≧ b ≧ 5 Formula (vii)
d ≧ 10 formula (viii)
上述した各式の数値は、接着剤として使用可能な粘度を確保し、その上で接着力及び耐熱性を確保するための基準である。使用する硬化剤及び硬化助剤を決定した後、式（i）〜式（iv）又は式（v）〜式（viii）のいずれかに従ってエポキシ樹脂を作成する。その後、充填材を添加し、さらに硬化剤及び硬化助剤を添加して１液性エポキシ接着剤とする。このようにして作成した１液性エポキシ接着剤は、耐熱性が極めて高いことが保証される。ＮＡＴの条件に適合するＡ７０７５アルミニウム合金片同士を、上記の式に従って作成した１液性エポキシ接着剤を使用して接着した結果、常温下においてせん断破断力は６０ＭＰａ〜７０ＭＰａ又はそれ以上を示し、１５０℃下では３０〜４０ＭＰａ又はそれ以上を示した。このような良好な性能を示すためのエポキシ樹脂の組成比は限定されており、それ故、硬化助剤の種類によって適用する式が異なる。 The numerical value of each formula mentioned above is a standard for ensuring a viscosity that can be used as an adhesive, and ensuring adhesive strength and heat resistance. After determining the curing agent and curing aid to be used, an epoxy resin is prepared according to any one of formula (i) to formula (iv) or formula (v) to formula (viii). Thereafter, a filler is added, and further a curing agent and a curing aid are added to form a one-component epoxy adhesive. The one-component epoxy adhesive prepared in this way is guaranteed to have extremely high heat resistance. As a result of adhering A7075 aluminum alloy pieces conforming to the conditions of NAT to each other using a one-component epoxy adhesive prepared according to the above formula, the shear fracture strength at room temperature is 60 MPa to 70 MPa or more, 150 Under 40 degreeC, 30-40 MPa or more was shown. The composition ratio of the epoxy resin for exhibiting such good performance is limited, and therefore the formula to be applied differs depending on the type of the curing aid.
［硬化剤］
硬化剤について述べる。１液性エポキシ接着剤と２液性エポキシ接着剤の違いは使用する硬化剤の違いによる。本発明は１液性エポキシ接着剤に関するものである。ＮＡＴの条件に適合する金属合金表面において、超微細凹凸に接着剤を侵入させようとした場合、２液性エポキシ接着剤では超微細凹凸に侵入する前にゲル化が開始される可能性が高い。ゲル化によって高分子量の巨大分子が増えた後では超微細凹凸に侵入させることが困難である。それ故、ＮＡＴの表面形状を十分に活用して高い接着力を確保するには１液性エポキシ接着剤の使用が好ましい。１液性エポキシ接着剤の場合、硬化剤として最もよく使用されるのが脂肪族アミン類以外のアミン類や広義のアミン系化合物である。具体的にはジシアンジアミド、芳香族ジアミン類であり、これらはＣＦＲＰ用マトリックス樹脂としても使用されている。その他には酸無水物類、フェノール樹脂もある。エポキシ樹脂に硬化剤を添加し、混合混練して１液性エポキシ接着剤とすると常温下においては液状物となり、常温（夏場以外）で１ヶ月間は保管できる。また、冷蔵状態であれば１年程度は保管できる。
[Curing agent]
The curing agent is described. The difference between the one-component epoxy adhesive and the two-component epoxy adhesive depends on the curing agent used. The present invention relates to a one-part epoxy adhesive. When trying to penetrate the adhesive into the ultra-fine irregularities on the surface of the metal alloy that meets the NAT conditions, the two-component epoxy adhesive is likely to start gelation before entering the ultra-fine irregularities . After high molecular weight macromolecules increase due to gelation, it is difficult to penetrate into ultrafine irregularities. Therefore, it is preferable to use a one-component epoxy adhesive in order to sufficiently utilize the surface shape of the NAT to ensure a high adhesive force. In the case of a one-component epoxy adhesive, amines other than aliphatic amines and amine compounds in a broad sense are most often used as curing agents. Specifically, dicyandiamide and aromatic diamines are used as a matrix resin for CFRP. In addition, there are acid anhydrides and phenol resins. When a curing agent is added to an epoxy resin and mixed and kneaded to form a one-component epoxy adhesive, it becomes a liquid at room temperature and can be stored for 1 month at room temperature (other than summer). Moreover, if it is refrigerated, it can be stored for about one year.
本発明で使用する接着剤は、作業現場で簡易な設備での接着を可能とするものであることが好ましい。即ち１液性エポキシ接着剤であって、硬化温度が低く、かつ耐熱性が高いものが最適である。硬化剤としてジシアンジアミド、芳香族ジアミン類を使用した１液性エポキシ接着剤について、各々常温下での接着力及び耐熱性を試験しようとしたが、芳香族ジアミン類を使用したものは、接着剤が常温よりもやや高い温度で固体となってしまったのでこれを除外した。 The adhesive used in the present invention is preferably one that enables bonding with simple equipment at the work site. That is, a one-component epoxy adhesive having a low curing temperature and high heat resistance is optimal. About one-component epoxy adhesives using dicyandiamide and aromatic diamines as curing agents, we tried to test the adhesive strength and heat resistance at room temperature, but those using aromatic diamines are This was excluded because it became solid at a temperature slightly higher than room temperature.
本発明者らは、硬化剤としてジシアンジアミドを使用することで接着剤の耐熱性を向上させることを試みた。通常は、硬化エポキシ樹脂のＴｇ（ガラス転移点）を上げて耐熱性を向上させるために、硬化剤として芳香族ジアミンを使用する。また、ＣＦＲＰプリプレグが航空機や自動車の部品に使用されるケースが増加することを想定し、その耐熱性能の向上を図る方法が開発されている。その場合に使用される硬化剤は決まって芳香族ジアミン類である。特に、４，４’−ジアミノジフェニルスルホン等が多い。しかし、本発明者らはジシアンジアミドを硬化剤とした場合でも芳香族ジアミンと同等の耐熱性を示し得ることを見出した。 The inventors tried to improve the heat resistance of the adhesive by using dicyandiamide as a curing agent. Usually, an aromatic diamine is used as a curing agent in order to increase the Tg (glass transition point) of the cured epoxy resin and improve the heat resistance. Also, assuming that the number of cases where CFRP prepregs are used in aircraft and automobile parts increases, a method for improving the heat resistance performance has been developed. The curing agent used in that case is always an aromatic diamine. In particular, there are many 4,4'-diaminodiphenyl sulfones and the like. However, the present inventors have found that even when dicyandiamide is used as a curing agent, the same heat resistance as that of the aromatic diamine can be exhibited.
１液性エポキシ接着剤としては、粒径５μｍ以下のジシアンジアミド粉体、より好ましくは粒径２μｍ以下のジシアンジアミド粉体が凝集せずにエポキシ樹脂及び溶剤からなるエポキシ樹脂液中に分散している状態が好ましい。ジシアンジアミド粉体は市販されており、市販品には平均粒径が数μｍから数十μｍのものが数種類ある。これら何れのジシアンジアミド粉体を使用する場合であっても、後述するサンドグラインドミル等の湿式粉砕機を用いて粉砕及び分散を行うことによって、粒径５μｍ以下の微粒子にすることが可能であり、且つエポキシ樹脂液中に均一に分散させられる。これは実験例５３において確認された。 As a one-component epoxy adhesive, a dicyandiamide powder having a particle diameter of 5 μm or less, more preferably a dicyandiamide powder having a particle diameter of 2 μm or less is dispersed in an epoxy resin liquid composed of an epoxy resin and a solvent without aggregation. Is preferred. Dicyandiamide powder is commercially available, and several commercially available products have an average particle size of several μm to several tens of μm. Even when any of these dicyandiamide powders is used, fine particles having a particle diameter of 5 μm or less can be obtained by performing pulverization and dispersion using a wet pulverizer such as a sand grind mill described later. And it is uniformly disperse | distributed in an epoxy resin liquid. This was confirmed in Experimental Example 53.
本発明者らはジシアンジアミド粉体の添加量を異ならせた多数の１液性エポキシ接着剤を作成し、各接着剤を塗布した試料によって接着力を測定した。結果として、エポキシ樹脂１００質量部に対してジシアンジアミド粉体を２．５〜５．５質量部（最適値は３．５〜４．５質量部）添加し、これに硬化助剤である２−フェニルイミダゾールを１．２５〜２．７５質量部（最適値は１．７５〜２．２５質量部）添加した１液性エポキシ接着剤に関しては高い接着力を示した。 The present inventors made a number of one-component epoxy adhesives with different amounts of dicyandiamide powder added, and measured the adhesive strength with the samples coated with each adhesive. As a result, 2.5 to 5.5 parts by mass (optimum value is 3.5 to 4.5 parts by mass) of dicyandiamide powder is added to 100 parts by mass of the epoxy resin, and this is a curing aid. The one-component epoxy adhesive added with 1.25 to 2.75 parts by mass of phenylimidazole (optimum value is 1.75 to 2.25 parts by mass) showed high adhesive strength.
［硬化助剤］
ジシアンジアミド粉体を単独で硬化剤としてエポキシ樹脂に添加した場合、完全硬化させるためには１７０℃で１時間以上加熱することが必要であり、硬化条件が厳しい。この硬化温度では、接着剤を硬化させるための設備を簡素化することが困難となる。従って、硬化助剤を使用することによって、より低温（１１０〜１２０℃程度）での硬化を図ることとした。
[Curing aid]
When the dicyandiamide powder is added alone to the epoxy resin as a curing agent, it is necessary to heat at 170 ° C. for 1 hour or longer in order to completely cure, and the curing conditions are severe. At this curing temperature, it is difficult to simplify the equipment for curing the adhesive. Therefore, it was decided to cure at a lower temperature (about 110 to 120 ° C.) by using a curing aid.
理論的には、硬化助剤はエポキシ樹脂に溶け込んでジシアンジアミド粉体のエポキシ樹脂への溶解を手助けする物が適している。それ故、エポキシ樹脂に溶け易い化合物（例えば芳香環を有している、炭化水素基を有している、分子量は高くない等の特徴を有するもの）であって、且つ親水性であり、さらに揮発性でない化合物が硬化助剤として適していると予期した。本発明者らは、先ずは芳香環又は芳香類似環を有し、窒素を含む化合物を検討対象にした。 Theoretically, a curing aid that dissolves in the epoxy resin and assists in dissolving the dicyandiamide powder in the epoxy resin is suitable. Therefore, it is a compound that is easily soluble in an epoxy resin (for example, has an aromatic ring, has a hydrocarbon group, has a characteristic that the molecular weight is not high, etc.) and is hydrophilic. It was expected that non-volatile compounds would be suitable as curing aids. The inventors first studied compounds having an aromatic ring or an aromatic-like ring and containing nitrogen.
硬化助剤として含窒素化合物を用意し、これをエポキシ樹脂１００質量部に対して数質量部添加して、接着剤が完全硬化する温度を測定した。１０数種の含窒素化合物についてこの実験を行った結果、劇的に硬化温度を低下させたのは、（i）３−（３，４−ジクロルフェニル）−１，１−ジメチルウレア、及び、（ii）Ｎ，Ｎ’−ジメチルピペラジンであった。その他、（iii）２−メチルイミダゾール、（iv）２−フェニルイミダゾールも硬化温度を大きく低下させたが、（i）及び（ii）と比較して硬化温度は１０℃程度高かった。 A nitrogen-containing compound was prepared as a curing aid, and several parts by mass of this were added to 100 parts by mass of the epoxy resin, and the temperature at which the adhesive was completely cured was measured. As a result of conducting this experiment on 10 kinds of nitrogen-containing compounds, it was found that (i) 3- (3,4-dichlorophenyl) -1,1-dimethylurea and drastically reduced the curing temperature, and (Ii) N, N′-dimethylpiperazine. In addition, (iii) 2-methylimidazole and (iv) 2-phenylimidazole also greatly reduced the curing temperature, but the curing temperature was about 10 ° C. higher than (i) and (ii).
これら（i）〜（iv）がジシアンジアミド粉体を使用するときに優れた硬化助剤として機能すると考え、耐熱性に関する実験を行った。このうち、２−フェニルイミダゾールは接着剤用の薬品ではなく、農薬用として販売されている化成品であり、顆粒形状である。それ故、接着剤に添加するために本発明者らはボールミルを使用してこれを微粉砕した。 These (i) to (iv) were considered to function as excellent curing aids when using dicyandiamide powder, and experiments on heat resistance were conducted. Among these, 2-phenylimidazole is not a chemical for adhesives but a chemical product sold for agricultural chemicals and has a granular shape. Therefore, we used a ball mill to pulverize this for addition to the adhesive.
その結果、接着剤の耐熱性に関しては、硬化助剤として（iv）２−フェニルイミダゾールを使用したものが最良であり、１５０℃下での接着力が最高となった。また、（i）３−（３，４−ジクロルフェニル）−１，１−ジメチルウレアは１５０℃下の接着力、即ち耐熱性は（iv）に劣っていたが、（iv）よりも硬化温度を大きく低下させられるという有利な点がある。 As a result, regarding the heat resistance of the adhesive, (iv) the one using 2-phenylimidazole as the curing aid was the best, and the adhesive strength at 150 ° C. was the highest. In addition, (i) 3- (3,4-dichlorophenyl) -1,1-dimethylurea was inferior to (iv) in adhesive strength at 150 ° C., ie, heat resistance, but harder than (iv) There is an advantage that the temperature can be greatly reduced.
一方、（ii）Ｎ，Ｎ’−ジメチルピペラジンを硬化助剤とした接着剤の耐熱性及び硬化温度は（i）と同等であったが、常温で１ヶ月放置することでゲル化してしまうケースが多く、実用面を考慮すると１液性エポキシ接着剤として使用し難い。（iii）２−メチルイミダゾールを硬化助剤とした接着剤の硬化温度は（iv）と同等だが、１５０℃下の接着力は（iv）よりも劣り、（i）及び（ii）と同等であった。 On the other hand, (ii) The heat resistance and curing temperature of the adhesive using N, N′-dimethylpiperazine as a curing aid was the same as (i), but the gelation occurred when left at room temperature for 1 month. In view of practical use, it is difficult to use as a one-component epoxy adhesive. (Iii) The curing temperature of an adhesive using 2-methylimidazole as a curing aid is equivalent to (iv), but the adhesive strength at 150 ° C. is inferior to that of (iv), equivalent to (i) and (ii) there were.
（硬化助剤の添加による新たな効果）
本発明らは、上述したように当初は硬化温度を低下させることを目的として硬化助剤を選択したが、結果として、前述した４つの硬化助剤（i）３−（３，４−ジクロルフェニル）−１，１−ジメチルウレア、（ii）Ｎ，Ｎ’−ジメチルピペラジン、（iii）２−メチルイミダゾール、及び（iv）２−フェニルイミダゾールのいずれを使用した場合であっても、硬化助剤を使用しない場合と比較して常温下における接着力が劇的に向上するという効果があった。
(New effect by adding curing aid)
As described above, the present inventors initially selected a curing aid for the purpose of lowering the curing temperature. As a result, the four curing aids (i) 3- (3,4-dichloro) described above were selected. Phenyl) -1,1-dimethylurea, (ii) N, N′-dimethylpiperazine, (iii) 2-methylimidazole, and (iv) 2-phenylimidazole are used as curing aids. Compared to the case where no agent is used, there is an effect that the adhesive force at room temperature is dramatically improved.
一方で、溶剤以外に関しては、本発明の１液性エポキシ接着剤と同じ組成である無溶剤型の１液性エポキシ接着剤とした場合、常温下での接着力に関しては、硬化助剤の有無は殆ど影響しなかった。ジシアンジアミド粉体を硬化剤とした無溶剤型の１液性エポキシ接着剤に関して、硬化助剤を使用しない場合、硬化温度は高くなるものの、常温下での接着力は硬化助剤を使用した場合と同等であった。即ち、無溶剤型の１液性エポキシ接着剤とした場合、硬化助剤の有無及びその種類が大きく影響するのは高温下の接着力である。このことから、溶剤型としたエポキシ接着剤においては、「硬化助剤を添加することで常温下の接着力が劇的に向上する」という、溶剤型にはみられない特段の効果が得られた。 On the other hand, with respect to other than the solvent, when a solventless one-component epoxy adhesive having the same composition as the one-component epoxy adhesive of the present invention is used, regarding the adhesive strength at room temperature, the presence or absence of a curing aid Had little effect. For solvent-free one-component epoxy adhesives with dicyandiamide powder as a curing agent, when no curing aid is used, the curing temperature increases, but the adhesive strength at room temperature is the same as when a curing aid is used. It was equivalent. That is, in the case of a solvent-free one-component epoxy adhesive, the presence or absence of the curing aid and the type thereof greatly affect the adhesive force at high temperatures. From this, in the solvent-type epoxy adhesive, a special effect not seen in the solvent-type is obtained that "addition of a curing aid dramatically improves the adhesive strength at room temperature". It was.
［無機充填材］
１液性エポキシ接着剤は通常、前述のエポキシ樹脂と硬化剤の他に、少なくとも無機充填材を含む。無機充填材が担う役割を以下に示す。接着剤硬化物層が破壊に至る経緯は、応力が集中している領域近辺の強度の弱い部分で微小な局所破壊が最初に起こり、この局所破壊が隣接する微小部分の応力集中を高めて局所破壊の連鎖が生じることにある。この局所破壊の連鎖は拡大し、破壊部の大きさは微小でなくなり大きなヒビとなり、最終的に完全破壊、即ち接着対象同士の破断に至る。実際、接着剤硬化物層の強度は全ての領域で同一ということはない。従って、仮に局所破壊が連鎖し易ければ容易に完全破壊に至る。それ故、完全破壊は接着剤硬化物層の強度の弱い部分における当該強度で決まることになる。このことことから、局所破壊が起こったとしても、これが連鎖しないようにすれば結果的に接着力は向上することになる。
[Inorganic filler]
The one-part epoxy adhesive usually contains at least an inorganic filler in addition to the above-described epoxy resin and curing agent. The role that the inorganic filler plays is shown below. The reason for the failure of the adhesive-cured material layer is that a small local failure occurs first in a weak portion near the area where the stress is concentrated, and this local failure increases the stress concentration in the adjacent small portion and increases the local concentration. There is a chain of destruction. This chain of local fractures expands, the size of the fractured part becomes smaller and becomes a large crack, and finally complete destruction, i.e., breaks between objects to be bonded. In fact, the strength of the cured adhesive layer is not the same in all regions. Therefore, if local destruction is easily chained, complete destruction is easily achieved. Therefore, complete destruction is determined by the strength of the weakened portion of the cured adhesive layer. From this, even if a local fracture occurs, if it is not chained, the adhesive force will be improved as a result.
無機充填材は、接着剤硬化物に外力がかかって硬化物内部に局所破壊が起こり、微細なヒビが発生した場合、この微細ヒビの連鎖拡大を防止して早期の壊れを止める役割がある。これが結果的に接着力向上に寄与することになる。本発明でも無機充填材の配合は必要条件であり、粒径分布の中心が５〜２５μｍの無機充填材を使用する。具体的には、タルク、クレー（粘土、カオリン）、炭酸カルシウム、シリカ、ガラス、アルミナ、又はアルミニウム等の金属合金の粉体を分級した物である。通常はエポキシ樹脂１００質量部に対して１〜１５質量部添加するが、２〜１２質量部の範囲で添加することで効果がより明確になる。 When an external force is applied to the cured adhesive product to cause local breakage inside the cured product and fine cracks are generated, the inorganic filler has a role of preventing early breakage by preventing chain expansion of the fine cracks. As a result, this contributes to an improvement in adhesive strength. In the present invention, blending of the inorganic filler is a necessary condition, and an inorganic filler having a particle size distribution center of 5 to 25 μm is used. Specifically, it is a product obtained by classifying powders of metal alloys such as talc, clay (clay, kaolin), calcium carbonate, silica, glass, alumina, or aluminum. Usually, 1 to 15 parts by mass is added to 100 parts by mass of the epoxy resin, but the effect becomes clearer by adding in the range of 2 to 12 parts by mass.
［金属粉体］
本発明者らは、以下の実験例においてタルク（接着剤１〜９）又はアルミニウム合金粉体（接着剤１０）を無機充填材として添加した１液性エポキシ接着剤を作成した。特に、純アルミニウムに近いアルミニウム合金、例えばアルミニウムが９９．０質量％以上を占めるのようなもの（１０５０、１０８０、１１００等の１０００番台のもの）は、他のアルミニウム合金と比較して柔らかいという特徴を有する。金属の結晶粒径は焼入れ及び焼き鈍し等の熱履歴で大きく変わり、同時に硬度も大きく変化する。高純度金属は一般に結晶粒径が大きく、熱履歴によって結晶粒径は変化するものの全般に硬度が低い。かかる点から本発明者らは、柔らかい純アルミニウム系アルミニウム合金粉体であれば、タルク以上の効果を奏しうると予期した。
[Metal powder]
In the following experimental examples, the present inventors created a one-component epoxy adhesive to which talc (adhesives 1 to 9) or aluminum alloy powder (adhesive 10) was added as an inorganic filler. In particular, aluminum alloys close to pure aluminum, such as those in which aluminum accounts for 99.0% by mass or more (thousands of 1050, 1080, 1100, etc.) are softer than other aluminum alloys. Have The crystal grain size of the metal changes greatly with the heat history such as quenching and annealing, and the hardness also changes greatly. High-purity metals generally have a large crystal grain size, and the crystal grain size varies depending on the thermal history, but the hardness is generally low. From this point of view, the present inventors anticipated that a soft pure aluminum-based aluminum alloy powder could achieve an effect that is superior to that of talc.
本発明者らが使用した純アルミニウム系アルミニウム合金粉体は、溶融物を噴霧して得られた粉体を分級した物で、粒径分布の中心が１６μｍというものであった。これをエポキシ樹脂１００質量部に対して１〜１５質量部添加して、接着力を測定した。その結果、常温下及び１００℃以上の高温下において、少なくとも接着力が低下することは全くなく、接着力が向上した例が多くあった。特に高温下における接着力向上よりも常温下での接着力向上に寄与する傾向があった。更には、接着剤硬化層が厚い場合にも効果があるようだった。少なくとも充填材の開発において、添加により接着性能が悪化しないという事実は極めて重要である。これは、その後の改良や用途開発によって充填材の添加による特段の効果が発揮されうるからである。かかる観点から、「純アルミニウム系アルミニウム合金粉体の添加によって１液性エポキシ接着剤の接着性能は悪化せず、接着力が向上するケースが多くある」ことが確認されたことは極めて重要である。 The pure aluminum-based aluminum alloy powder used by the present inventors was a product obtained by classifying powder obtained by spraying a melt, and the center of particle size distribution was 16 μm. 1-15 mass parts of this was added with respect to 100 mass parts of epoxy resins, and the adhesive force was measured. As a result, there were many examples in which the adhesive force was not reduced at all at room temperature and at a high temperature of 100 ° C. or higher, and the adhesive force was improved. In particular, there was a tendency to contribute to improving the adhesive strength at room temperature rather than improving the adhesive strength at high temperatures. Furthermore, it seemed to be effective when the adhesive hardened layer was thick. At least in the development of fillers, the fact that adhesion performance does not deteriorate with addition is extremely important. This is because a special effect due to the addition of the filler can be exhibited by subsequent improvements and application development. From this point of view, it is extremely important that it has been confirmed that "the addition of pure aluminum-based aluminum alloy powder does not deteriorate the adhesive performance of the one-part epoxy adhesive and there are many cases where the adhesive strength is improved". .
［超微細無機充填材］
超微細無機充填材とは粒径が１００ｎｍ以下の超微細な無機物粉体である。本発明者らは、１液性エポキシ接着剤に超微細無機充填材を添加することで高温下での接着力が向上する場合があることを発見した。ＮＡＴの条件に適合する表面とした金属合金同士を超微細無機充填材（ヒュームドシリカ）添加の１液性エポキシ接着剤によって接着させた場合、常温下での接着力は超微細無機充填材を添加していない接着剤と同等であったが、１００℃以上の高温下での接着力は明確に向上した。一方で、ＣＦＲＰ部材同士を接着させる場合、又は脱脂処理のみを施した金属合金同士を接着させるような場合には、１液性エポキシ接着剤に超微細無機充填材を添加する効果は殆ど認められない。
[Ultra fine inorganic filler]
The ultrafine inorganic filler is an ultrafine inorganic powder having a particle size of 100 nm or less. The present inventors have discovered that the adhesive strength at high temperatures may be improved by adding an ultrafine inorganic filler to a one-component epoxy adhesive. When metal alloys with surfaces conforming to NAT conditions are bonded together with a one-component epoxy adhesive with an ultrafine inorganic filler (fumed silica) added, the adhesive strength at room temperature is the same as that of an ultrafine inorganic filler. Although it was equivalent to the adhesive which was not added, the adhesive force under high temperature of 100 ° C. or higher was clearly improved. On the other hand, when bonding CFRP members together, or when bonding metal alloys that have undergone only a degreasing treatment, the effect of adding an ultrafine inorganic filler to a one-component epoxy adhesive is almost recognized. Absent.
具体的には粒径十数ｎｍ〜数十ｎｍの酸化珪素（シリカ）微粉であるヒュームドシリカの使用が好ましい。接着対象がＮＡＴの条件に適合する金属合金の場合を想定すると、ヒュームドシリカが金属合金表面上のミクロンオーダーの粗度に係る凹部内にも侵入し、高温下に置かれて接着剤硬化物中の樹脂分の硬度が低下した場合、即ち前記凹部内のスパイク効果が低下した場合に、その凹部内の接着剤硬化物の形状を保って簡単に接着剤硬化物が抜け出せないようにする効果がある。このような理由であるから逆に常温下の使用では効果は認められない。よって高温下で使用しない場合、又は高温下で接着力が低下しても製品として実害がない場合は添加する意味はあまりないが、実用品に於いては８０〜１００℃まで昇温する可能性は常に考えておくべきであるから、超微細無機充填材の添加は非常に重要な役割を果たす。 Specifically, it is preferable to use fumed silica, which is a fine powder of silicon oxide (silica) having a particle size of several tens of nanometers to several tens of nanometers. Assuming the case where the object to be bonded is a metal alloy that conforms to the conditions of NAT, fumed silica also penetrates into the concave portion with a micron order roughness on the surface of the metal alloy and is placed under high temperature to cure the adhesive. When the hardness of the resin content in the resin is reduced, that is, when the spike effect in the recess is reduced, the effect of preventing the adhesive cured product from easily coming out while maintaining the shape of the adhesive cured product in the recess. There is. For this reason, on the contrary, no effect is observed when used at room temperature. Therefore, if it is not used at high temperature, or if there is no actual harm as a product even if the adhesive strength is reduced at high temperature, there is not much meaning to add it, but there is a possibility of raising the temperature to 80-100 ° C in practical products Should always be considered, the addition of ultrafine inorganic fillers plays a very important role.
ヒュームドシリカには２種あり、１種は酸化珪素（シリカ）砂を原料にして還元し、金属珪素を得る還元工程の排気ガスから回収された超微細な溶融シリカである。これは半導体基盤材料である金属珪素の製造工程における副製品である。もう１種は、四塩化珪素を気化させ燃焼して超微細溶融シリカとしたものである。これは意図的に作成されたものであり、「アエロジル」商標として多種市販されている。本発明者らは安定した性質を求めてアエロジルを使用した。 There are two types of fumed silica, and one type is ultrafine fused silica recovered from the exhaust gas in the reduction process in which silicon oxide (silica) sand is reduced to obtain metallic silicon. This is a by-product in the manufacturing process of metallic silicon, which is a semiconductor substrate material. The other is vaporized silicon tetrachloride and burned to form ultrafine fused silica. This was intentionally created and is commercially available under the “Aerosil” trademark. The inventors used Aerosil in search of stable properties.
通常、ミクロンオーダーより小さい粒径の粉末は凝集しており、アエロジルも通常の粉体に見えるが実際には数十個以上の超微粒子が凝集した凝集体である。凝集力は粉体が超微粉になるほど強く、接着剤に投入して自動乳鉢で混練したくらいでは凝集は解けず本発明で想定する分散状態にならない。それゆえ、エポキシ樹脂への添加後に高性能の分散機にかける必要がある。具体的には、前述のＣＮＴの分散で用いた最新型の湿式粉砕機を用いて強制分散させるのが好ましい。実験結果から、超微細無機充填材の添加量はエポキシ樹脂１００質量部に対して０．２質量部以上が好ましく、特に０．２〜２．０質量部が好ましい。２．０質量部を超えて添加した場合、粘度が高くなって使用し難いだけでなく、使用した場合には、接着力は同等か又は低下した。 Usually, powder having a particle size smaller than a micron order is agglomerated, and aerosil also appears to be a normal powder, but in reality it is an agglomerate in which several tens or more ultrafine particles are agglomerated. The agglomeration force becomes stronger as the powder becomes ultrafine powder, and the agglomeration cannot be solved and the dispersed state assumed in the present invention cannot be achieved as long as it is put into an adhesive and kneaded in an automatic mortar. Therefore, it is necessary to apply to a high performance disperser after addition to the epoxy resin. Specifically, it is preferable to forcibly disperse using the latest wet pulverizer used for the dispersion of CNTs. From the experimental results, the addition amount of the ultrafine inorganic filler is preferably 0.2 parts by mass or more, particularly preferably 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the epoxy resin. When added in excess of 2.0 parts by mass, not only was the viscosity increased and it was difficult to use, but when used, the adhesive strength was equivalent or decreased.
［熱可塑性樹脂粉体］
本発明では、１液性エポキシ接着剤に、熱可塑性樹脂粉体としてエラストマー成分を添加した。少なくとも接着剤にエラストマー成分を添加することで、常温下及び高温下において接着力が大きく低下することはなかった。また、硬化条件に影響を与えることもなかった。しかし接着対象及び接着物がおかれる環境によっては、このようなエラストマー成分の添加が必要な場面がある。例えば、変形し易い金属合金同士を接着する場合にはエラストマー成分の添加が好ましい。また、振動や衝撃が加わる環境下で使用される接着物については、接着剤の弾性化は全体としての性能向上に寄与する。そのため、少なくとも接着力が低下しないという事実は重要である。
[Thermoplastic resin powder]
In the present invention, an elastomer component is added as a thermoplastic resin powder to the one-component epoxy adhesive. Addition of an elastomer component to at least the adhesive did not significantly reduce the adhesive strength at room temperature and high temperature. In addition, the curing conditions were not affected. However, depending on the environment in which the object to be bonded and the adhesive are placed, there are situations where the addition of such an elastomer component is necessary. For example, when bonding easily deformable metal alloys, it is preferable to add an elastomer component. In addition, for an adhesive used in an environment where vibration or impact is applied, the elasticization of the adhesive contributes to the improvement of the performance as a whole. Therefore, the fact that at least the adhesive strength does not decrease is important.
各種加硫ゴム、各種加硫ゴムの表面を変性した粉末ゴム、各種生ゴム、各種生ゴムを変性した変性ゴム、塩化ビニル樹脂（以下「ＰＶＣ」）、酢酸ビニル樹脂（以下「ＰＶＡ」）、ポリビニルホルマール樹脂（以下「ＰＶＦ」）、エチレン酢酸ビニル樹脂（以下「ＥＶＡ」）、ポリオレフィン樹脂類、ポリエチレンテレフタレート樹脂（以下「ＰＥＴ」）、各種ポリアミド樹脂（以下「ＰＡ類」）、ポリエーテルスルホン樹脂（以下「ＰＥＳ」）、ポリウレタン樹脂、熱可塑性ポリエステルエラストマー（以下「ＴＰＥＥ」）、熱可塑性ポリウレタンエラストマー（以下「ＴＰＵ」）、熱可塑性ポリアミドエラストマー（以下「ＴＰＡ」）、熱可塑性ポリオレフィン系エラストマー（以下「ＴＰＯ」）等が本発明で言うエラストマー成分である。 Various vulcanized rubbers, powder rubbers modified on the surface of various vulcanized rubbers, various raw rubbers, modified rubbers modified from various raw rubbers, vinyl chloride resin (hereinafter “PVC”), vinyl acetate resin (hereinafter “PVA”), polyvinyl formal Resin (hereinafter “PVF”), ethylene vinyl acetate resin (hereinafter “EVA”), polyolefin resin, polyethylene terephthalate resin (hereinafter “PET”), various polyamide resins (hereinafter “PA”), polyethersulfone resin (hereinafter referred to as “PET”) "PES"), polyurethane resin, thermoplastic polyester elastomer (hereinafter "TPEE"), thermoplastic polyurethane elastomer (hereinafter "TPU"), thermoplastic polyamide elastomer (hereinafter "TPA"), thermoplastic polyolefin elastomer (hereinafter "TPO"). )) Etc. are elastomer components as referred to in the present invention. .
これらの中には一般的にはエラストマーと定義されないものが含まれているが、硬化したエポキシ樹脂は硬質であり、これと比較すれば上記熱可塑性樹脂はいずれも軟質である。それ故、接着剤に添加する場合には上記熱可塑性樹脂はエラストマー成分として機能する。上記熱可塑性樹脂を添加することで、硬化物の靭性はエラストマー成分の軟質によって高められる。粒径５〜３０μｍの微粉とし、さらに、その表面を親エポキシ樹脂型に改良したものを添加することが好ましい。高温下でエポキシ樹脂と反応するのはアミノ基や水酸基であるからエラストマー端部等にこれらを持たせるのも有効な変性処理である。 Some of these are generally not defined as elastomers, but the cured epoxy resin is hard. Compared to this, the thermoplastic resins are all soft. Therefore, when added to the adhesive, the thermoplastic resin functions as an elastomer component. By adding the thermoplastic resin, the toughness of the cured product is enhanced by the softness of the elastomer component. It is preferable to add fine powder having a particle size of 5 to 30 μm and further improve the surface to a parent epoxy resin mold. Since it is an amino group or a hydroxyl group that reacts with the epoxy resin at a high temperature, it is an effective modification treatment to have these at the ends of the elastomer.
また、本発明では常温下だけでなく、比較的高温下でも強い接着力を示す接着剤を求めているので、柔らか過ぎる物は好ましくない。これらを勘案しつつ入手が容易なものを列記すると、水酸基ができ易いＰＶＦ、端部に水酸基のあるウレタン樹脂、アミノ基が無数にあるＰＡ類、さらには意図的に水酸基を付けたＰＥＳ等がある。 In the present invention, since an adhesive that exhibits a strong adhesive force not only at room temperature but also at a relatively high temperature is required, an excessively soft material is not preferable. Listed here are those that are easy to obtain while taking these into consideration: PVF that easily forms hydroxyl groups, urethane resins with hydroxyl groups at the ends, PAs with countless amino groups, and PES with intentionally hydroxyl groups. is there.
エラストマー性を考慮すると、加硫ゴム粉体が充填材として最も適していると考えられが、５〜３０μｍの粒径物は入手困難である。この範囲の粒径物を生産可能な熱可塑性樹脂もあるので、その群から選んで使用する。部品や弾性塗料としてＳＢＲ、ＮＢＲ（ニトリルゴム）、ウレタン樹脂、その他の軟質の熱可塑性樹脂（熱可塑性エラストマーを含む）が市販されており、常温付近での接着剤の弾性化には、これらが適している。 Considering elastomeric properties, vulcanized rubber powder is considered to be most suitable as a filler, but a particle size of 5 to 30 μm is difficult to obtain. There are also thermoplastic resins that can produce particles in this range, so they are selected from the group. SBR, NBR (nitrile rubber), urethane resin, and other soft thermoplastic resins (including thermoplastic elastomers) are commercially available as parts and elastic paints. Is suitable.
また、金属合金とＣＦＲＰの接着複合体の主な用途としては、移動機械の構造体等であるから高温環境下での信頼性も要求される。従って、１００〜１５０℃程度の高温下で過度に軟化しない程度の弾性を有する熱可塑性樹脂が適している。この点から言えば軟化点の高いポリエーテルスルホン樹脂（以下「ＰＥＳ」という）が好ましい。ＰＥＳは耐熱弾性塗料用フィラーとしての用途があり、微粉砕が工業的に為されているので粒径分布の中心が１０〜２０μｍの物が容易に入手できる。熱可塑性樹脂粉体の添加量はエポキシ樹脂１００質量部に対して１０質量部以下であり、６質量部以下が特に好ましい。なお、後述する実験で主に使用した熱可塑性樹脂粉体は、粒径分布の中心が十数μｍのＰＥＳ粉体であった。 In addition, as a main application of the adhesive composite of the metal alloy and CFRP, since it is a structure of a mobile machine or the like, reliability in a high temperature environment is also required. Therefore, a thermoplastic resin having elasticity that is not excessively softened at a high temperature of about 100 to 150 ° C. is suitable. In this respect, a polyethersulfone resin (hereinafter referred to as “PES”) having a high softening point is preferable. PES has a use as a filler for heat resistant elastic coatings, and since fine pulverization is industrially performed, a product having a particle size distribution center of 10 to 20 μm can be easily obtained. The addition amount of the thermoplastic resin powder is 10 parts by mass or less, particularly preferably 6 parts by mass or less, with respect to 100 parts by mass of the epoxy resin. The thermoplastic resin powder mainly used in the experiments described later was a PES powder having a particle size distribution center of several tens of μm.
［ケトン系溶剤］
本発明の１液性エポキシ接着剤に含めるケトン系溶剤としては、アセトン、ＭＥＫ、ＭＩＢＫ等を使用できるが、特にＭＥＫ、ＭＩＢＫが適している。アセトンも使用できるが、ジシアンジアミドの溶解度がＭＥＫ、ＭＩＢＫより僅かに高いためゲル化が進む可能性があり、完成した１液性エポキシ接着剤は常温以下で保管する必要がある。ケトン系溶剤は、エポキシ樹脂１００質量部に対して３０質量部以上使用できる。噴霧器の能力や、得られる接着剤の粘度によって添加量を調整する。本発明者らが作成した１液性エポキシ接着剤の組成であれば、エポキシ樹脂１００質量部に対してケトン系溶剤３０質量部以上を添加することで、通常の噴霧器によって噴霧可能となる。
[Ketone solvent]
Acetone, MEK, MIBK or the like can be used as the ketone solvent to be included in the one-component epoxy adhesive of the present invention, and MEK and MIBK are particularly suitable. Acetone can also be used, but since the solubility of dicyandiamide is slightly higher than MEK and MIBK, gelation may proceed, and the completed one-part epoxy adhesive must be stored at room temperature or lower. The ketone solvent can be used in an amount of 30 parts by mass or more based on 100 parts by mass of the epoxy resin. The addition amount is adjusted depending on the ability of the sprayer and the viscosity of the obtained adhesive. If it is the composition of the 1-component epoxy adhesive which the present inventors created, it will become sprayable with a normal sprayer by adding 30 mass parts or more of ketone type solvents with respect to 100 mass parts of epoxy resins.
［接着剤の作成方法］
溶剤としてＭＩＢＫを使用した１液性エポキシ接着剤の作成方法について説明する。但し、作成方法は以下に示す方法に限られるものではない。先ず、選択した各種エポキシ樹脂を大型ビーカーに取って、そのビーカーを熱風乾燥機に入れ、１４０〜１７０℃に加熱し、各種エポキシ樹脂をガラス棒で攪拌して溶解させつつ均一化する。さらに、このエポキシ樹脂の混合物にＭＩＢＫを混合し、溶解させて透明な低粘度の混合液とする。次いで、この混合液をサンドグラインドミルに充填する。さらに混合液を循環させつつ湿式粉砕処理を開始し、この状態で順次充填材を添加して分散を進める。即ち、無機充填材、超微細無機充填材、及び熱可塑性樹脂粉体を添加する。超微細無機充填材を添加した後、添加後に１５〜３０分は粉砕を続けた方がよい。その後、硬化剤であるジシアンジアミド粉体を添加し、湿式粉砕処理を１０分以上続けてジシアンジアミド粉体の破壊及び分散を行った後、混合液をサンドグラインドミルから回収する。この混合液は低粘度であり、粉砕室を水冷しておけばサンドグラインド内でゲル化が生じることはない。
[How to create an adhesive]
A method for producing a one-component epoxy adhesive using MIBK as a solvent will be described. However, the creation method is not limited to the method shown below. First, various selected epoxy resins are taken into a large beaker, the beaker is put into a hot air dryer, heated to 140 to 170 ° C., and the various epoxy resins are stirred and dissolved with a glass rod to be uniform. Furthermore, MIBK is mixed with this epoxy resin mixture and dissolved to obtain a transparent low viscosity mixed liquid. Next, this mixed liquid is filled in a sand grind mill. Further, the wet pulverization process is started while circulating the mixed liquid, and in this state, the filler is sequentially added and the dispersion is advanced. That is, an inorganic filler, an ultrafine inorganic filler, and a thermoplastic resin powder are added. After adding the ultrafine inorganic filler, it is better to continue grinding for 15 to 30 minutes after the addition. Thereafter, dicyandiamide powder as a curing agent is added, and the wet pulverization treatment is continued for 10 minutes or more to destroy and disperse the dicyandiamide powder, and then the mixed solution is recovered from the sand grind mill. This mixed solution has a low viscosity, and if the grinding chamber is cooled with water, gelation does not occur in the sand grind.
この混合液は５℃に保った冷蔵庫に保管した。そして使用する際には冷蔵庫から混合液を取り出し、３５℃とした温風乾燥機に入れて１５分加熱することで常温付近に戻す。その後、常温に近い混合液に硬化助剤を添加し、よく撹拌して１液性エポキシ接着剤を完成させた。このように硬化助剤は、接着剤を使用する直前に常温に戻した混合液に加えて撹拌するのが好ましい。これは接着剤の保存性を考慮した措置であり、当然、サンドグラインドミル等の湿式粉砕機でジシアンジアミド粉体を添加する際に、併せて硬化助剤を添加するようにしても良い。 This mixed solution was stored in a refrigerator kept at 5 ° C. And when using, it takes out a liquid mixture from a refrigerator, puts it in 35 degreeC warm air dryer, and returns it to normal temperature vicinity by heating for 15 minutes. Thereafter, a curing aid was added to the liquid mixture close to room temperature and stirred well to complete a one-part epoxy adhesive. Thus, it is preferable to stir the curing aid in addition to the mixed solution returned to room temperature just before using the adhesive. This is a measure in consideration of the storage stability of the adhesive. Naturally, when adding the dicyandiamide powder with a wet grinder such as a sand grind mill, a curing aid may be added together.
本発明に関しては、前述した４つの硬化助剤（i）３−（３，４−ジクロルフェニル）−１，１−ジメチルウレア、（ii）Ｎ，Ｎ’−ジメチルピペラジン、（iii）２−メチルイミダゾール、及び（iv）２−フェニルイミダゾールのいずれを使用した場合であっても、硬化助剤を使用しない場合と比較して常温下における接着力が劇的に向上するという効果があった。硬化助剤がジシアンジアミドの作用を劇的に高めた理由を以下のように推測した。接着対象表面に形成した極めて薄い接着剤層は均一になり難く、またジシアンジアミド粒子は偏在していると考えられる。このときに硬化助剤が不在であると硬化が層全体として均一に進行し難いと推定される。硬化助剤はエポキシ樹脂とジシアンジアミドの間に介在してジシアンジアミドの融解を助ける役割を果たすため、偏在していたジシアンジアミドもこの助けによって融解して周囲に拡散し、それから硬化反応が起こることが推定される。 In connection with the present invention, the four curing aids (i) 3- (3,4-dichlorophenyl) -1,1-dimethylurea, (ii) N, N′-dimethylpiperazine, (iii) 2- Even when either methyl imidazole or (iv) 2-phenylimidazole is used, the adhesive force at room temperature is dramatically improved as compared with the case where no curing aid is used. The reason why the curing aid dramatically increased the action of dicyandiamide was estimated as follows. An extremely thin adhesive layer formed on the surface to be bonded is difficult to be uniform, and dicyandiamide particles are considered to be unevenly distributed. If the curing aid is absent at this time, it is estimated that the curing is difficult to proceed uniformly as a whole layer. Since the curing aid plays a role in helping to melt the dicyandiamide by interposing between the epoxy resin and the dicyandiamide, the ubiquitous dicyandiamide is also melted and diffused to the surroundings by this help, and then it is estimated that the curing reaction occurs. The
硬化助剤の直接的な役目はエポキシ樹脂中でのジシアンジアミド粉体の難溶性を緩和することであるが、そのことが同時に、ジシアンジアミドの拡散及び均一化に寄与していると考えられる。特に、本発明のように１液性エポキシ接着剤を噴霧器によって接着対象表面に噴霧した場合、溶剤が揮発した後の塗膜の厚さは数十ミクロン程度の薄い箇所も存在する。この点、通常の無溶剤型１液性エポキシ接着剤を接着対象表面にヘラ塗りして形成される厚い接着剤層と事情が異なる。即ち、噴霧により接着剤を塗布した場合においては、ジシアンジアミドの偏在が生じ、これが接着力を大きく低下させる要因となるが、硬化助剤はこの偏在を緩和させるというのが、本発明者らの推論である。 The direct role of the curing aid is to alleviate the poor solubility of the dicyandiamide powder in the epoxy resin, which is considered to contribute to the diffusion and homogenization of dicyandiamide at the same time. In particular, when the one-component epoxy adhesive is sprayed onto the surface to be bonded by a sprayer as in the present invention, the thickness of the coating film after the solvent is volatilized may be as thin as several tens of microns. This is different from a thick adhesive layer formed by applying a normal solventless one-component epoxy adhesive on the surface to be bonded. That is, when the adhesive is applied by spraying, dicyandiamide is unevenly distributed, which is a factor that greatly reduces the adhesive force, but the inference of the present inventors is that the curing aid reduces this uneven distribution. It is.
この推論によれば、硬化助剤の添加は塗布作業の直前に行うことが好ましい。硬化助剤を含む全ての充填材が添加され、混合された状態で長く保管された場合、硬化助剤の働きによってジシアンジアミドの一部がエポキシ樹脂に溶け込み、ゲル化反応が進む可能性があるからである。即ち、保管状態によっては１液性エポキシ接着剤として作用しなくなるおそれがある。それ故、接着作業の前日又は当日に硬化助剤を加えることが適当である。但し、硬化助剤添加後の接着剤を冷蔵庫に入れておいた場合、１ヶ月程度保管した後でもゲル化反応は進行しておらず、噴霧器によって噴霧可能であり、接着力の低下もみられなかった。従って本発明の溶剤型エポキシ接着剤は、２液性エポキシ接着剤として区分するのは妥当ではなく、１液性エポキシ接着剤に区分することが適切である。 According to this reasoning, it is preferable to add the curing aid immediately before the coating operation. When all the fillers including the curing aid are added and stored for a long time in a mixed state, part of the dicyandiamide may dissolve in the epoxy resin due to the action of the curing aid and the gelation reaction may proceed. It is. That is, depending on the storage state, there is a risk that it will not function as a one-component epoxy adhesive. Therefore, it is appropriate to add a curing aid the day before or on the day of the bonding operation. However, if the adhesive after adding the curing aid is kept in the refrigerator, the gelation reaction does not proceed even after storage for about one month, it can be sprayed with a sprayer, and the adhesive strength is not reduced. It was. Therefore, it is not appropriate to classify the solvent-type epoxy adhesive of the present invention as a two-component epoxy adhesive, and it is appropriate to classify it into a one-component epoxy adhesive.
本発明の溶剤型エポキシ接着剤は、噴霧が可能な１液性エポキシ接着剤であり、かつ、無溶剤型に近い又はこれと同等の接着力を有する。本発明の溶剤型エポキシ接着剤を噴霧器によって接着対象に噴霧し、接着対象表面を塗装することができる。ヘラ等によって塗布する場合と異なり、接着対象の形状が単純形状ではない場合にも噴霧器によって容易に接着剤の塗装をなし得る。また、接着剤を塗布すべき範囲の周囲を遮蔽物により覆って、当該範囲にのみ接着剤を噴霧させることが可能なので、接着剤の正確な塗装が可能であり、接着剤層の厚さの制御も容易になる。ここで、特に硬化助剤として２−フェニルイミダゾールを使用することによって、耐熱性の向上を図ることができた。さらに、エポキシ樹脂の組成を最適化することによって、更なる耐熱性の向上を図ることができた。 The solvent-type epoxy adhesive of the present invention is a one-component epoxy adhesive that can be sprayed, and has an adhesive force close to or equivalent to that of a solventless type. The solvent-type epoxy adhesive of the present invention can be sprayed onto the object to be bonded by a sprayer to coat the surface to be bonded. Unlike the case of applying with a spatula or the like, even when the shape to be bonded is not a simple shape, the adhesive can be easily applied with a sprayer. In addition, since the periphery of the area where the adhesive is to be applied is covered with a shield and the adhesive can be sprayed only on the area, the adhesive can be accurately applied, and the thickness of the adhesive layer can be reduced. Control is also easy. Here, the heat resistance could be improved by using 2-phenylimidazole as a curing aid. Furthermore, the heat resistance could be further improved by optimizing the composition of the epoxy resin.
本発明の塗装型エポキシ接着剤によって、金属合金同士、又は金属合金とＣＦＲＰを強固に接着させることが可能である。ＣＦＲＰは超軽量で鋼並みの強度を示す先端材料である。上記技術によって部品の主構造をＣＦＲＰとし、その端部にのみ金属合金を接着接合することも可能である。即ち、全体として極めて軽量であり、且つ剛性が要求される部分は金属合金で構成することができる。このような部品は、金属合金部をネジ止め又はボルトナット等で他の部品と結合することで容易に組み立てが可能である。具体的には、超々ジュラルミン等の高強度アルミニウム合金やチタン合金をＣＦＲＰと一体化し、極めて軽量な構造部材を製造できる。例えば、金属合金板の表面に本発明のエポキシ接着剤を噴霧し、ＣＦＲＰ板材と面接着させることで、両部材が強固に接着されたサンドイッチ型積層材を構成することができる。これは超軽量の板バネ材となり、多分野において有用な構造体である。 With the paint type epoxy adhesive of the present invention, metal alloys or metal alloys and CFRP can be firmly bonded. CFRP is an advanced material that is ultralight and exhibits the same strength as steel. With the above technique, the main structure of the component is CFRP, and a metal alloy can be bonded and bonded only to the end portion. That is, the portion that is extremely lightweight as a whole and requires rigidity can be made of a metal alloy. Such parts can be easily assembled by joining the metal alloy part to other parts by screws or bolts and nuts. Specifically, a very lightweight structural member can be manufactured by integrating a high-strength aluminum alloy such as ultraduralumin or a titanium alloy with CFRP. For example, a sandwich-type laminated material in which both members are firmly bonded can be formed by spraying the epoxy adhesive of the present invention on the surface of a metal alloy plate and adhering it to the CFRP plate. This becomes an ultralight leaf spring material and is a useful structure in many fields.
［被着材としての金属合金］
本発明の溶剤型エポキシ接着剤は、接着対象を特に限定するものではない。しかし、本発明者らが開発した無溶剤型の１液性エポキシ接着剤は、接着対象がＮＡＴの条件に適合する金属合金である場合に極めて高い接着力を発揮するものであったため、これとの比較を行う上で同じ接着対象を選択した。
[Metal alloys as adherends]
The solvent-type epoxy adhesive of the present invention does not particularly limit the object to be bonded. However, the solventless one-component epoxy adhesive developed by the present inventors exhibited extremely high adhesive strength when the object to be bonded is a metal alloy that meets the NAT conditions. The same adhesion target was selected in the comparison.
（ＮＡＴの条件に適合する金属合金）
前述の「ＮＡＴ」に基づく表面構造を具備する金属合金としては、理論上特にその種類に制限はない。しかし、実際に「ＮＡＴ」を適用できるのは、硬質で実用的な金属合金である。本発明者等は、アルミニウム、マグネシウム、銅、チタン、及び鉄を主成分とする金属合金種に関して「ＮＡＴ」が適用可能であることを確認した。特許文献１にアルミニウム合金に関する記載をした。特許文献２にマグネシウム合金に関する記載をした。特許文献３に銅合金に関する記載をした。特許文献４にチタン合金に関する記載をした。特許文献５にステンレス鋼に関する記載をした。特許文献６に一般鋼材に関する記載をした。しかし、「ＮＡＴ」ではアンカー効果により接着力の向上を図っているので、少なくともこれらの金属合金種に限定されるものではない。以下、金属合金表面を「ＮＡＴ」の条件に適合する表面構造とするための表面処理工程について述べる。
(Metal alloy that meets NAT requirements)
The metal alloy having a surface structure based on the above-described “NAT” is not particularly limited in theory. However, “NAT” can actually be applied to hard and practical metal alloys. The inventors of the present invention have confirmed that “NAT” can be applied to metal alloy types mainly composed of aluminum, magnesium, copper, titanium, and iron. Patent Document 1 describes an aluminum alloy. Patent Document 2 describes a magnesium alloy. Patent Document 3 describes a copper alloy. Patent Document 4 describes a titanium alloy. Patent Document 5 describes stainless steel. Patent Document 6 describes general steel materials. However, since “NAT” aims to improve the adhesive force by the anchor effect, it is not limited to at least these metal alloy types. Hereinafter, a surface treatment process for making the surface of the metal alloy into a surface structure conforming to the “NAT” condition will be described.
（化学エッチング）
この表面処理工程における化学エッチングは、金属合金表面にミクロンオーダーの粗度を生じさせることを目的とする。腐食には全面腐食、孔食、疲労腐食など種類があるが、その金属合金に対して全面腐食を生じる薬品種を選んで試行錯誤し、適当なエッチング剤を選ぶことができる。文献記録（例えば「化学工学便覧（化学工学協会編集）」）によれば、アルミニウム合金は塩基性水溶液、マグネシウム合金は酸性水溶液、ステンレス鋼や一般鋼材全般は、塩酸等ハロゲン化水素酸、亜硫酸、硫酸、これらの塩、等の水溶液で全面腐食するとの記録がある。
(Chemical etching)
The chemical etching in this surface treatment process is intended to produce a roughness on the order of microns on the surface of the metal alloy. There are various types of corrosion, such as general corrosion, pitting corrosion, and fatigue corrosion, but it is possible to select an appropriate etching agent by selecting a chemical species that causes general corrosion for the metal alloy and performing trial and error. According to literature records (for example, "Chemical Engineering Handbook (edited by Chemical Engineering Association)"), aluminum alloys are basic aqueous solutions, magnesium alloys are acidic aqueous solutions, stainless steel and general steel materials in general are hydrohalic acid such as hydrochloric acid, sulfurous acid, There is a record that the entire surface is corroded by an aqueous solution of sulfuric acid or a salt thereof.
又、耐食性の強い銅合金は、高濃度の硝酸水溶液や強酸性とした過酸化水素などの酸化性酸や酸化剤配合液によって全面腐食させられるし、チタン合金は蓚酸や弗化水素酸系の特殊な酸で全面腐食させられることが専門書や特許文献から散見される。実際に市場で販売されている金属合金類は、純銅系銅合金や純チタン系チタン合金のように純度が９９．９％以上で合金とは言い難い物もあるが、これらも本発明の金属合金に含まれる。実際に使用されている金属合金の殆どは、特徴的な物性を求めて多種多用な元素が混合されて純金属系の物は少なく、実質的にも合金である。 In addition, copper alloys with strong corrosion resistance can be corroded entirely by highly concentrated nitric acid aqueous solution or strongly acidic oxidizing acid such as hydrogen peroxide or oxidizer compound liquid, and titanium alloys are oxalic acid or hydrofluoric acid based It can be seen from technical books and patent literature that it can be totally corroded with a special acid. The metal alloys that are actually sold in the market, such as pure copper-based copper alloys and pure titanium-based titanium alloys, have a purity of 99.9% or more and are hardly called alloys. Included in the alloy. Most of the metal alloys that are actually used are mixed with a wide variety of elements in order to obtain characteristic physical properties, and there are few pure metal materials, and they are substantially alloys.
即ち、金属合金の殆どは、元々の金属物性を低下させることなく耐食性を向上させることを目的として純金属から合金化されたものである。それ故、金属合金によっては、前記酸・塩基類や特定の化学物質を使っても、目標とする化学エッチングができない場合もよくある。実際には使用する酸・塩基水溶液の濃度、液温度、浸漬時間、場合によっては添加物を工夫しつつ試行錯誤して適正な化学エッチングを行うことになる。 That is, most metal alloys are alloyed from pure metal for the purpose of improving corrosion resistance without deteriorating the original metal properties. Therefore, depending on the metal alloy, even if the acid / base or a specific chemical substance is used, the target chemical etching is often not possible. In practice, appropriate chemical etching is performed by trial and error while devising the concentration of the acid / base aqueous solution to be used, the liquid temperature, the immersion time, and, in some cases, the additive.
化学エッチング法については、特許文献１にアルミニウム合金に関する記載、特許文献２にマグネシウム合金に関する記載、特許文献３に銅合金に関する記載、特許文献４にチタン合金に関する記載、特許文献５にステンレス鋼に関する記載、及び特許文献６に一般鋼材に関する記載をした。 Regarding the chemical etching method, Patent Document 1 describes an aluminum alloy, Patent Document 2 describes a magnesium alloy, Patent Document 3 describes a copper alloy, Patent Document 4 describes a titanium alloy, and Patent Document 5 describes a stainless steel. And Patent Document 6 described general steel materials.
実際に行う作業として全般的に共通する点を説明する。金属合金を所定の形状に形状化した後、当該金属合金用の脱脂剤を溶かした水溶液に浸漬して脱脂し、水洗する。この工程は、金属合金を形状化する工程で付着した機械油や指脂の大部分を除くための処理であり、常に行うことが好ましい。次いで、薄く希釈した酸・塩基水溶液に浸漬して水洗するのが好ましい。これは本発明者等が予備酸洗浄や予備塩基洗浄と称している工程である。一般鋼材のように酸で腐食するような金属合金では、塩基性水溶液に浸漬し水洗する。また、アルミニウム合金のように塩基性水溶液で特に腐食が早い金属合金では、希薄酸水溶液に浸漬し水洗する。これらは、化学エッチングに使用する水溶液と逆性のものを前もって金属合金に付着（吸着）させる工程であり、その後の化学エッチングが誘導期間なしに始まることになって処理の再現性が著しく向上する。それ故にこの予備酸洗浄、予備塩基洗浄工程は本質的なものではないが、実務上、採用することが好ましい。これらの工程の後に化学エッチング工程を行う。 The points that are generally common in the work actually performed will be described. After shaping the metal alloy into a predetermined shape, the metal alloy is degreased by immersing it in an aqueous solution in which a degreasing agent for the metal alloy is dissolved and washed with water. This process is a process for removing most of the machine oil and finger grease adhering in the process of shaping the metal alloy, and it is preferably always performed. Then, it is preferably immersed in a thinly diluted acid / base aqueous solution and washed with water. This is a process that the present inventors have referred to as preliminary acid cleaning and preliminary base cleaning. In the case of a metal alloy that corrodes with an acid such as a general steel material, it is immersed in a basic aqueous solution and washed with water. Further, in the case of a metal alloy that is particularly rapidly corroded with a basic aqueous solution such as an aluminum alloy, it is immersed in a dilute acid aqueous solution and washed with water. These are processes in which a solution opposite to the aqueous solution used for chemical etching is attached (adsorbed) to the metal alloy in advance, and the subsequent chemical etching starts without an induction period, so that the reproducibility of the process is remarkably improved. . Therefore, the preliminary acid cleaning and preliminary base cleaning steps are not essential, but are preferably employed in practice. After these steps, a chemical etching step is performed.
（微細エッチング・表面硬化処理）
また上記表面処理工程における微細エッチングは、金属合金表面に超微細凹凸を形成することを目的とする。また本発明における表面硬化処理は、金属合金の表層を金属酸化物又は金属リン酸化物の薄層とすることを目的とする。金属合金種によっては前記化学エッチングを行っただけで同時にナノオーダーの微細エッチングもなされ、超微細凹凸が形成される場合がある。さらに、金属合金種によっては表面の自然酸化層が元よりも厚くなって表面硬化処理も完了している場合もある。例えば、純チタン系のチタン合金は化学エッチングだけを行うことで、表面がミクロンオーダーの粗度を有し、且つ超微細凹凸も形成される。即ち、化学エッチングと併せて微細エッチングもなされる。しかし、多くは化学エッチングによりミクロンオーダーの大きな凹凸面を作った後で微細エッチングや表面硬化処理を行う必要がある。
(Fine etching and surface hardening treatment)
The purpose of the fine etching in the surface treatment step is to form ultra-fine irregularities on the surface of the metal alloy. Moreover, the surface hardening process in this invention aims at making the surface layer of a metal alloy into a thin layer of a metal oxide or a metal phosphate. Depending on the type of metal alloy, nano-order fine etching may be performed at the same time by performing the chemical etching, and ultra-fine irregularities may be formed. Furthermore, depending on the type of metal alloy, the natural oxide layer on the surface may be thicker than the original and the surface hardening process may be completed. For example, a pure titanium-based titanium alloy is only subjected to chemical etching, so that the surface has a roughness on the order of microns and ultra-fine irregularities are also formed. That is, fine etching is performed together with chemical etching. However, in many cases, it is necessary to perform fine etching or surface hardening treatment after forming a large uneven surface on the order of microns by chemical etching.
この時でも予測できない化学現象に見舞われることが多い。即ち、表面硬化処理や表面安定化処理を目的に化学エッチング後の金属合金に酸化剤等を反応させたり化成処理をしたとき、得られる表面に偶然ながら超微細凹凸が形成される場合がある。マグネシウム合金を過マンガン酸カリ系水溶液で化成処理した場合に生じた酸化マンガンとみられる表面層は１０万倍電子顕微鏡でようやく判別つく５〜１０ｎｍ直径の棒状結晶が錯綜したものである。この試料をＸＲＤ（Ｘ線回折計）で分析したが、酸化マンガン類由来の回折線は検出できなかったが、表面が酸化マンガンで覆われていることはＸＰＳ分析で明らかである。ＸＲＤで検出できなかった理由は、結晶が検出限界を超えた薄い層であったからである。要するに、マグネシウム合金では表面硬化処理としての化成処理を施したことで、微細エッチングも併せて完了していたことになった。 Even at this time, we are often hit by unpredictable chemical phenomena. That is, when a metal alloy after chemical etching is reacted with an oxidizing agent or chemical conversion treatment for the purpose of surface hardening treatment or surface stabilization treatment, ultra fine irregularities may be formed on the resulting surface by chance. The surface layer that appears to be manganese oxide formed when a magnesium alloy is subjected to chemical conversion treatment with a potassium permanganate aqueous solution is a complex of rod-like crystals having a diameter of 5 to 10 nm that can be finally identified with a 100,000-fold electron microscope. Although this sample was analyzed by XRD (X-ray diffractometer), diffraction lines derived from manganese oxides could not be detected, but it is clear by XPS analysis that the surface was covered with manganese oxide. The reason why XRD could not be detected is that the crystal was a thin layer exceeding the detection limit. In short, the magnesium alloy was subjected to a chemical conversion treatment as a surface hardening treatment, so that fine etching was also completed.
銅合金でも同様で、塩基性下の酸化で表面を酸化第２銅に変化させる表面硬化処理を行ったところ、純銅系銅合金では、その表面は楕円形の穴開口部で覆われた特有の超微細凹凸面になる。一方、純銅系でない銅合金では凹部型でなく１０〜１５０ｎｍ径の粒径物又は不定多角形状物が連なり、一部融け合って積み重なった形の超微細凹凸面になる。この場合でも表面の殆どは酸化第２銅で覆われており、表面の硬化と超微細凹凸の形成が同時に起こる。 The same applies to copper alloys. When surface hardening treatment was performed to change the surface to cupric oxide by oxidation under basic conditions, the surface of pure copper-based copper alloys was covered with an elliptical hole opening. It becomes an ultra fine uneven surface. On the other hand, in the case of a copper alloy that is not pure copper-based, not a concave shape but a particle size or an indefinite polygonal shape having a diameter of 10 to 150 nm is continuous, and an ultrafine uneven surface in a form of being partially melted and stacked. Even in this case, most of the surface is covered with cupric oxide, and the hardening of the surface and the formation of ultrafine irregularities occur simultaneously.
一般鋼材に関しては、更なる検証が必要ではあるものの、ミクロンオーダーの粗度を形成するための化学エッチングだけで超微細凹凸も併せて形成されていることが多く、元来表層（自然酸化層）が硬いこともあって、表面硬化処理や微細エッチング処理を改めて行わずとも、「ＮＡＴ」の条件を備える場合があった。その際の問題は、自然酸化層の耐食性が十分でないために接着工程までに腐食が開始してしまうこと、また、接着後の環境如何では短時間で接着力が低下することであった。これらは化成処理によって防ぐことができる。例を挙げると、化成処理をしていない一般鋼材（ＳＰＣＣ：冷間圧延鋼材）同士をフェノール樹脂系接着剤で接着した接合体に関しては、４週間という短期間で接着力が急激に低下した。一方、化成処理をした一般鋼材（ＳＰＣＣ）同士をフェノール樹脂系接着剤で接着した接合体に関しては、同じ期間では当初の接着力から低下しなかった。 For general steel materials, although further verification is required, ultra-fine irregularities are often formed only by chemical etching to form micron-order roughness, and originally the surface layer (natural oxide layer) In some cases, the condition of “NAT” is provided without performing a surface hardening process or a fine etching process again. The problem at that time is that the corrosion resistance of the natural oxide layer is not sufficient, so that corrosion starts before the bonding step, and the adhesive strength is reduced in a short time depending on the environment after bonding. These can be prevented by chemical conversion treatment. For example, regarding a joined body in which general steel materials (SPCC: cold rolled steel materials) not subjected to chemical conversion treatment are bonded with a phenol resin adhesive, the adhesive strength rapidly decreased in a short period of 4 weeks. On the other hand, regarding the joined body in which the general steel materials (SPCC) subjected to the chemical conversion treatment were bonded to each other with the phenol resin-based adhesive, they did not decrease from the initial adhesive force in the same period.
また、本発明者らは、一般に、化成処理によって金属合金表面に形成された被膜（化成被膜）の膜厚が厚いと、接着力が低下することが多いことを確認している。前記のマグネシウム合金に付着した酸化マンガン薄層のように、ＸＲＤで回折線が検出されないような薄層である方が、強い接着力が得られる。化成被膜が厚い金属合金同士をエポキシ接着剤で接着し、破壊試験した場合、破壊面は殆どが化成皮膜と金属合金層との間となる。本発明者らが行った実験では、厚い化成皮膜とエポキシ接着剤硬化物との接合力は、その化成皮膜と金属合金との接合力より常に強かった。即ち、一般鋼材でも、化成処理時間を更に長くして化成処理層を厚くすれば、接着力は長期間低下しないと考えられる。しかしながら化成皮膜を厚くすれば、接着力自体が低下する。従って、どの程度でバランスを取るかは、使用目的、用途等にもよる。 In addition, the present inventors have generally confirmed that when the thickness of a film (chemical conversion film) formed on the surface of a metal alloy by chemical conversion treatment is thick, the adhesive force often decreases. A strong adhesive force can be obtained when the thin layer is such that the diffraction line is not detected by XRD, such as the thin layer of manganese oxide adhered to the magnesium alloy. When metal alloys having a thick chemical conversion film are bonded to each other with an epoxy adhesive and subjected to a destructive test, most of the fracture surface is between the chemical conversion film and the metal alloy layer. In experiments conducted by the present inventors, the bonding force between the thick chemical conversion film and the cured epoxy adhesive was always stronger than the bonding force between the chemical conversion film and the metal alloy. That is, even with a general steel material, it is considered that the adhesive strength does not decrease for a long period of time if the chemical conversion treatment time is further increased to increase the thickness of the chemical conversion treatment layer. However, if the chemical conversion film is thickened, the adhesive strength itself is lowered. Therefore, the degree of balance depends on the purpose of use and application.
[接着剤の染み込まし処理]
接着対象がＮＡＴの条件に適合する表面を有する金属合金である場合、その表面の必要箇所に上記１液性エポキシ系接着剤を塗布する。本発明の溶剤型エポキシ接着剤をスプレーガン等の噴霧器に取り、塗装と同様にして金属合金表面の必要箇所に噴霧し、薄い接着剤層（塗装膜）を形成する。その後、約５０℃の温風下に３０分程度放置して溶剤を揮発させる。次いでオートクレーブに金属合金を入れ、内部を７０〜８０℃に昇温してから真空近く（１００ｍｍＨｇ以下であり、好ましくは３０ｍｍＨｇ）まで減圧する操作を行うのが好ましい。減圧させた状態に数十秒以上おいた後に常圧に戻してオートクレーブから取り出す。この一連の操作を染み込まし処理という。染み込まし処理において、この減圧／常圧戻しを複数回繰り返すことがさらに好ましい。金属合金を７０〜８０℃にすることで溶剤が完全に揮発したとしても、残ったエポキシ接着剤の粘度は５０Ｐ以下の低粘度になるので、減圧／常圧戻しによってエポキシ接着剤は金属合金表面の超微細凹凸に侵入し得る。
[Adhesive soaking treatment]
When the object to be bonded is a metal alloy having a surface that conforms to the conditions of NAT, the one-component epoxy adhesive is applied to a necessary portion of the surface. The solvent-type epoxy adhesive of the present invention is taken in a spraying device such as a spray gun and sprayed onto a necessary portion of the metal alloy surface in the same manner as coating to form a thin adhesive layer (paint film). Thereafter, the solvent is volatilized by leaving it for about 30 minutes under warm air of about 50 ° C. Next, it is preferable to put the metal alloy into the autoclave, raise the temperature to 70 to 80 ° C., and then reduce the pressure to near vacuum (100 mmHg or less, preferably 30 mmHg). After tens of seconds or more in a decompressed state, return to normal pressure and remove from the autoclave. This series of operations is soaked and called processing. More preferably, the pressure reduction / return to normal pressure is repeated a plurality of times in the soaking process. Even if the solvent is completely volatilized by setting the metal alloy to 70 to 80 ° C., the viscosity of the remaining epoxy adhesive becomes a low viscosity of 50 P or less. Can penetrate into the ultra-fine irregularities.
なお、後述する実験例では上記手法に則って、溶剤を揮発させた後に染み込まし処理を行ったが、染み込まし処理を行った後に金属合金を加熱して溶剤を揮発させるようにしても良い。さらに粘度が低い状態で染み込まし処理が行われることで、より確実に超微細凹凸に溶剤型エポキシ接着剤が侵入しうる。その後の揮発処理によって溶剤成分が揮発する一方、エポキシ接着剤成分のみが超微細凹凸に残存し、接着に寄与することとなる。噴霧という形態を考慮すると、特に溶剤成分が比較的少ない場合等には、こちらの方法が適している場合もあると考えられる。噴霧直後の低粘度状態を活用しうるからである。その他にも、以下に示すようにして溶剤の揮発と染み込まし処理を併せて行うことも可能である。 In the experimental examples to be described later, the treatment was performed after the solvent was volatilized in accordance with the above method. However, the metal alloy may be heated to volatilize the solvent after the soaking and the treatment. Furthermore, the solvent-type epoxy adhesive can penetrate into the ultra fine irregularities more reliably by being soaked and processed in a state where the viscosity is low. While the solvent component is volatilized by the subsequent volatilization process, only the epoxy adhesive component remains in the ultra-fine irregularities and contributes to adhesion. Considering the form of spraying, this method may be suitable particularly when the solvent component is relatively small. This is because the low viscosity state immediately after spraying can be utilized. In addition, it is also possible to perform the treatment by soaking and volatilizing the solvent as described below.
接着対象が大きくてオートクレーブが用意できない場合、以下の方法で溶剤の揮発及び染み込まし処理を行うことができる。トンネル型乾燥機等を使用し、７０〜８０℃のやや高めの温度で、溶剤型エポキシ接着剤を噴霧した金属合金を５〜１０分程度加熱する。このとき、金属合金表面に噴霧された溶剤型エポキシ接着剤がより低粘度の液状物となり、且つその溶剤成分が揮発するときに超微細凹凸内に閉ざされていた空気が抜けて、その箇所にエポキシ接着剤成分が侵入する。この方法は簡易な設備で行うことができるが、温度が均一でないとエポキシ接着剤成分の侵入が不十分となる箇所が生じるので、温度分布に十分留意すべきである。 When the object to be bonded is large and an autoclave cannot be prepared, the solvent can be volatilized and soaked by the following method. Using a tunnel dryer or the like, the metal alloy sprayed with the solvent-type epoxy adhesive is heated at a slightly higher temperature of 70 to 80 ° C. for about 5 to 10 minutes. At this time, the solvent-type epoxy adhesive sprayed on the surface of the metal alloy becomes a low-viscosity liquid, and when the solvent component volatilizes, the air closed in the ultra-fine irregularities escapes, and in that place The epoxy adhesive component enters. Although this method can be performed with simple equipment, if the temperature is not uniform, there will be locations where the epoxy adhesive component is not sufficiently penetrated, so the temperature distribution should be sufficiently noted.
［接着実験］
以下、本発明の溶剤型エポキシ接着剤を使用した接着実験の結果を示す。
（ａ）Ｘ線表面観察（ＸＰＳ観察）
数μｍ径の表面を深さ１〜２ｎｍまでの範囲で構成元素を観察する形式のＥＳＣＡ「ＡＸＩＳ−Ｎｏｖａ（クレイトス（米国）／株式会社 島津製作所（日本国京都府）製）」を使用した。
（ｂ）電子顕微鏡観察
ＳＥＭ型の電子顕微鏡「Ｓ−４８００（株式会社 日立製作所製）」及び「ＪＳＭ−６７００Ｆ（日本電子株式会社（日本国東京都）製）」を使用し１〜２ＫＶにて観察した。
（ｃ）走査型プローブ顕微鏡観察
ダイナミックフォース型の走査型プローブ顕微鏡「ＳＰＭ−９６００（株式会社 島津製作所製）」を使用した。
（ｄ）Ｘ線回折分析（ＸＲＤ分析）
「ＸＲＤ−６１００（株式会社 島津製作所製）」を使用した。
（ｅ）複合体の接合強度の測定
引っ張り試験機「ＡＧ−１０ｋＮＸ（株式会社 島津製作所製）」を使用し、引っ張り速度１０ｍｍ／分でせん断破断力を測定した。
（ｆ）充填材の分散（湿式粉砕機の使用）
直径０．１〜０．５ｍｍのジルコニアビーズをサンドとするサンドグラインドミル「ミニツエア（アシザワ・ファインテック株式会社製）」を使用した。
次に金属合金の表面処理について説明する。
[Adhesion experiment]
Hereinafter, the result of the adhesion experiment using the solvent-type epoxy adhesive of the present invention will be shown.
(A) X-ray surface observation (XPS observation)
ESCA “AXIS-Nova (Kraitos (USA) / Shimadzu Corporation (Kyoto Prefecture, Japan))” in the form of observing constituent elements on a surface having a diameter of several μm in a depth range of 1 to 2 nm was used.
(B) Electron microscope observation Using SEM type electron microscopes “S-4800 (manufactured by Hitachi, Ltd.)” and “JSM-6700F (manufactured by JEOL Ltd. (Tokyo, Japan))” at 1-2 KV Observed.
(C) Scanning Probe Microscope Observation A dynamic force scanning probe microscope “SPM-9600 (manufactured by Shimadzu Corporation)” was used.
(D) X-ray diffraction analysis (XRD analysis)
“XRD-6100 (manufactured by Shimadzu Corporation)” was used.
(E) Measurement of joint strength of composites Using a tensile tester “AG-10kNX (manufactured by Shimadzu Corporation)”, the shear breaking strength was measured at a pulling speed of 10 mm / min.
(F) Dispersion of filler (use of wet pulverizer)
A sand grind mill “Minitsu Air (manufactured by Ashizawa Finetech Co., Ltd.)” using zirconia beads having a diameter of 0.1 to 0.5 mm as sand was used.
Next, the surface treatment of the metal alloy will be described.
［実験例１］（Ａ７０７５アルミニウム合金片の表面処理）
市販の厚さ３ｍｍのアルミニウム合金板材「Ａ７０７５」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＡ７０７５片を多数作成した。槽の水に市販のアルミニウム合金用脱脂剤「ＮＥ−６（メルテックス株式会社（日本国東京都）製）」を投入して濃度７．５％の水溶液（６０℃）とした。これに前記Ａ７０７５片を７分浸漬し、よく水洗した。続いて別の槽に１％濃度の塩酸水溶液（４０℃）を用意し、これに前記Ａ７０７５片を１分浸漬してよく水洗した。次いで別の槽に１．５％濃度の苛性ソーダ水溶液（４０℃）を用意し、これに前記Ａ７０７５片を４分浸漬してよく水洗した。続いて別の槽に３％濃度の硝酸水溶液（４０℃）を用意し、これに前記Ａ７０７５片を１分浸漬し、水洗した。次いで別の槽に一水和ヒドラジンを３．５％含む水溶液（６０℃）を用意し、これに前記Ａ７０７５片を２分浸漬し、水洗した。次いで５％濃度の過酸化水素水溶液（４０℃）を用意し、これに前記Ａ７０７５片を５分浸漬し、水洗した。次いで前記Ａ７０７５片を、６７℃にした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 1] (A7075 aluminum alloy piece surface treatment)
A commercially available aluminum alloy plate “A7075” having a thickness of 3 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular A7075 pieces. A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co., Ltd. (Tokyo, Japan))” was added to the water in the tank to prepare an aqueous solution (60 ° C.) having a concentration of 7.5%. The A7075 pieces were immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution (40 ° C.) was prepared in another tank, and the A7075 piece was immersed in the tank for 1 minute and washed with water. Next, a 1.5% strength aqueous caustic soda solution (40 ° C.) was prepared in another tank, and the A7075 pieces were immersed in this for 4 minutes and washed with water. Subsequently, a 3% nitric acid aqueous solution (40 ° C.) was prepared in another tank, and the A7075 pieces were immersed in the tank for 1 minute and washed with water. Next, an aqueous solution (60 ° C.) containing 3.5% monohydric hydrazine was prepared in another tank, and the A7075 pieces were immersed in this for 2 minutes and washed with water. Next, a 5% hydrogen peroxide aqueous solution (40 ° C.) was prepared, and the A7075 piece was immersed in the solution for 5 minutes and washed with water. Next, the A7075 pieces were dried in a hot air dryer at 67 ° C. for 15 minutes.
前記と同じ処理をしたＡ７０７５片を電子顕微鏡観察したところ、４０〜１００ｎｍ径の凹部で覆われていることが分かった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図１に示した（（ａ）：１万倍，（ｂ）：１０万倍）。又、走査型プローブ顕微鏡にかけて粗度データを得た。これによるとＲＳｍは３〜４μｍ、Ｒｚは１〜２μｍであった。 When the A7075 piece treated in the same manner as described above was observed with an electron microscope, it was found that the A7075 piece was covered with a recess having a diameter of 40 to 100 nm. A photograph of the electron microscope observed at 10,000 times and 100,000 times is shown in FIG. 1 ((a): 10,000 times, (b): 100,000 times). The roughness data was obtained by scanning probe microscope. According to this, RSm was 3-4 μm, and Rz was 1-2 μm.
［実験例２］（Ａ５０５２アルミニウム合金片の表面処理）
市販の厚さ１．６ｍｍのアルミニウム合金板材「Ａ５０５２」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＡ５０５２片を多数作成した。槽の水に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を投入して濃度７．５％の水溶液（６０℃）とした。これに前記Ａ５０５２片を７分浸漬し、よく水洗した。続いて別の槽に１％濃度の塩酸水溶液（４０℃）を用意し、これに前記Ａ５０５２片を１分浸漬してよく水洗した。次いで別の槽に１．５％濃度の苛性ソーダ水溶液（４０℃）を用意し、これに前記Ａ５０５２片を２分浸漬してよく水洗した。続いて別の槽に３％濃度の硝酸水溶液（４０℃）を用意し、これに前記Ａ５０５２片を１分浸漬し、水洗した。次いで別の槽に一水和ヒドラジンを３．５％含む水溶液（６０℃）を用意し、これに前記Ａ５０５２片を２分浸漬し、水洗した。次いで前記Ａ５０５２片を、６７℃にした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 2] (Surface treatment of A5052 aluminum alloy piece)
A commercially available 1.6 mm thick aluminum alloy sheet “A5052” was obtained and cut to produce a large number of 45 mm × 18 mm rectangular A5052 pieces. A commercially available degreasing agent “NE-6” for aluminum alloy was added to the water in the tank to prepare an aqueous solution (60 ° C.) having a concentration of 7.5%. The A5052 piece was immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution (40 ° C.) was prepared in another tank, and the A5052 pieces were immersed in this for 1 minute and washed with water. Next, a 1.5% strength aqueous sodium hydroxide solution (40 ° C.) was prepared in another tank, and the A5052 pieces were immersed in this for 2 minutes and washed with water. Subsequently, a 3% nitric acid aqueous solution (40 ° C.) was prepared in another tank, and the A5052 piece was immersed in this for 1 minute and washed with water. Next, an aqueous solution (60 ° C.) containing 3.5% monohydric hydrazine was prepared in another tank, and the A5052 pieces were immersed in this for 2 minutes and washed with water. Next, the A5052 pieces were dried in a hot air dryer set at 67 ° C. for 15 minutes.
前記と同じ処理をしたＡ５０５２片を電子顕微鏡観察したところ、３０〜１００ｎｍ径の凹部で覆われていることが分かった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図２に示した（（ａ）：１万倍，（ｂ）：１０万倍）。又、走査型プローブ顕微鏡にかけて粗度データを得た。これによるとＲＳｍは１．８〜２．６μｍ、Ｒｚは０．３〜０．５μｍであった。 When the A5052 piece treated in the same manner as described above was observed with an electron microscope, it was found that the A5052 piece was covered with a recess having a diameter of 30 to 100 nm. A photograph when the electron microscope is observed at 10,000 times and 100,000 times is shown in FIG. 2 ((a): 10,000 times, (b): 100,000 times). The roughness data was obtained by scanning probe microscope. According to this, RSm was 1.8 to 2.6 μm, and Rz was 0.3 to 0.5 μm.
［実験例３］（ＡＺ３１Ｂマグネシウム合金片の表面処理）
市販の厚さ１ｍｍのマグネシウム合金板材「ＡＺ３１Ｂ」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＡＺ３１Ｂ片を多数作成した。槽の水に市販のマグネシウム合金用脱脂剤「クリーナー１６０（メルテックス株式会社製）」を投入して濃度７．５％の水溶液（６５℃）とした。これに前記ＡＺ３１Ｂ片を５分浸漬し、よく水洗した。続いて別の槽に１％濃度の水和クエン酸水溶液（４０℃）を用意し、これに前記ＡＺ３１Ｂ片を６分浸漬してよく水洗した。次いで別の槽に１％濃度の炭酸ナトリウムと１％濃度の炭酸水素ナトリウムを含む水溶液（６５℃）を用意し、これに前記ＡＺ３１Ｂ片を５分浸漬してよく水洗した。続いて別の槽に１５％濃度の苛性ソーダ水溶液（６５℃）を用意し、これに前記ＡＺ３１Ｂ片を５分浸漬し、水洗した。次いで別の槽に０．２５％濃度の水和クエン酸水溶液（４０℃）を用意し、これに前記ＡＺ３１Ｂ片を１分浸漬して水洗した。次いで過マンガン酸カリを２％、酢酸を１％、水和酢酸ナトリウムを０．５％含む水溶液（４５℃）を用意し、これに前記ＡＺ３１Ｂ片を１分浸漬し、１５秒水洗した。次いで前記ＡＺ３１Ｂ片を、９０℃にした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 3] (Surface treatment of AZ31B magnesium alloy piece)
A commercially available magnesium alloy sheet “AZ31B” having a thickness of 1 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular AZ31B pieces. A commercially available degreasing agent for magnesium alloy “Cleaner 160 (manufactured by Meltex Co., Ltd.)” was added to the water in the tank to prepare an aqueous solution (65 ° C.) having a concentration of 7.5%. The AZ31B piece was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% strength aqueous hydrated citric acid solution (40 ° C.) was prepared in another tank, and the AZ31B piece was dipped in this for 6 minutes and washed with water. Next, an aqueous solution (65 ° C.) containing 1% concentration sodium carbonate and 1% concentration sodium hydrogen carbonate was prepared in another tank, and the AZ31B piece was immersed in this for 5 minutes and washed with water. Subsequently, a 15% strength aqueous caustic soda solution (65 ° C.) was prepared in another tank, and the AZ31B piece was immersed in this for 5 minutes and washed with water. Next, a 0.25% strength aqueous hydrated citric acid solution (40 ° C.) was prepared in another tank, and the AZ31B piece was immersed in this for 1 minute and washed with water. Next, an aqueous solution (45 ° C.) containing 2% potassium permanganate, 1% acetic acid and 0.5% hydrated sodium acetate was prepared, and the AZ31B piece was immersed in this for 1 minute and washed with water for 15 seconds. Next, the AZ31B piece was placed in a hot air dryer set at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＡＺ３１Ｂ片を電子顕微鏡観察したところ、５〜２０ｎｍ径の棒状結晶が複雑に絡み合って１００ｎｍ径程度の塊となり、その塊が面を作っている超微細凹凸形状で覆われている箇所があった。電子顕微鏡を１０万倍として観察したときの写真を図３（ａ）及び（ｂ）に示した。又、走査型プローブ顕微鏡で走査して粗度観測を行ったところＲＳｍが２〜３μｍ、Ｒｚが１〜１．５μｍであった。 When the AZ31B piece treated in the same manner as described above was observed with an electron microscope, 5 to 20 nm diameter rod-shaped crystals were intertwined into a lump with a diameter of about 100 nm, and the lump was covered with a super fine uneven shape forming a surface. There was a place. 3A and 3B show photographs when the electron microscope is observed at a magnification of 100,000. Further, when the roughness was observed by scanning with a scanning probe microscope, RSm was 2 to 3 μm and Rz was 1 to 1.5 μm.
［実験例４］（Ｃ１１００銅合金片の表面処理）
市販の厚さ１．４ｍｍの純銅系銅合金であるタフピッチ銅板材「Ｃ１１００」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＣ１１００片を多数作成した。槽に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これに前記Ｃ１１００片を５分浸漬して水洗した。次いで１．５％濃度の苛性ソーダ水溶液（４０℃）に前記Ｃ１１００片を１分浸漬して水洗することで予備塩基洗浄した。次いで銅合金用エッチング材「ＣＢ−５００２（メック株式会社（日本国兵庫県）製）」を２０％、３０％過酸化水素を１８％含む水溶液（２５℃）をエッチング用水溶液として用意し、これに前記Ｃ１１００片をを１０分浸漬し、水洗した。次いで別の槽に苛性ソーダを１０％、亜塩素酸ナトリウムを５％含む水溶液（６５℃）を酸化用水溶液として用意し、これに前記Ｃ１１００片を１分浸漬してよく水洗した。次いで、前記Ｃ１１００片を再び前記エッチング用水溶液に１分浸漬して水洗した後、前記酸化用水溶液に１分浸漬し、よく水洗した。その後、前記Ｃ１１００片を、９０℃とした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 4] (Surface treatment of C1100 copper alloy piece)
A commercially available tough pitch copper plate material “C1100”, which is a pure copper-based copper alloy with a thickness of 1.4 mm, was obtained and cut to produce a large number of rectangular C1100 pieces of 45 mm × 18 mm. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and the C1100 pieces were immersed in this for 5 minutes and washed with water. Next, the base was washed by immersing the C1100 piece in a 1.5% strength aqueous caustic soda solution (40 ° C.) for 1 minute and washing with water. Next, an aqueous solution (25 ° C.) containing 20% of an etching material for copper alloy “CB-5002 (MEC Co., Ltd., Hyogo, Japan)” and 18% of 30% hydrogen peroxide was prepared as an aqueous solution for etching. The C1100 piece was immersed in 10 minutes and washed with water. Next, an aqueous solution (65 ° C.) containing 10% caustic soda and 5% sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the C1100 pieces were immersed in this for 1 minute and washed with water. Next, the C1100 piece was again immersed in the aqueous solution for etching for 1 minute and washed with water, then immersed in the aqueous solution for oxidation for 1 minute, and thoroughly washed with water. Thereafter, the C1100 piece was placed in a warm air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＣ１１００片を走査型プローブ顕微鏡にかけた。その結果、ＲＳｍは３〜７μｍ、Ｒｚは３〜５μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図４に示した（（ａ）：１万倍，（ｂ）：１０万倍）。１０万倍電子顕微鏡で観察したところ、直径又は長径短径の平均が１０〜１５０ｎｍの孔開口部又は凹部が３０〜３００ｎｍの非定期な間隔で全面に存在する超微細凹凸形状でほぼ全面が覆われていた。 A piece of C1100 treated in the same manner as described above was applied to a scanning probe microscope. As a result, RSm was 3 to 7 μm, and Rz was 3 to 5 μm. A photograph of the electron microscope observed at 10,000 times and 100,000 times is shown in FIG. 4 ((a): 10,000 times, (b): 100,000 times). When observed with an electron microscope of 100,000 times, the hole or opening having a diameter or an average of a major axis and a minor axis having an average of 10 to 150 nm is covered with an ultrafine irregular shape having irregular intervals of 30 to 300 nm. It was broken.
［実験例５］（Ｃ５１９１銅合金片の表面処理）
市販の厚さ１ｍｍのリン青銅板材「Ｃ５１９１」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＣ５１９１片を多数作成した。槽に市販のアルミ合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これを脱脂用水溶液とした。この脱脂用水溶液に前記Ｃ５１９１片を５分浸漬して脱脂し、よく水洗した。続いて別の槽に銅合金用エッチング材「ＣＢ−５００２」を２０％分、３０％過酸化水素水を１８％分含む水溶液（２５℃）をエッチング用水溶液として用意し、これに前記Ｃ５１９１片を１５分浸漬し、水洗した。次いで別の槽に苛性ソーダを１０％、亜塩素酸ナトリウムを５％含む水溶液（６５℃）を酸化用水溶液として用意し、これに前記Ｃ５１９１片を１分浸漬してよく水洗した。次いで、前記Ｃ５１９１片を再び前記エッチング用水溶液に１分浸漬して水洗した後、前記酸化用水溶液に１分浸漬し、水洗した。その後、前記Ｃ５１９１片を、９０℃にした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 5] (Surface treatment of C5191 copper alloy piece)
A commercially available phosphor bronze plate material “C5191” with a thickness of 1 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular C5191 pieces. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and this was used as a degreasing aqueous solution. The C5191 piece was immersed in this degreasing aqueous solution for 5 minutes for degreasing and thoroughly washed with water. Subsequently, an aqueous solution (25 ° C.) containing 20% of an etching material for copper alloy “CB-5002” and 18% of 30% hydrogen peroxide was prepared as an aqueous solution for etching in another tank, and the C5191 piece was added thereto. Was immersed for 15 minutes and washed with water. Next, an aqueous solution (65 ° C.) containing 10% caustic soda and 5% sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the C5191 pieces were immersed in this for 1 minute and washed with water. Next, the C5191 piece was again immersed in the etching aqueous solution for 1 minute and washed with water, and then immersed in the oxidizing aqueous solution for 1 minute and washed with water. Thereafter, the C5191 pieces were placed in a hot air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＣ５１９１片を走査型プローブ顕微鏡にかけた。その結果、ＲＳｍは１〜３μｍ、Ｒｚは０．３〜０．４μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図５に示した（（ａ）：１万倍，（ｂ）：１０万倍）。１０万倍電子顕微鏡で観察したところ、直径又は長径短径の平均が１０〜２００ｎｍの凸部が混ざり合って全面に存在する超微細凹凸形状であり、純銅系であるタフピッチ銅の微細構造とは全く異なった形状であった。 A C5191 piece treated in the same manner as described above was applied to a scanning probe microscope. As a result, RSm was 1 to 3 μm and Rz was 0.3 to 0.4 μm. A photograph when the electron microscope is observed at 10,000 times and 100,000 times is shown in FIG. 5 ((a): 10,000 times, (b): 100,000 times). When observed with a 100,000-fold electron microscope, a convex or concave portion having an average diameter or major axis and minor axis of 10 to 200 nm is mixed and is present on the entire surface. What is the microstructure of tough pitch copper that is pure copper? It was a completely different shape.
［実験例６］（ＫＦＣ銅合金片の表面処理）
市販の厚さ１ｍｍの鉄含有銅合金板材「ＫＦＣ（株式会社 神戸製鋼所製）」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＫＦＣ片を多数作成した。槽に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これに前記ＫＦＣ片を５分浸漬し、水洗した。次いで１．５％濃度の苛性ソーダ水溶液（４０℃）に前記ＫＦＣ片を１分浸漬して水洗することで予備塩基洗浄した。次いで銅合金用エッチング材「ＣＢ５００２」を２０％分、３０％過酸化水素水を１８％分含む水溶液（２５℃）をエッチング用水溶液として用意し、これに前記ＫＦＣ片を８分浸漬し、水洗した。次いで別の槽に苛性ソーダを１０％、亜塩素酸ナトリウムを５％含む水溶液（６５℃）を酸化用水溶液として用意し、これに前記ＫＦＣ片を１分浸漬してよく水洗した。次いで、前記ＫＦＣ片を再び前記エッチング用水溶液に１分浸漬して水洗した後、前記酸化用水溶液に１分浸漬してよく水洗した。その後、前記ＫＦＣ片を、９０℃とした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 6] (Surface treatment of KFC copper alloy piece)
A commercially available iron-containing copper alloy sheet “KFC (manufactured by Kobe Steel, Ltd.)” having a thickness of 1 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular KFC pieces. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and the KFC pieces were immersed in this for 5 minutes and washed with water. Next, the KFC pieces were immersed in a 1.5% strength aqueous caustic soda solution (40 ° C.) for 1 minute and washed with water to perform preliminary base washing. Next, an aqueous solution (25 ° C.) containing 20% of an etching material for copper alloy “CB5002” and 18% of 30% hydrogen peroxide is prepared as an aqueous solution for etching. The KFC piece is immersed in this for 8 minutes and washed with water. did. Next, an aqueous solution (65 ° C.) containing 10% caustic soda and 5% sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the KFC pieces were immersed in this for 1 minute and washed with water. Next, the KFC piece was again immersed in the etching aqueous solution for 1 minute and washed with water, and then immersed in the oxidizing aqueous solution for 1 minute and washed with water. Thereafter, the KFC pieces were placed in a hot air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＫＦＣ片を走査型プローブ顕微鏡にかけた。その結果、ＲＳｍは１〜３μｍ、Ｒｚは０．３〜０．５μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図６に示した（（ａ）：１万倍，（ｂ）：１０万倍）。１０万倍電子顕微鏡で観察したところ、直径又は長径短径の平均が１０〜２００ｎｍの凸部が混ざり合って全面に存在する超微細凹凸形状で全面が覆われていた。 A KFC piece treated in the same manner as described above was applied to a scanning probe microscope. As a result, RSm was 1 to 3 μm and Rz was 0.3 to 0.5 μm. The photograph when observing the electron microscope at 10,000 times and 100,000 times is shown in FIG. 6 ((a): 10,000 times, (b): 100,000 times). When observed with a 100,000-fold electron microscope, the entire surface was covered with an ultrafine uneven shape in which convex portions having an average diameter or major axis and minor axis of 10 to 200 nm were mixed and present on the entire surface.
［実験例７］（ＫＬＦ５銅合金の表面処理）
市販の厚さ０．４ｍｍの特殊銅合金板材「ＫＬＦ５（株式会社 神戸製鋼所製）」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＫＬＦ５片を多数作成した。槽に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これに前記ＫＬＦ５片を５分浸漬し、水洗した。次いで１．５％濃度の苛性ソーダ水溶液（４０℃）に前記ＫＬＦ５片を１分浸漬して水洗することで予備塩基洗浄した。次いで銅合金用エッチング材「ＣＢ５００２」を２０％分、３０％過酸化水素水を１８％分含む水溶液（２５℃）をエッチング用水溶液として用意し、これに前記ＫＬＦ５片を８分浸漬し、水洗した。次いで別の槽に苛性ソーダを１０％、亜塩素酸ナトリウムを５％含む水溶液（６５℃）を酸化用水溶液として用意し、これに前記ＫＬＦ５片を１分浸漬してよく水洗した。次いで、前記ＫＬＦ５片を再び前記エッチング用水溶液に１分浸漬して水洗した後、前記酸化用水溶液に１分浸漬してよく水洗した。その後、前記ＫＬＦ５片を、９０℃とした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 7] (Surface treatment of KLF5 copper alloy)
Commercially available 0.4 mm thick special copper alloy sheet “KLF5 (manufactured by Kobe Steel, Ltd.)” was obtained and cut to produce a large number of 45 mm × 18 mm rectangular KLF5 pieces. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and the KLF5 pieces were immersed in this for 5 minutes and washed with water. Subsequently, the KLF5 pieces were immersed in a 1.5% strength aqueous caustic soda solution (40 ° C.) for 1 minute and washed with water to perform preliminary base washing. Next, an aqueous solution (25 ° C.) containing 20% of an etching material for copper alloy “CB5002” and 18% of 30% hydrogen peroxide is prepared as an aqueous solution for etching. The KLF5 pieces are immersed in this for 8 minutes and washed with water. did. Next, an aqueous solution (65 ° C.) containing 10% caustic soda and 5% sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the KLF5 pieces were immersed in this for 1 minute and washed with water. Subsequently, the KLF5 piece was again immersed in the etching aqueous solution for 1 minute and washed with water, and then immersed in the oxidizing aqueous solution for 1 minute and washed with water. Thereafter, the KLF5 pieces were placed in a hot air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＫＬＦ５片を走査型プローブ顕微鏡にかけた。その結果、ＲＳｍは１〜３μｍ、Ｒｚは０．３〜０．５μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図７に示した（（ａ）：１万倍，（ｂ）：１０万倍）。１０万倍電子顕微鏡で観察したところ、直径１０〜２０ｎｍの粒径物及び５０〜１５０ｎｍ径の不定多角形状物が混ざり合って積み重なった形状、言わば溶岩台地斜面ガラ場状の超微細凹凸形状でほぼ全面が覆われていた。 A KLF5 piece treated in the same manner as described above was applied to a scanning probe microscope. As a result, RSm was 1 to 3 μm and Rz was 0.3 to 0.5 μm. A photograph when the electron microscope is observed at 10,000 times and 100,000 times is shown in FIG. 7 ((a): 10,000 times, (b): 100,000 times). When observed with a 100,000-fold electron microscope, the shape is a mixture of 10 to 20 nm diameter particles and 50 to 150 nm indefinite polygonal shapes mixed together, in other words, a lava plateau slope-like ultra-fine uneven shape. The entire surface was covered.
［実験例８］（ＫＳ４０チタン合金片の表面処理）
市販の厚さ１ｍｍの純チタン型チタン合金板材「ＫＳ４０（株式会社 神戸製鋼所製）」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＫＳ４０片を多数作成した。槽に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これを脱脂用水溶液とした。この脱脂用水溶液に前記ＫＳ４０片を５分浸漬して脱脂し、よく水洗した。次いで別の槽に１水素２弗化アンモニウムを４０％含む万能エッチング材「ＫＡ−３（株式会社 金属化工技術研究所（日本国東京都）製）」を２％含む水溶液（６０℃）を用意し、これに前記ＫＳ４０片を３分浸漬し、イオン交換水でよく水洗した。次いで前記ＫＳ４０片を３％濃度の硝酸水溶液に１分浸漬し、水洗した。その後、前記ＫＳ４０片を、９０℃とした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 8] (Surface treatment of KS40 titanium alloy piece)
A commercially available pure titanium type titanium alloy plate “KS40 (manufactured by Kobe Steel, Ltd.)” having a thickness of 1 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular KS40 pieces. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and this was used as a degreasing aqueous solution. The KS40 pieces were immersed in this degreasing aqueous solution for 5 minutes to degrease and washed thoroughly with water. Next, an aqueous solution (60 ° C.) containing 2% of a universal etching material “KA-3 (manufactured by Metallurgy Engineering Laboratory (Tokyo, Japan))” containing 40% ammonium difluoride 40% in a separate tank is prepared. Then, the KS40 piece was immersed in this for 3 minutes and washed thoroughly with ion-exchanged water. Next, the KS40 piece was immersed in a 3% strength aqueous nitric acid solution for 1 minute and washed with water. Thereafter, the KS40 pieces were placed in a hot air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＫＳ４０片を走査型プローブ顕微鏡で観察した。その結果、ＲＳｍは１〜３μｍ、Ｒｚは０．８〜１．５μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図８に示した（（ａ）：１万倍，（ｂ）：１０万倍）。電子顕微鏡での観察から、幅と高さが１０〜数百ｎｍで長さが数百〜数μｍの湾曲した連山状突起が間隔周期１０〜数百ｎｍで面上に林立している超微細凹凸形状であることが分かった。さらに、ＸＰＳによる分析から、表面には酸素とチタンが大量に観察され、少量の炭素が観察された。これらから表層は酸化チタンが主成分であることが分かり、しかも暗色であることから３価のチタンの酸化物と推定された。 A KS40 piece treated in the same manner as described above was observed with a scanning probe microscope. As a result, RSm was 1 to 3 μm and Rz was 0.8 to 1.5 μm. Photographs obtained by observing the electron microscope at 10,000 times and 100,000 times are shown in FIG. 8 ((a): 10,000 times, (b): 100,000 times). From observation with an electron microscope, a curved continuous mountain-like projection having a width and height of 10 to several hundred nm and a length of several hundred to several μm stands on the surface with an interval period of 10 to several hundred nm. It was found to be an uneven shape. Furthermore, from the analysis by XPS, a large amount of oxygen and titanium were observed on the surface, and a small amount of carbon was observed. From these, it was found that the surface layer was composed mainly of titanium oxide, and because it was dark, it was estimated to be a trivalent titanium oxide.
［実験例９］（ＫＳＴｉ−９チタン合金片の表面処理）
市販の厚さ１ｍｍのα−β型チタン合金板材「ＫＳＴｉ−９（株式会社 神戸製鋼所製）」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＫＳＴｉ−９片を多数作成した。槽に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これを脱脂用水溶液とした。この脱脂用水溶液に前記ＫＳＴｉ−９片を５分浸漬して脱脂し、よく水洗した。次いで別の槽に苛性ソーダ１．５％濃度の水溶液（４０℃）を用意し、これに前記ＫＳＴｉ−９片を１分浸漬し、水洗した。次いで別の槽に、市販汎用エッチング試薬「ＫＡ−３」を２重量％溶解した水溶液（６０℃）を用意し、これに前記ＫＳＴｉ−９片を３分浸漬し、イオン交換水でよく水洗した。このＫＳＴｉ−９片には黒色のスマットが付着していたので、３％濃度の硝酸水溶液（４０℃）に３分浸漬し、次いで超音波を効かしたイオン交換水に５分浸漬してスマットを落とし、再び３％硝酸水溶液に０．５分浸漬し、水洗した。次いで前記ＫＳＴｉ−９片を、９０℃とした温風乾燥機に１５分入れて乾燥した。乾燥後のＫＳＴｉ−９片に金属光沢はなく暗褐色であった。
[Experimental Example 9] (Surface treatment of KSTi-9 titanium alloy piece)
A commercially available α-β type titanium alloy plate “KSTi-9 (manufactured by Kobe Steel, Ltd.)” having a thickness of 1 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular KSTi-9 pieces. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and this was used as a degreasing aqueous solution. The KSTi-9 pieces were immersed in this degreasing aqueous solution for 5 minutes for degreasing and thoroughly washed with water. Next, an aqueous solution (40 ° C.) having a caustic soda concentration of 1.5% was prepared in another tank, and the KSTi-9 piece was immersed in this for 1 minute and washed with water. Next, an aqueous solution (60 ° C.) in which 2% by weight of a commercially available general-purpose etching reagent “KA-3” was dissolved was prepared in another tank, and the KSTi-9 piece was immersed in this for 3 minutes and washed thoroughly with ion-exchanged water. . Since this KSTi-9 piece had a black smut attached, it was immersed in a 3% nitric acid aqueous solution (40 ° C.) for 3 minutes, and then immersed in ion-exchanged water subjected to ultrasonic waves for 5 minutes. Then, it was again immersed in a 3% nitric acid aqueous solution for 0.5 minutes and washed with water. Next, the KSTi-9 pieces were placed in a hot air dryer at 90 ° C. for 15 minutes and dried. The dried KSTi-9 pieces had a dark brown color with no metallic luster.
前記と同じ処理をしたＫＳＴｉ−９片を走査型プローブ顕微鏡で観察した。走査解析によるとＲＳｍは４〜６μｍ、Ｒｚは１〜２μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図９に示した（（ａ）：１万倍，（ｂ）：１０万倍）。その様子は実験例８の図８に酷似した部分に加え、表現が難しい枯葉状の部分が多く見られた。 The KSTi-9 piece treated in the same manner as described above was observed with a scanning probe microscope. According to scanning analysis, RSm was 4-6 μm and Rz was 1-2 μm. A photograph of the electron microscope observed at 10,000 times and 100,000 times is shown in FIG. 9 ((a): 10,000 times, (b): 100,000 times). In addition to the part very similar to FIG. 8 of Experimental Example 8, many dead leaf-like parts that are difficult to express were seen.
［実験例１０］（ＳＵＳ３０４ステンレス鋼片の表面処理）
市販の厚さ１ｍｍのステンレス鋼板材「ＳＵＳ３０４」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＳＵＳ３０４片を多数作成した。槽に市販のアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％含む水溶液（６０℃）を用意し、これを脱脂用水溶液とした。この脱脂用水溶液に前記ＳＵＳ３０４片を５分浸漬して脱脂し、よく水洗した。続いて別の槽に１水素２弗化アンモニウムを１％と９８％硫酸を５％含む水溶液（６５℃）を用意し、これに前記ＳＵＳ３０４片を４分浸漬し、イオン交換水でよく水洗した。次いで、前記ＳＵＳ３０４片を、３％濃度の硝酸水溶液（４０℃）に３分浸漬して水洗した。次いで前記ＳＵＳ３０４片を、９０℃とした温風乾燥機に１５分入れて乾燥した。
[Experimental Example 10] (Surface treatment of SUS304 stainless steel piece)
A commercially available stainless steel plate material “SUS304” having a thickness of 1 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular SUS304 pieces. An aqueous solution (60 ° C.) containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6” was prepared in a tank, and this was used as a degreasing aqueous solution. The SUS304 piece was immersed in this degreasing aqueous solution for 5 minutes to degrease and washed thoroughly with water. Subsequently, an aqueous solution (65 ° C.) containing 1% ammonium difluoride 1% and 98% sulfuric acid 5% was prepared in another tank, and the SUS304 piece was immersed in this for 4 minutes and washed thoroughly with ion-exchanged water. . Next, the SUS304 piece was immersed in a 3% nitric acid aqueous solution (40 ° C.) for 3 minutes and washed with water. Next, the SUS304 pieces were placed in a hot air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＳＵＳ３０４片を走査型プローブ顕微鏡で観察した。走査解析によると、ＲＳｍは１〜２μｍであり、Ｒｚは０．３〜０．４μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図１０に示した（（ａ）：１万倍，（ｂ）：１０万倍）。電子顕微鏡による観察から、表面が直径２０〜７０ｎｍの粒径物や不定多角形状物が積み重なった形状、言わば溶岩台地斜面ガラ場状の超微細凹凸形状で覆われていた。更に別の１個をＸＰＳ分析にかけた。このＸＰＳ分析から、表面には酸素と鉄が大量に、又、少量のニッケル、クロム、炭素、ごく少量のモリブデン、珪素が観察された。これらから表層は金属酸化物が主成分であることが分かった。この分析パターンはエッチング前のＳＵＳ３０４と殆ど同じであった。 A SUS304 piece treated in the same manner as described above was observed with a scanning probe microscope. According to scanning analysis, RSm was 1-2 μm and Rz was 0.3-0.4 μm. A photograph of the electron microscope observed at 10,000 times and 100,000 times is shown in FIG. 10 ((a): 10,000 times, (b): 100,000 times). From observation with an electron microscope, the surface was covered with a shape in which particle diameters having a diameter of 20 to 70 nm and indefinite polygonal shapes were stacked, in other words, a lava plateau slope-like ultra fine uneven shape. Another one was subjected to XPS analysis. From this XPS analysis, a large amount of oxygen and iron was observed on the surface, and a small amount of nickel, chromium, carbon, a very small amount of molybdenum and silicon were observed. From these, it was found that the surface layer was mainly composed of metal oxide. This analysis pattern was almost the same as SUS304 before etching.
［実験例１１］（ＳＰＣＣ鋼材片の表面処理）
市販の厚さ１．６ｍｍの冷間圧延鋼板材「ＳＰＣＣ」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＳＰＣＣ片を多数作成した。槽にアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％を含む水溶液（６０℃）を用意し、これに前記ＳＰＣＣ片を５分浸漬して水道水（群馬県太田市）で水洗した。次いで別の槽に１．５％苛性ソーダ水溶液（４０℃）を用意し、これに前記ＳＰＣＣ片を１分浸漬し、水洗した。次いで別の槽に９８％硫酸を１０％含む水溶液（５０℃）を用意し、これに前記ＳＰＣＣ片を６分浸漬し、イオン交換水で十分に水洗した。次いで前記ＳＰＣＣ片を、１％濃度のアンモニア水（２５℃）に１分浸漬して水洗した。次いで前記ＳＰＣＣ片を、２％濃度の過マンガン酸カリ、１％濃度の酢酸、及び０．５％濃度の水和酢酸ナトリウムを含む水溶液（４５℃）に１分浸漬して十分に水洗した。その後、前記ＳＰＣＣ片を、９０℃とした温風乾燥機内に１５分入れて乾燥した。
[Experiment 11] (Surface treatment of SPCC steel piece)
A commercially available cold rolled steel plate material “SPCC” having a thickness of 1.6 mm was obtained and cut to produce a large number of 45 mm × 18 mm rectangular SPCC pieces. An aqueous solution (60 ° C.) containing 7.5% of an aluminum alloy degreasing agent “NE-6” was prepared in a tank, and the SPCC pieces were immersed in this for 5 minutes and washed with tap water (Ota City, Gunma Prefecture). . Next, a 1.5% caustic soda aqueous solution (40 ° C.) was prepared in another tank, and the SPCC pieces were immersed in this for 1 minute and washed with water. Next, an aqueous solution (50 ° C.) containing 10% of 98% sulfuric acid was prepared in another tank, and the SPCC pieces were immersed in this for 6 minutes and sufficiently washed with ion-exchanged water. Next, the SPCC piece was immersed in 1% aqueous ammonia (25 ° C.) for 1 minute and washed with water. The SPCC pieces were then immersed in an aqueous solution (45 ° C.) containing 2% potassium permanganate, 1% acetic acid, and 0.5% sodium hydrate acetate for 1 minute and thoroughly washed with water. Thereafter, the SPCC piece was placed in a warm air dryer at 90 ° C. for 15 minutes and dried.
前記と同じ処理をしたＳＰＣＣ片を走査型プローブ顕微鏡で観察した。走査解析によると、ＲＳｍが１〜３μｍ、Ｒｚが０．３〜１．０μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図１１に示した（（ａ）：１万倍，（ｂ）：１０万倍）。１０万倍電子顕微鏡による観察結果から、高さ及び奥行きが８０〜２００ｎｍで幅が数百〜数千ｎｍの階段が無限に続いた形状の超微細凹凸形状でほぼ全面が覆われていることが分かる。パーライト構造が剥き出しになった様子であり化成処理層はごく薄いことが分かる。 The SPCC piece treated in the same manner as described above was observed with a scanning probe microscope. According to scanning analysis, RSm was 1 to 3 μm and Rz was 0.3 to 1.0 μm. Photographs obtained by observing the electron microscope at 10,000 times and 100,000 times are shown in FIG. 11 ((a): 10,000 times, (b): 100,000 times). From the observation result with a 100,000 times electron microscope, it is found that the entire surface is almost covered with an ultra fine uneven shape having a height and depth of 80 to 200 nm and a width of several hundred to several thousand nm that is infinitely continuous. I understand. It can be seen that the pearlite structure is exposed and the chemical conversion treatment layer is very thin.
［実験例１２］（ＳＰＨＣ鋼材片の表面処理）
市販の厚さ１．６ｍｍの熱間圧延鋼材「ＳＰＨＣ」を入手し、切断して４５ｍｍ×１８ｍｍの長方形のＳＰＨＣ片を多数作成した。槽にアルミニウム合金用脱脂剤「ＮＥ−６」を７．５％を含む水溶液（６０℃）を用意し、これに前記ＳＰＨＣ片を５分浸漬して水道水（群馬県太田市）で水洗した。次いで別の槽に１．５％苛性ソーダ水溶液（４０℃）を用意し、これに前記ＳＰＨＣ片を１分浸漬し、水洗した。次いで別の槽に９８％硫酸を１０％と１水素２弗化アンモニウム１％を含む水溶液（６５℃）を用意し、これに前記ＳＰＨＣ片を２分浸漬し、イオン交換水で十分に水洗した。次いで前記ＳＰＨＣ片を、１％濃度のアンモニア水（２５℃）に１分浸漬して水洗した。次いで前記ＳＰＨＣ片を、８０％正リン酸を１．５％、亜鉛華を０．２１％、珪弗化ナトリウムを０．１６％、塩基性炭酸ニッケルを０．２３％含む水溶液（５５℃）に１分浸漬して十分に水洗した。その後、前記ＳＰＨＣ片を、９０℃とした温風乾燥機内に１５分入れて乾燥した。
[Experiment 12] (Surface treatment of SPHC steel piece)
A commercially available 1.6 mm thick hot rolled steel “SPHC” was obtained and cut to produce a large number of 45 mm × 18 mm rectangular SPHC pieces. An aqueous solution (60 ° C.) containing 7.5% of an aluminum alloy degreasing agent “NE-6” was prepared in a tank, and the SPHC pieces were immersed in this for 5 minutes and washed with tap water (Ota City, Gunma Prefecture). . Next, a 1.5% caustic soda aqueous solution (40 ° C.) was prepared in another tank, and the SPHC pieces were immersed in this for 1 minute and washed with water. Next, an aqueous solution (65 ° C.) containing 10% 98% sulfuric acid and 1% ammonium difluoride was prepared in another tank, and the SPHC pieces were immersed in this for 2 minutes and washed thoroughly with ion-exchanged water. . Next, the SPHC pieces were immersed in 1% aqueous ammonia (25 ° C.) for 1 minute and washed with water. Next, the SPHC piece was an aqueous solution (55 ° C.) containing 80% orthophosphoric acid 1.5%, zinc white 0.21%, sodium silicofluoride 0.16% and basic nickel carbonate 0.23%. For 1 minute and thoroughly washed with water. Thereafter, the SPHC pieces were placed in a warm air dryer at 90 ° C. for 15 minutes and dried.
乾燥後、前記ＳＰＨＣ片を走査型プローブ顕微鏡で観察した。走査解析によると、ＲＳｍが１〜３μｍ、Ｒｚが０．３〜１．０μｍであった。電子顕微鏡を１万倍、１０万倍として観察したときの写真を図１２に示した（（ａ）：１万倍，（ｂ）：１０万倍）。１０万倍電子顕微鏡による観察結果から、高さ及び奥行きが８０〜５００ｎｍで幅が数百〜数万ｎｍの階段が無限に続いた形状の超微細凹凸形状でほぼ全面が覆われていることが分かり、これもパーライト構造であった。 After drying, the SPHC pieces were observed with a scanning probe microscope. According to scanning analysis, RSm was 1 to 3 μm and Rz was 0.3 to 1.0 μm. Photographs obtained by observing the electron microscope at 10,000 times and 100,000 times are shown in FIG. 12 ((a): 10,000 times, (b): 100,000 times). According to the result of observation with an electron microscope of 100,000 times, it was found that the entire surface was covered with an ultra-fine concavo-convex shape having an infinite number of steps having a height and depth of 80 to 500 nm and a width of several hundred to several tens of thousands of nm. Okay, this was also a pearlite structure.
［実験例１３］（接着剤の作成）
ビスフェノールＡ型エポキシ樹脂の単量体が主成分の分子量約３７０のエポキシ樹脂「ＪＥＲ８２８（ジャパンエポキシレジン株式会社製）」、固体である分子量約１６００の多量体のビスフェノールＡ型エポキシ樹脂「ＪＥＲ１００４（ジャパンエポキシレジン株式会社製）」、多官能型のフェノールノボラック型エポキシ樹脂「ＪＥＲ１５４（ジャパンエポキシレジン株式会社製）」、アニリン型の３官能エポキシ樹脂「ＪＥＲ６３０（ジャパンエポキシレジン株式会社製）」、平均粒径が十数μｍ程度のＰＥＳ粉体「ＰＥＳ４１００ＭＰ（住友化学株式会社製）」、平均粒径が８〜１２μｍの微粉タルク「ハイミクロンＨＥ５（竹原化学工業株式会社（日本国兵庫県）製）」、ヒュームドシリカ「アエロジルＲ８０５（日本アエロジル株式会社製）」、エポキシ樹脂の硬化剤である微粉型ジシアンジアミド「ＤＩＣＹ７（ジャパンエポキシレジン株式会社製）」、２−メチルイミダゾールの微粉「２ＭＩ（日本合成化学工業株式会社製）」、２−フェニルイミダゾールの顆粒「２ＰＩ（日本合成化学工業株式会社製）」、Ｎ，Ｎ’−ジメチルピペラジン「ジメチルピペラジン（昭和化学株式会社（日本国東京都）製）」、及び、３−（３，４−ジクロルフェニル）−１，１−ジメチルウレアの微粉「ＤＣＭＵ９９（保土谷化学工業株式会社（日本国東京都）製）」を入手した。
[Experimental Example 13] (Preparation of adhesive)
The epoxy resin “JER828 (manufactured by Japan Epoxy Resin Co., Ltd.)” having a molecular weight of about 370, the main component of which is a monomer of bisphenol A type epoxy resin, and the solid bisphenol A type epoxy resin “JER1004” (Japan) having a molecular weight of about 1600 Epoxy Resin Co., Ltd.) ”, multifunctional phenol novolac type epoxy resin“ JER154 (Japan Epoxy Resin Co., Ltd.) ”, aniline type trifunctional epoxy resin“ JER630 (Japan Epoxy Resin Co., Ltd.) ”, average grain PES powder “PES4100MP (manufactured by Sumitomo Chemical Co., Ltd.)” with a diameter of about a few tens of μm, fine powder talc “Hymicron HE5 (manufactured by Takehara Chemical Co., Ltd. (Hyogo, Japan))” with an average particle size of 8-12 μm , Fumed silica "Aerosil R805 (Nippon Aerosil Co., Ltd.) ”, Fine powdered dicyandiamide“ DICY7 (made by Japan Epoxy Resin Co., Ltd.) ”, 2-methylimidazole fine powder“ 2MI (made by Nippon Synthetic Chemical Industry Co., Ltd.) ”, 2-phenyl Imidazole granules “2PI (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)”, N, N′-dimethylpiperazine “dimethylpiperazine (manufactured by Showa Chemical Co., Ltd. (Tokyo, Japan))”, and 3- (3,4- Dichlorophenyl) -1,1-dimethylurea fine powder “DCMU99 (Hodogaya Chemical Co., Ltd., Tokyo, Japan)” was obtained.
入手した薬剤のうち、「２ＰＩ」は粉末でなく顆粒であったので、直径１５０ｍｍのセラミック製ボールミルに２００ｇ入れて３０分粉砕してボールを篩分けし、更に３００メッシュ通過品を粉末「２ＰＩ」として保管した。 Among the drugs obtained, “2PI” was not a powder but a granule. Therefore, 200 g was put in a ceramic ball mill having a diameter of 150 mm, pulverized for 30 minutes, and the balls were sieved. Stored as.
［接着剤１（Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）の作成］
「ＪＥＲ８２８」を４００ｇ（１００質量部）使用して１液性エポキシ接着剤を作成した。直径０．３ｍｍのジルコニアビーズを粉砕室容量の８０％充填したサンドグラインドミル「ツエア（アシザワ・ファインテック株式会社製）」を用意し、その入口側に循環ポンプと撹拌機付きのオープンタンクを繋いだ。一方、サンドグラインドミルの出口はオープンタンクに開放した。「ＪＥＲ８２８」１００質量部（４００ｇ）をオープンタンクに投入し、循環ポンプで粉砕室を完全に満たしてからミルの運転を開始した。ミルには水冷ラインがあるので通水を調整して粉砕室内が６０℃以下になるようにした。ミル回転子の周速は１１〜１２ｍ／秒とした。
[Creation of Adhesive 1 (A, PES, DICY, DCMU)]
One-component epoxy adhesive was prepared using 400 g (100 parts by mass) of “JER828”. A sand grind mill “Tuea (made by Ashizawa Finetech Co., Ltd.)” filled with zirconia beads with a diameter of 0.3 mm and 80% of the grinding chamber capacity is prepared, and an open tank with a circulation pump and a stirrer is connected to the inlet side. It is. On the other hand, the exit of the sand grind mill was opened to an open tank. 100 parts by mass (400 g) of “JER828” was put into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, the water flow was adjusted so that the inside of the grinding chamber became 60 ° C. or lower. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.
その後、オープンタンクにヒュームドシリカ「アエロジルＲ８０５」を０．４質量部（１．６ｇ）入れて循環粉砕を進め、次いで微粉タルク「ハイミクロンＨＥ５」を２．４質量部（９．６ｇ）徐々に入れて循環粉砕を進め、次いでＰＥＳ粉体「ＰＥＳ４１００ＭＰ」３．２質量部（１２．８ｇ）を徐々に加えた後、６０分間湿式粉砕（実質的にはエポキシ樹脂中に充填材を分散させる操作となる。）を続けた。その後、ミルの出口をオープンタンクからポリエチ瓶に向くようにし、このポリエチ瓶内に混合物を得た。この混合物１０６質量部には、エポキシ樹脂１００質量部、無機充填材「ハイミクロンＨＥ５」２．４質量部、超微細無機充填材「アエロジルＲ８０５」０．４質量部、及び熱可塑性樹脂粉体「ＰＥＳ４１００ＭＰ」３．２質量部が含まれる。 After that, 0.4 parts by mass (1.6 g) of fumed silica “Aerosil R805” was put into an open tank, followed by circulating pulverization, and then 2.4 parts by mass (9.6 g) of fine talc “Himicron HE5” was gradually added. Then, after adding PES powder “PES4100MP” 3.2 parts by mass (12.8 g) gradually, wet grinding (substantially dispersing the filler in the epoxy resin for 60 minutes) Continued operation). Thereafter, the outlet of the mill was directed from the open tank to the polyethylene bottle, and a mixture was obtained in the polyethylene bottle. 106 parts by mass of this mixture include 100 parts by mass of an epoxy resin, 2.4 parts by mass of an inorganic filler “Himicron HE5”, 0.4 parts by mass of an ultrafine inorganic filler “Aerosil R805”, and thermoplastic resin powder “ 3.2 parts by mass of “PES4100MP” are included.
次いで乳鉢に、前記混合物１０６質量部、硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」４質量部、及び硬化助剤として３−（３，４−ジクロルフェニル）−１，１−ジメチルウレアの微粉「ＤＣＭＵ９９」２質量部を取って、これらをよく混練した。これをポリエチ瓶に取り、その後５℃とした冷蔵庫に保管した。この接着剤の名称を接着剤１（Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）とした。この接着剤の組成を表１に示す（実験例１３）。 Next, in a mortar, 106 parts by mass of the mixture, 4 parts by mass of fine powder dicyandiamide “DICY7” as a curing agent, and 3- (3,4-dichlorophenyl) -1,1-dimethylurea fine powder “DCMU99” as a curing aid. “Two parts by mass were taken and kneaded well. This was taken in a polyethylene bottle and then stored in a refrigerator at 5 ° C. This adhesive was named Adhesive 1 (A, PES, DICY, DCMU). The composition of this adhesive is shown in Table 1 (Experimental Example 13).
［実験例１４］（接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）の作成）
「ＪＥＲ８２８」２００質量部（８００ｇ）とＭＩＢＫ１００質量部（４００ｇ）をビーカー内で混合して均一化し、低粘度の混合液３００質量部（１２００ｇ）を作成した。直径０．３ｍｍのジルコニアビーズを粉砕室容量の８０％充填したサンドグラインドミル「ツエア（アシザワ・ファインテック株式会社製）」を用意し、その入口側に循環ポンプと撹拌機付きのオープンタンクを繋いだ。一方、サンドグラインドミルの出口はオープンタンクに開放した。前記混合液のうち７５質量部（３００ｇ）をオープンタンクに投入し、循環ポンプで粉砕室を完全に満たしてからミルの運転を開始した。ミルには水冷ラインがあるので通水を調整して粉砕室内が５０℃以下になるようにした。ミル回転子の周速は１１〜１２ｍ／秒とした。
[Experimental Example 14] (Preparation of Adhesive 2 (MIBK, A, PES, DICY))
200 parts by mass (800 g) of “JER828” and 100 parts by mass (400 g) of MIBK were mixed and homogenized in a beaker to prepare 300 parts by mass (1200 g) of a low-viscosity liquid mixture. A sand grind mill “Tuea (made by Ashizawa Finetech Co., Ltd.)” filled with zirconia beads with a diameter of 0.3 mm and 80% of the grinding chamber capacity is prepared, and an open tank with a circulation pump and a stirrer is connected to the inlet side. It is. On the other hand, the exit of the sand grind mill was opened to an open tank. 75 parts by mass (300 g) of the mixed solution was charged into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, the water flow was adjusted so that the inside of the grinding chamber became 50 ° C. or lower. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.
その後、オープンタンクに硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」２質量部（８ｇ）を入れて、粉砕を２０分続けた。その後、ヒュームドシリカ「アエロジルＲ８０５」を０．２質量部（０．８ｇ）を徐々に入れて循環粉砕を進め、次いで微粉タルク「ハイミクロンＨＥ５」を１．２質量部（４．８ｇ）徐々に入れて循環粉砕を進め、次いでＰＥＳ粉体「ＰＥＳ４１００ＭＰ」１．６質量部（６．４ｇ）を徐々に加えた後、１５分間湿式粉砕を続けた。その後、ミルの出口をオープンタンクからポリエチ瓶に向くようにし、このポリエチ瓶内に混合物を得た。この混合物中にはエポキシ樹脂１００質量部に対して、ＭＩＢＫ５０質量部、無機充填材「ハイミクロンＨＥ５」２．４質量部、超微細無機充填材「アエロジルＲ８０５」０．４質量部、及び熱可塑性樹脂粉体「ＰＥＳ４１００ＭＰ」３．２質量部が含まれ、さらに硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」４質量部が含まれる。これを５℃とした冷蔵庫に保管した。この接着剤の名称を接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）とした。この接着剤の組成を表１に示す（実験例１４）。 Thereafter, 2 parts by mass (8 g) of fine powder type dicyandiamide “DICY7” as a curing agent was put in an open tank, and pulverization was continued for 20 minutes. Thereafter, 0.2 parts by mass (0.8 g) of fumed silica “Aerosil R805” was gradually added to circulate and pulverize, and then 1.2 parts by mass (4.8 g) of fine talc “Hymicron HE5” was gradually added. The pulverization was continued, and 1.6 parts by mass (6.4 g) of the PES powder “PES4100MP” was gradually added, and then the wet pulverization was continued for 15 minutes. Thereafter, the outlet of the mill was directed from the open tank to the polyethylene bottle, and a mixture was obtained in the polyethylene bottle. In this mixture, 100 parts by mass of epoxy resin, 50 parts by mass of MIBK, 2.4 parts by mass of inorganic filler “Himicron HE5”, 0.4 parts by mass of ultrafine inorganic filler “Aerosil R805”, and thermoplasticity 3.2 parts by mass of the resin powder “PES4100MP” is included, and further 4 parts by mass of fine powder type dicyandiamide “DICY7” is included as a curing agent. This was stored in a refrigerator at 5 ° C. This adhesive was named Adhesive 2 (MIBK, A, PES, DICY). The composition of this adhesive is shown in Table 1 (Experimental Example 14).
［実験例１５］（接着剤３（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）の作成）
実験例１４に示した方法により作成した接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）１６０質量部に対して、硬化助剤として３−（３，４−ジクロルフェニル）−１，１−ジメチルウレアの微粉「ＤＣＭＵ９９」２質量部をよく混練した。この接着剤の名称を接着剤３（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）とした。この接着剤の組成を表１に示す（実験例１５）。
[Experimental Example 15] (Preparation of Adhesive 3 (MIBK, A, PES, DICY, DCMU))
With respect to 160 parts by mass of the adhesive 2 (MIBK, A, PES, DICY) prepared by the method shown in Experimental Example 14, 3- (3,4-dichlorophenyl) -1,1-dimethyl as a curing aid 2 parts by mass of urea fine powder “DCMU99” was well kneaded. This adhesive was named Adhesive 3 (MIBK, A, PES, DICY, DCMU). The composition of this adhesive is shown in Table 1 (Experimental Example 15).
［実験例１６］（接着剤１を使用した接着試験）
実験例１の表面処理を施したＡ７０７５片１２枚に対して接着剤１（Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）をヘラによって塗布した後、これらをデシケータに入れて蓋をした。このデシケータは予め温風乾燥機内で６０℃に暖めておいたものである。その後、Ａ７０７５片を入れたデシケータ内を真空ポンプで減圧し、３分ほど置いてから常圧に戻した。この減圧／常圧戻し操作を計３回行った（これは染み込まし処理である）。その後、Ａ７０７５片をデシケータから取り出し、Ａ７０７５片２枚の接着剤塗布範囲同士を密着させて対にする。その際、接着面積が０．６〜０．７ｃｍ２となるようにする。この対をクリップで固定し、図１３に示す試験片の形状とした。このようにしてＡ７０７５片同士の対を６組作成した。熱風乾燥機内を９０℃とし、これに対としたＡ７０７５片を入れて、５分加熱した。次いで、熱風乾燥機内を１３５℃に昇温し、１３５℃で４０分加熱した。次いで、熱風乾燥機内を１６５℃に昇温し、１６５℃で２０分加熱した。その後放冷してＡ７０７５片同士の接合体である試験片を６組得た。翌日に試験片を引っ張り試験機にかけて破断させた。この試験は常温下及び１５０℃下において、それぞれ３組の試験片に対して行った。その際のせん断破断力（３組の平均値）を表２に示す（実験例１６）。
[Experimental Example 16] (Adhesion test using adhesive 1)
Adhesive 1 (A, PES, DICY, DCMU) was applied to twelve A7075 pieces subjected to the surface treatment of Experimental Example 1 with a spatula, and these were placed in a desiccator and covered. This desiccator is preheated to 60 ° C. in a hot air dryer. Thereafter, the inside of the desiccator containing the A7075 piece was depressurized with a vacuum pump, and after about 3 minutes, the pressure was returned to normal pressure. This decompression / return to normal pressure operation was performed three times in total (this is a soaking process). Thereafter, the A7075 piece is taken out from the desiccator, and the two A7075 piece adhesive application ranges are brought into close contact with each other to form a pair. At that time, the adhesion area is set to 0.6 to 0.7 cm 2 . This pair was fixed with a clip to obtain the shape of the test piece shown in FIG. In this way, six pairs of A7075 pieces were created. The inside of the hot air dryer was set to 90 ° C., and a pair of A7075 pieces was put therein and heated for 5 minutes. Next, the inside of the hot air dryer was heated to 135 ° C. and heated at 135 ° C. for 40 minutes. Next, the temperature inside the hot air dryer was raised to 165 ° C. and heated at 165 ° C. for 20 minutes. Thereafter, it was allowed to cool to obtain 6 sets of test pieces which are joined bodies of A7075 pieces. On the next day, the test piece was broken by a tensile tester. This test was performed on three sets of test pieces at room temperature and 150 ° C., respectively. The shear breaking force (average value of three sets) at that time is shown in Table 2 (Experimental Example 16).
［実験例１７］（接着剤２を使用した接着試験）
実験例１の表面処理を施したＡ７０７５片１２枚を厚紙上に並列に配置し、これら全てのＡ７０７５片の接着剤塗布領域以外を別の厚紙によって覆った。これにより接着剤塗布領域のみが表出した状態となっている。その後、これらの接着剤塗布領域に、噴霧器によって接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）を噴霧した。その後、Ａ７０７５片を３０分間放置して、溶剤分を殆ど揮発させてから、これらをデシケータに入れて蓋をした。このデシケータは予め温風乾燥機内で６０℃に暖めておいたものである。その後、Ａ７０７５片を入れたデシケータ内を真空ポンプで減圧し、３分ほど置いてから常圧に戻した。この減圧／常圧戻し操作を計３回行った（これは染み込まし処理である）。その後、Ａ７０７５片をデシケータから取り出し、Ａ７０７５片２枚の接着剤塗布範囲同士を密着させて対にする。その際、接着面積が０．６〜０．７ｃｍ２となるようにする。この対をクリップで固定し、図１３に示す試験片の形状とした。このようにしてＡ７０７５片同士の対を６組作成した。熱風乾燥機内を９０℃とし、これに対としたＡ７０７５片を入れて、５分加熱した。次いで、熱風乾燥機内を１３５℃に昇温し、１３５℃で４０分加熱した。次いで、熱風乾燥機内を１７０℃に昇温し、１７０℃で６０分加熱した。その後放冷してＡ７０７５片同士の接合体である試験片を６組得た。翌日に試験片を引っ張り試験機にかけて破断させた。この試験は常温下及び１５０℃下において、それぞれ３組の試験片に対して行った。その際のせん断破断力（３組の平均値）を表２に示す（実験例１７）。
[Experimental Example 17] (Adhesion test using adhesive 2)
Twelve A7075 pieces subjected to the surface treatment of Experimental Example 1 were arranged in parallel on a cardboard, and all the A7075 pieces other than the adhesive application area were covered with another cardboard. Thereby, only the adhesive application region is exposed. Thereafter, the adhesive 2 (MIBK, A, PES, DICY) was sprayed onto these adhesive application areas by a sprayer. Thereafter, the A7075 pieces were allowed to stand for 30 minutes to volatilize most of the solvent, and then these were placed in a desiccator and covered. This desiccator is preheated to 60 ° C. in a hot air dryer. Thereafter, the inside of the desiccator containing the A7075 piece was depressurized with a vacuum pump, and after about 3 minutes, the pressure was returned to normal pressure. This decompression / return to normal pressure operation was performed three times in total (this is a soaking process). Thereafter, the A7075 piece is taken out from the desiccator, and the two A7075 piece adhesive application ranges are brought into close contact with each other to form a pair. At that time, the adhesion area is set to 0.6 to 0.7 cm 2 . This pair was fixed with a clip to obtain the shape of the test piece shown in FIG. In this way, six pairs of A7075 pieces were created. The inside of the hot air dryer was set to 90 ° C., and a pair of A7075 pieces was put therein and heated for 5 minutes. Next, the inside of the hot air dryer was heated to 135 ° C. and heated at 135 ° C. for 40 minutes. Next, the temperature inside the hot air dryer was raised to 170 ° C. and heated at 170 ° C. for 60 minutes. Thereafter, it was allowed to cool to obtain 6 sets of test pieces which are joined bodies of A7075 pieces. On the next day, the test piece was broken by a tensile tester. This test was performed on three sets of test pieces at room temperature and 150 ° C., respectively. The shear breaking force (average value of three sets) at that time is shown in Table 2 (Experimental Example 17).
［実験例１８］（接着剤３を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤３（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例１８）。
[Experimental example 18] (Adhesion test using adhesive 3)
An experiment similar to the experiment example 17 was performed using the adhesive 3 (MIBK, A, PES, DICY, DCMU) instead of the adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental Example 18).
表２に示す結果から、硬化助剤（ＤＣＭＵ９９）を含んでいない溶剤型の接着剤２は、常温下でのせん断破断力が５．７ＭＰａと極めて低く、無溶剤型である接着剤１（６５．５ＭＰａ）比較して大きく劣るのみならず、このまま接着剤として使用することが困難であるといえる。一方で硬化助剤（ＤＣＭＵ９９）を含んでいる溶剤型の接着剤３は常温下でのせん断破断力が６２．３ＭＰａであり、無溶剤型である接着剤１（６５．５ＭＰａ）と同等であるといえる。なお、接着剤１〜３のいずれを使用した場合であっても、１５０℃下におけるせん断破断力は５ＭＰａ以下と低かった。特に接着剤２を使用した場合、殆ど接着力を発揮しなかった。 From the results shown in Table 2, the solvent-type adhesive 2 that does not contain a curing aid (DCMU99) has an extremely low shear breaking force at room temperature of 5.7 MPa, and is a solvent-free adhesive 1 (65 It is difficult to use as an adhesive as it is. On the other hand, the solvent-type adhesive 3 containing a curing aid (DCMU99) has a shear breaking force at room temperature of 62.3 MPa, which is equivalent to the solventless adhesive 1 (65.5 MPa). It can be said. In addition, even if it was a case where any of the adhesive agents 1-3 was used, the shear fracture | rupture force in 150 degreeC was as low as 5 Mpa or less. In particular, when the adhesive 2 was used, the adhesive force was hardly exhibited.
［実験例１９］（接着剤４（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）の作成）
実験例１４に示した方法により作成した接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）１６０質量部に対して、硬化助剤として２−フェニルイミダゾール「２ＰＩ」２質量部をよく混練した。この接着剤の名称を接着剤４（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）とした。この接着剤の組成を表１に示す（実験例１９）。
[Experimental Example 19] (Preparation of adhesive 4 (MIBK, A, PES, DICY, 2PI))
With respect to 160 parts by mass of the adhesive 2 (MIBK, A, PES, DICY) prepared by the method shown in Experimental Example 14, 2 parts by mass of 2-phenylimidazole “2PI” was thoroughly kneaded. This adhesive was named Adhesive 4 (MIBK, A, PES, DICY, 2PI). The composition of this adhesive is shown in Table 1 (Experimental Example 19).
［実験例２０］（接着剤５（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＭＩ）の作成）
実験例１４に示した方法により作成した接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）１６０質量部に対して、硬化助剤として２−メチルイミダゾール「２ＭＩ」２質量部をよく混練した。この接着剤の名称を接着剤５（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＭＩ）とした。この接着剤の組成を表１に示す（実験例２０）。
[Experiment 20] (Creation of adhesive 5 (MIBK, A, PES, DICY, 2MI))
With respect to 160 parts by mass of the adhesive 2 (MIBK, A, PES, DICY) prepared by the method shown in Experimental Example 14, 2 parts by mass of 2-methylimidazole “2MI” was thoroughly kneaded. This adhesive was named Adhesive 5 (MIBK, A, PES, DICY, 2MI). The composition of this adhesive is shown in Table 1 (Experimental Example 20).
［実験例２１］（接着剤６（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、ＤＭＰ）の作成）
実験例１４に示した方法により作成した接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）１６０質量部に対して、硬化助剤としてＮ，Ｎ’−ジメチルピペラジン「ジメチルピペラジン」、２質量部をよく混練した。この接着剤の名称を接着剤６（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、ＤＭＰ）とした。この接着剤の組成を表１に示す（実験例２１）。
[Experimental Example 21] (Preparation of adhesive 6 (MIBK, A, PES, DICY, DMP))
With respect to 160 parts by mass of adhesive 2 (MIBK, A, PES, DICY) prepared by the method shown in Experimental Example 14, 2 parts by mass of N, N′-dimethylpiperazine “dimethylpiperazine” is often used as a curing aid. Kneaded. This adhesive was named adhesive 6 (MIBK, A, PES, DICY, DMP). The composition of this adhesive is shown in Table 1 (Experimental Example 21).
［実験例２２］（接着剤４を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤４（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例２２）。
[Experimental example 22] (Adhesion test using adhesive 4)
An experiment similar to Experimental Example 17 was performed using adhesive 4 (MIBK, A, PES, DICY, 2PI) instead of adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental example 22).
［実験例２３］（接着剤５を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤５（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＭＩ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例２３）。
[Experimental example 23] (Adhesion test using adhesive 5)
An experiment similar to Experimental Example 17 was performed using the adhesive 5 (MIBK, A, PES, DICY, 2MI) instead of the adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental Example 23).
［実験例２４］（接着剤６を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤６（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、ＤＭＰ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例２４）。
[Experimental Example 24] (Adhesion test using adhesive 6)
An experiment similar to Experimental Example 17 was performed using adhesive 6 (MIBK, A, PES, DICY, DMP) instead of adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental example 24).
表２に示す結果から、硬化助剤として「２ＰＩ」を使用した接着剤４は、常温下でのせん断破断力は５５．７ＭＰａであり、硬化助剤として「ＤＣＭＵ９９」を使用した接着剤３（６２．３ＭＰａ）には及ばないものの、５０ＭＰａを上回る極めて高い数値を示している。また、接着剤４の１５０℃下におけるせん断破断力は１２．５ＭＰａを示しており、これは接着剤３（４．５ＭＰａ）より明らかに良好な数値であり、高い耐熱性を示すものであった。また、硬化助剤として「２ＭＩ」を使用した接着剤５に関しては、常温下では５３．２ＭＰａという高いせん断破断力を示したが、接着剤３と比較して低かった。また、１５０℃下におけるせん断破断力は５．５ＭＰａであり、接着剤３と同等であるが、接着剤４と比較すると低かった。また、硬化助剤として「ジメチルピペラジン」を使用した接着剤６に関しては、常温下では６０．５ＭＰａという高いせん断破断力を示し、接着剤３と同等であった。一方、１５０℃下においては接着力を発揮しなかった。 From the results shown in Table 2, the adhesive 4 using “2PI” as the curing aid has a shear breaking force at room temperature of 55.7 MPa, and the adhesive 3 using “DCMU99” as the curing aid ( Although it does not reach 62.3 MPa), it shows a very high numerical value exceeding 50 MPa. Further, the shear breaking force at 150 ° C. of the adhesive 4 is 12.5 MPa, which is clearly better than that of the adhesive 3 (4.5 MPa) and exhibits high heat resistance. . In addition, regarding the adhesive 5 using “2MI” as a curing aid, a high shear breaking force of 53.2 MPa was exhibited at room temperature, but it was lower than that of the adhesive 3. Further, the shear breaking force at 150 ° C. was 5.5 MPa, which was the same as that of the adhesive 3, but was lower than that of the adhesive 4. Further, the adhesive 6 using “dimethylpiperazine” as a curing aid showed a high shear breaking force of 60.5 MPa at room temperature and was equivalent to the adhesive 3. On the other hand, the adhesive strength was not exhibited at 150 ° C.
これらの結果から、常温下における接着力と耐熱性を兼備しているのは、硬化助剤として「２ＰＩ」を使用した接着剤４であるといえる。また、いずれの硬化助剤を使用した場合であっても、硬化助剤を使用していない接着剤２より劇的に接着力が改善した。 From these results, it can be said that the adhesive 4 using “2PI” as a curing aid has both adhesive strength and heat resistance at room temperature. Moreover, even if it was a case where any hardening adjuvant was used, adhesive force improved dramatically rather than the adhesive agent 2 which does not use the hardening adjuvant.
［実験例２５］（接着剤７（Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）の作成）
「ＪＥＲ８２８」を６０質量部、「ＪＥＲ１００４」を１５質量部、「ＪＥＲ１５４」を８質量部、及び「ＪＥＲ６３０」１７質量部をビーカーに取り、１６５℃とした熱風乾燥機内に放置して加熱し、固体型「ＪＥＲ１００４」を溶融すると同時によく撹拌し、全体を均一化した。その後、放冷し、エポキシ樹脂液として保管した。このエポキシ樹脂の組成比は、前述した式（i）〜式（iv）の全ての条件に合致する。
[Experiment 25] (Preparation of adhesive 7 (A, PES, DICY, 2PI))
Take 60 parts by weight of "JER828", 15 parts by weight of "JER1004", 8 parts by weight of "JER154", and 17 parts by weight of "JER630" in a beaker and leave in a hot air drier at 165 ° C to heat. The solid type “JER1004” was melted and stirred at the same time to make the whole uniform. Then, it stood to cool and stored as an epoxy resin liquid. The composition ratio of this epoxy resin matches all the conditions of the above-mentioned formulas (i) to (iv).
直径０．３ｍｍのジルコニアビーズを粉砕室容量の８０％充填したサンドグラインドミル「ツエア（アシザワ・ファインテック株式会社製）」を用意し、その入口側に循環ポンプと撹拌機付きのオープンタンクを繋いだ。一方、サンドグラインドミルの出口はオープンタンクに開放した。上記のエポキシ樹脂液１００質量部（４００ｇ）をオープンタンクに投入し、循環ポンプで粉砕室を完全に満たしてからミルの運転を開始した。ミルには水冷ラインがあるので通水を調整して粉砕室内が６０℃以下になるようにした。ミル回転子の周速は１１〜１２ｍ／秒とした。 A sand grind mill “Tuea (made by Ashizawa Finetech Co., Ltd.)” filled with zirconia beads with a diameter of 0.3 mm and 80% of the grinding chamber capacity is prepared, and an open tank with a circulation pump and a stirrer is connected to the inlet side. It is. On the other hand, the exit of the sand grind mill was opened to an open tank. 100 parts by mass (400 g) of the above epoxy resin liquid was put into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, the water flow was adjusted so that the inside of the grinding chamber became 60 ° C. or lower. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.
その後、オープンタンクにヒュームドシリカ「アエロジルＲ８０５」を０．４質量部（１．６ｇ）徐々に入れて循環粉砕を進め、次いで微粉タルク「ハイミクロンＨＥ５」を２．４質量部（９．６ｇ）徐々に入れて循環粉砕を進め、次いでＰＥＳ粉体「ＰＥＳ４１００ＭＰ」３．２質量部（１２．８ｇ）を徐々に加えた後、６０分間湿式粉砕（実質的にはエポキシ樹脂中に充填材を分散させる操作となる。）を続けた。その後、ミルの出口をオープンタンクからポリエチ瓶に向くようにし、このポリエチ瓶内に混合物を得た。この混合物１０６質量部には、エポキシ樹脂１００質量部、無機充填材「ハイミクロンＨＥ５」２．４質量部、超微細無機充填材「アエロジルＲ８０５」０．４質量部、及び熱可塑性樹脂粉体「ＰＥＳ４１００ＭＰ」３．２質量部が含まれる。 Thereafter, 0.4 parts by mass (1.6 g) of fumed silica “Aerosil R805” was gradually added to the open tank, followed by circulating pulverization, and then 2.4 parts by mass (9.6 g of fine talc “Himicron HE5”). ) Gradually add and proceed with cyclic pulverization, then gradually add 3.2 parts by mass of PES powder “PES4100MP” (12.8 g), then wet pulverize for 60 minutes (substantially add filler in epoxy resin) It was an operation to disperse). Thereafter, the outlet of the mill was directed from the open tank to the polyethylene bottle, and a mixture was obtained in the polyethylene bottle. 106 parts by mass of this mixture include 100 parts by mass of an epoxy resin, 2.4 parts by mass of an inorganic filler “Himicron HE5”, 0.4 parts by mass of an ultrafine inorganic filler “Aerosil R805”, and thermoplastic resin powder “ 3.2 parts by mass of “PES4100MP” are included.
次いで乳鉢に、前記混合物１０６質量部、硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」４質量部、及び硬化助剤として２−フェニルイミダゾール粉体「２ＰＩ」２質量部を取って、よく混練した。これをポリエチ瓶に取り、１日間室内で放置してエージングし、その後５℃とした冷蔵庫に保管した。この接着剤の名称を接着剤７（Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）とした。この接着剤の組成を表１に示す（実験例２５）。 Next, 106 parts by mass of the mixture, 4 parts by mass of fine dicyandiamide “DICY7” as a curing agent, and 2 parts by mass of 2-phenylimidazole powder “2PI” as a curing aid were mixed in a mortar and mixed well. This was taken up in a polyethylene bottle, left aged indoors for 1 day, and then stored in a refrigerator at 5 ° C. This adhesive was named Adhesive 7 (A, PES, DICY, 2PI). The composition of this adhesive is shown in Table 1 (Experimental Example 25).
［実験例２６］（接着剤８（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）の作成）
「ＪＥＲ８２８」を６０質量部、「ＪＥＲ１００４」を１５質量部、「ＪＥＲ１５４」を８質量部、及び「ＪＥＲ６３０」１７質量部をビーカーに取り、１６５℃とした熱風乾燥機内に放置して加熱し、固体型「ＪＥＲ１００４」を溶融すると同時によく撹拌し、全体を均一化した。その後、放冷し、エポキシ樹脂液として保管した。このエポキシ樹脂の組成比は、前述した式（i）〜式（iv）の全ての条件に合致する。このエポキシ樹脂液を２００質量部（８００ｇ）とＭＩＢＫ１００質量部（４００ｇ）をビーカー内で混合して均一化し、低粘度の混合液３００質量部（１２００ｇ）を作成した。直径０．３ｍｍのジルコニアビーズを粉砕室容量の８０％充填したサンドグラインドミル「ツエア（アシザワ・ファインテック株式会社製）」を用意し、その入口側に循環ポンプと撹拌機付きのオープンタンクを繋いだ。一方、サンドグラインドミルの出口はオープンタンクに開放した。前記混合液のうち７５質量部（３００ｇ）をオープンタンクに投入し、循環ポンプで粉砕室を完全に満たしてからミルの運転を開始した。ミルには水冷ラインがあるので通水を調整して粉砕室内が５０℃以下になるようにした。ミル回転子の周速は１１〜１２ｍ／秒とした。
[Experiment 26] (Preparation of adhesive 8 (MIBK, A, PES, DICY))
Take 60 parts by weight of "JER828", 15 parts by weight of "JER1004", 8 parts by weight of "JER154", and 17 parts by weight of "JER630" in a beaker and leave in a hot air drier at 165 ° C to heat. The solid type “JER1004” was melted and stirred at the same time to make the whole uniform. Then, it stood to cool and stored as an epoxy resin liquid. The composition ratio of this epoxy resin matches all the conditions of the above-mentioned formulas (i) to (iv). 200 parts by mass (800 g) of this epoxy resin solution and 100 parts by mass (400 g) of MIBK were mixed and homogenized in a beaker to prepare 300 parts by mass (1200 g) of a low-viscosity mixture. A sand grind mill “Tuea (made by Ashizawa Finetech Co., Ltd.)” filled with zirconia beads with a diameter of 0.3 mm and 80% of the grinding chamber capacity is prepared, and an open tank with a circulation pump and a stirrer is connected to the inlet side. It is. On the other hand, the exit of the sand grind mill was opened to an open tank. 75 parts by mass (300 g) of the mixed solution was charged into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, the water flow was adjusted so that the inside of the grinding chamber became 50 ° C. or lower. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.
その後、オープンタンクにヒュームドシリカ「アエロジルＲ８０５」を０．２質量部（０．８ｇ）を徐々に入れて循環粉砕を進め、次いで微粉タルク「ハイミクロンＨＥ５」を１．２質量部（４．８ｇ）徐々に入れて循環粉砕を進め、次いでＰＥＳ粉体「ＰＥＳ４１００ＭＰ」１．６質量部（６．４ｇ）を徐々に加えた後、６０分間湿式粉砕を続けた。次いで硬化剤として、ジシアンジアミド粉体「ＤＩＣＹ７」２質量部（８ｇ）を加え、粉砕を２０分続けた後に湿式粉砕を終了し、ミルの出口をオープンタンクからポリエチ瓶に向くようにし、このポリエチ瓶内に混合物を得た。この混合物中にはエポキシ樹脂１００質量部に対して、ＭＩＢＫ５０質量部、無機充填材「ハイミクロンＨＥ５」２．４質量部、超微細無機充填材「アエロジルＲ８０５」０．４質量部、及び熱可塑性樹脂粉体「ＰＥＳ４１００ＭＰ」３．２質量部が含まれ、さらに硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」４質量部が含まれる。これを５℃とした冷蔵庫に保管した。この接着剤の名称を接着剤８（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）とした。この接着剤の組成を表１に示す（実験例２６）。 Thereafter, 0.2 parts by mass (0.8 g) of fumed silica “Aerosil R805” is gradually added to the open tank, and the circulating pulverization proceeds. Then, 1.2 parts by mass of fine talc “Hymicron HE5” (4. 8 g) After gradually adding and circulating pulverization, 1.6 parts by mass (6.4 g) of PES powder “PES4100MP” was gradually added, and then wet pulverization was continued for 60 minutes. Next, 2 parts by mass (8 g) of dicyandiamide powder “DICY7” was added as a curing agent, and the pulverization was continued for 20 minutes. Then, the wet pulverization was terminated, and the outlet of the mill was directed from the open tank to the polyethylene bottle. A mixture was obtained inside. In this mixture, 100 parts by mass of epoxy resin, 50 parts by mass of MIBK, 2.4 parts by mass of inorganic filler “Himicron HE5”, 0.4 parts by mass of ultrafine inorganic filler “Aerosil R805”, and thermoplasticity 3.2 parts by mass of the resin powder “PES4100MP” is included, and further 4 parts by mass of fine powder type dicyandiamide “DICY7” is included as a curing agent. This was stored in a refrigerator at 5 ° C. This adhesive was named adhesive 8 (MIBK, A, PES, DICY). The composition of this adhesive is shown in Table 1 (Experimental Example 26).
［実験例２７］（接着剤９（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）の作成）
実験例２６で得た接着剤８（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）１６０質量部に対して、硬化助剤として「２ＰＩ」２質量部をよく混練した。この接着剤の名称を接着剤９（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）とした。この接着剤の組成を表１に示す（実験例２７）。
[Experiment 27] (Preparation of adhesive 9 (MIBK, A, PES, DICY, 2PI))
2 parts by mass of “2PI” was thoroughly kneaded with 160 parts by mass of the adhesive 8 (MIBK, A, PES, DICY) obtained in Experimental Example 26. The name of this adhesive was named Adhesive 9 (MIBK, A, PES, DICY, 2PI). The composition of this adhesive is shown in Table 1 (Experimental Example 27).
［実験例２８］（接着剤７を使用した接着試験）
接着剤１（Ａ、ＰＥＳ、ＤＩＣＹ、ＤＣＭＵ）に代えて、接着剤７（Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用して実験例１６と同様の実験を行った。その結果を表２に示す（実験例２８）。
[Experiment 28] (Adhesion test using adhesive 7)
An experiment similar to the experiment example 16 was performed using the adhesive 7 (A, PES, DICY, 2PI) instead of the adhesive 1 (A, PES, DICY, DCMU). The results are shown in Table 2 (Experimental Example 28).
［実験例２９］（接着剤８を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤８（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例２９）。
[Experimental example 29] (Adhesion test using adhesive 8)
An experiment similar to the experiment example 17 was performed using the adhesive 8 (MIBK, A, PES, DICY) instead of the adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental example 29).
［実験例３０］（接着剤９を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤９（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例３０）。
[Experiment 30] (Adhesion test using adhesive 9)
An experiment similar to Experimental Example 17 was performed using adhesive 9 (MIBK, A, PES, DICY, 2PI) instead of adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental example 30).
表２に示す結果から、無溶剤型の接着剤７（Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用した場合には、常温下におけるせん断破断力が６７．５ＭＰａ、１５０℃下でのせん断破断力が４２．１ＭＰａといずれも極めて高い数値を示した。ビスフェノールＡ型エポキシ樹脂単量体「ＪＥＲ８２８」のみをエポキシ樹脂分とした同じく無溶剤型の接着剤１を使用した場合、１５０℃下でのせん断破断力が４．１ＭＰａであるから、エポキシ樹脂の組成を改良したことによって耐熱性は大きく改善したことになる。溶剤型の接着剤８に関しては、エポキシ樹脂の組成を改良したものの常温下におけるせん断破断力は５．３ＭＰａと極めて低く、１５０℃下においては接着力を発揮しなかった。これは硬化助剤を添加していないことによる。この結果から、接着剤８はこのまま接着剤としては使用できない。 From the results shown in Table 2, when solvent-free adhesive 7 (A, PES, DICY, 2PI) is used, the shear breaking force at room temperature is 67.5 MPa, and the shear breaking force at 150 ° C. Both were extremely high, 42.1 MPa. When the same solventless type adhesive 1 containing only the bisphenol A type epoxy resin monomer “JER828” as an epoxy resin is used, the shear breaking strength at 150 ° C. is 4.1 MPa. The heat resistance is greatly improved by improving the composition. Regarding the solvent-type adhesive 8, although the composition of the epoxy resin was improved, the shear breaking strength at room temperature was as extremely low as 5.3 MPa, and the adhesive strength was not exhibited at 150 ° C. This is because no curing aid is added. From this result, the adhesive 8 cannot be used as an adhesive as it is.
一方、エポキシ樹脂の組成を改良し、かつ硬化助剤として「２ＰＩ」を使用している溶剤型の接着剤９に関しては、常温下におけるせん断破断力は６５．５ＭＰａと極めて高く、無溶剤型の接着剤７と同等であった。この数値は溶剤型エポキシ接着剤として特筆すべきものである。また、１５０℃下におけるせん断破断力も３２．７ＭＰａと極めて高く、従来になく高い耐熱性を有する溶剤型エポキシ接着剤となった。接着剤９とエポキシ樹脂の組成のみが異なる接着剤４を比較しても、常温下におけるせん断破断力が１０ＭＰａ、１５０℃におけるせん断破断力に関しては２０ＭＰａも向上していることから、エポキシ樹脂の組成を改良した効果が明確に把握された。 On the other hand, for the solvent-type adhesive 9 that improves the composition of the epoxy resin and uses “2PI” as a curing aid, the shear breaking force at room temperature is as extremely high as 65.5 MPa. It was equivalent to adhesive 7. This value is notable as a solvent-type epoxy adhesive. In addition, the shear breaking force at 150 ° C. was as extremely high as 32.7 MPa, and thus a solvent-type epoxy adhesive having high heat resistance, which was unprecedented. Even when the adhesive 9 and the adhesive 4 differing only in the composition of the epoxy resin are compared, the shear breaking force at room temperature is 10 MPa, and the shear breaking force at 150 ° C. is improved by 20 MPa. The effect of improving was clearly grasped.
［実験例３１〜５２］（各種金属合金の接着試験）
実験例２〜１２の表面処理を施した各々の金属合金について、実験例２８と同様の実験を行った。即ち、無溶剤型の接着剤７（Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用した接着実験を行った。その結果を、表３に示す。また、実験例２〜１２の表面処理を施した各々の金属合金について、実験例３０と同様の実験を行った。即ち、溶剤型の接着剤９（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用した接着実験を行った。その結果を、表３に示す。いずれの金属合金が接着対象となった場合でも、本発明に係る溶剤型の１液性エポキシ接着剤である接着剤９は常温下において高い接着力を示し、１５０℃下における高い耐熱性を示した。本発明の溶剤型エポキシ接着剤は、実用面で十分に強固な接着を可能とするものであり、かつ耐熱性を兼備するものである。特に、接着対象がＡ７０７５アルミニウム合金、Ａ５０５２アルミニウム合金、ＫＦＣ銅合金、ＫＬＦ５銅合金、ＳＰＣＣ冷間圧延鋼材、及びＳＰＨＣ熱間圧延鋼材の場合には、無溶剤型の接着剤７と同等の接着力及び耐熱性が得られることを確認できた。
[Experimental examples 31 to 52] (Adhesion test of various metal alloys)
Experiments similar to Experiment 28 were performed on each metal alloy subjected to the surface treatment of Experiment Examples 2 to 12. That is, an adhesion experiment using a solventless adhesive 7 (A, PES, DICY, 2PI) was performed. The results are shown in Table 3. Moreover, the same experiment as Experimental Example 30 was performed about each metal alloy which performed the surface treatment of Experimental Examples 2-12. That is, an adhesion experiment using a solvent-type adhesive 9 (MIBK, A, PES, DICY, 2PI) was performed. The results are shown in Table 3. Regardless of which metal alloy is to be bonded, the adhesive 9 which is a solvent-type one-part epoxy adhesive according to the present invention exhibits high adhesive strength at room temperature and high heat resistance at 150 ° C. It was. The solvent-type epoxy adhesive of the present invention enables sufficiently strong adhesion in practical use and also has heat resistance. In particular, when the object to be bonded is A7075 aluminum alloy, A5052 aluminum alloy, KFC copper alloy, KLF5 copper alloy, SPCC cold-rolled steel material, and SPHC hot-rolled steel material, the same adhesive strength as the solventless adhesive 7 It was also confirmed that heat resistance was obtained.
［実験例５３］（ジシアンジアミド粉体の粒径確認）
「ＪＥＲ８２８」２００質量部（８００ｇ）とＭＩＢＫ１００質量部（４００ｇ）をビーカー内で混合して均一化し、低粘度の混合液３００質量部（１２００ｇ）を作成した。直径０．３ｍｍのジルコニアビーズを粉砕室容量の８０％充填したサンドグラインドミル「ツエア」を用意し、その入口側に循環ポンプと撹拌機付きのオープンタンクを繋いだ。一方、サンドグラインドミルの出口はオープンタンクに開放した。前記混合液のうち７５質量部（３００ｇ）をオープンタンクに投入し、循環ポンプで粉砕室を完全に満たしてからミルの運転を開始した。ミルには水冷ラインがあるので通水を調整して粉砕室内が５０℃以下になるようにした。ミル回転子の周速は１１〜１２ｍ／秒とした。
[Experimental Example 53] (Confirmation of particle diameter of dicyandiamide powder)
200 parts by mass (800 g) of “JER828” and 100 parts by mass (400 g) of MIBK were mixed and homogenized in a beaker to prepare 300 parts by mass (1200 g) of a low-viscosity liquid mixture. A sand grind mill “Zuea” filled with zirconia beads having a diameter of 0.3 mm and having a grinding chamber capacity of 80% was prepared, and a circulation pump and an open tank with a stirrer were connected to the inlet side. On the other hand, the exit of the sand grind mill was opened to an open tank. 75 parts by mass (300 g) of the mixed solution was charged into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, the water flow was adjusted so that the inside of the grinding chamber became 50 ° C. or lower. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.
その後、オープンタンクに硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」２質量部（８ｇ）を入れて、粉砕を３０分続けた後、湿式粉砕を終了し、ミルの出口をオープンタンクからポリエチ瓶に向くようにし、このポリエチ瓶内に混合物を得た。試験管にこの混合物３ｇを取り、これにＭＩＢＫを５ｇ加えてよく振り混ぜ、２日間放置した。その結果、試験管下部に沈殿が生じ上部は透明になった。この透明液部の大部分を捨て、さらにＭＩＢＫを加えて液量を戻し、よく振り混ぜて再び懸濁液とした上で２日間放置した。その結果、同様に試験管下部に沈殿が生じ上部は透明になった。この透明液部の大部分を捨て、さらにＭＩＢＫを加えて液量を戻し、よく振り混ぜて再び懸濁液とした。ピペットを使用して、この懸濁液を脱脂したガラス板の上に０．２ｃｃ滴下した。これを放置して乾燥させた。若干のエポキシ樹脂が残存しているためにＭＩＢＫが揮発した後もガラス板にジシアンジアミド粉末が付着する。このガラス板を３０００倍の光学顕微鏡で観察した結果、５μｍ以上の粒体が存在しないことを確認できた。なおジシアンジアミドを原料とした「ＤＩＣＹ７（ジャパンエポキシレジン社製）」はメーカーによると重量の５０％以上は数μｍ径以下の微粒子だが最大粒径物は粒径２５μｍまで含むとされる。光学顕微鏡の観察でガラス板を移動させて観察したが５μｍ以上の物は確認出来なかった。 After that, 2 parts by mass (8 g) of fine powder type dicyandiamide “DICY7” as a curing agent is put in the open tank, and after pulverization is continued for 30 minutes, the wet pulverization is finished and the outlet of the mill faces the polyethylene bottle from the open tank. A mixture was obtained in this polyethylene bottle. 3 g of this mixture was taken in a test tube, 5 g of MIBK was added thereto, and the mixture was shaken well and left for 2 days. As a result, precipitation occurred in the lower part of the test tube and the upper part became transparent. Most of the clear liquid was discarded, and MIBK was added to restore the liquid volume. The liquid was shaken well to form a suspension again and left for 2 days. As a result, similarly, precipitation occurred in the lower part of the test tube, and the upper part became transparent. Most of the transparent liquid was discarded, and MIBK was added to restore the liquid volume. Using a pipette, 0.2 cc of this suspension was dropped on a degreased glass plate. This was left to dry. Since some epoxy resin remains, the dicyandiamide powder adheres to the glass plate even after MIBK volatilizes. As a result of observing this glass plate with a 3000 × optical microscope, it was confirmed that there were no particles of 5 μm or more. According to the manufacturer, “DICY7 (manufactured by Japan Epoxy Resin Co.)” using dicyandiamide as a raw material is a fine particle having a diameter of several μm or less, but the maximum particle size is up to 25 μm. Observation with an optical microscope was carried out by moving the glass plate, but an object of 5 μm or more could not be confirmed.
［実験例５４］（接着剤１０（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）の作成）
実験例２７で作成した接着剤９（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）の無機充填材であるタルク「ハイミクロンＨＥ５」に代えて、アルミニウム粉体を使用したものを作成した。「ＪＥＲ８２８」を６０質量部、「ＪＥＲ１００４」を１５質量部、「ＪＥＲ１５４」を８質量部、及び「ＪＥＲ６３０」１７質量部をビーカーに取り、１６５℃とした熱風乾燥機内に放置して加熱し、固体型「ＪＥＲ１００４」を溶融すると同時によく撹拌し、全体を均一化した。その後、放冷し、エポキシ樹脂液として保管した。このエポキシ樹脂の組成比は、前述した式（i）〜式（iv）の全ての条件に合致する。
[Experimental Example 54] (Preparation of adhesive 10 (MIBK, A, PES, DICY, 2PI))
Instead of talc “High Micron HE5”, which is an inorganic filler of adhesive 9 (MIBK, A, PES, DICY, 2PI) prepared in Experimental Example 27, an aluminum powder was used. Take 60 parts by weight of "JER828", 15 parts by weight of "JER1004", 8 parts by weight of "JER154", and 17 parts by weight of "JER630" in a beaker and leave in a hot air drier at 165 ° C to heat. The solid type “JER1004” was melted and stirred at the same time to make the whole uniform. Then, it stood to cool and stored as an epoxy resin liquid. The composition ratio of this epoxy resin matches all the conditions of the above-mentioned formulas (i) to (iv).
このエポキシ樹脂液を２００質量部（８００ｇ）とＭＩＢＫ１００質量部（４００ｇ）をビーカー内で混合して均一化し、低粘度の混合液３００質量部（１２００ｇ）を作成した。直径０．３ｍｍのジルコニアビーズを粉砕室容量の８０％充填したサンドグラインドミル「ツエア（アシザワ・ファインテック株式会社製）」を用意し、その入口側に循環ポンプと撹拌機付きのオープンタンクを繋いだ。一方、サンドグラインドミルの出口はオープンタンクに開放した。前記混合液のうち７５質量部（３００ｇ）をオープンタンクに投入し、循環ポンプで粉砕室を完全に満たしてからミルの運転を開始した。ミルには水冷ラインがあるので通水を調整して粉砕室内が５０℃以下になるようにした。ミル回転子の周速は１１〜１２ｍ／秒とした。 200 parts by mass (800 g) of this epoxy resin solution and 100 parts by mass (400 g) of MIBK were mixed and homogenized in a beaker to prepare 300 parts by mass (1200 g) of a low-viscosity mixture. A sand grind mill “Tuea (made by Ashizawa Finetech Co., Ltd.)” filled with zirconia beads with a diameter of 0.3 mm and 80% of the grinding chamber capacity is prepared, and an open tank with a circulation pump and a stirrer is connected to the inlet side. It is. On the other hand, the exit of the sand grind mill was opened to an open tank. 75 parts by mass (300 g) of the mixed solution was charged into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, the water flow was adjusted so that the inside of the grinding chamber became 50 ° C. or lower. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.
その後、オープンタンクにヒュームドシリカ「アエロジルＲ８０５」を０．２質量部（０．８ｇ）徐々に入れて循環粉砕を進め、次いでＰＥＳ粉体「ＰＥＳ４１００ＭＰ」１．６質量部（６．４ｇ）を徐々に加えた後、６０分間湿式粉砕を続けた。その後、ミルの出口をオープンタンクからポリエチ瓶に向くようにし、このポリエチ瓶内に混合物を得た。この混合物中にはエポキシ樹脂１００質量部に対して、ＭＩＢＫ５０質量部、超微細無機充填材「アエロジルＲ８０５」０．４質量部、及び熱可塑性樹脂粉体「ＰＥＳ４１００ＭＰ」３．２質量部が含まれる。 Thereafter, 0.2 parts by mass (0.8 g) of fumed silica “Aerosil R805” was gradually added to the open tank, and the circulating pulverization was continued. Then, 1.6 parts by mass (6.4 g) of PES powder “PES4100MP” was added. After the slow addition, wet grinding was continued for 60 minutes. Thereafter, the outlet of the mill was directed from the open tank to the polyethylene bottle, and a mixture was obtained in the polyethylene bottle. This mixture contains 50 parts by mass of MIBK, 0.4 parts by mass of the ultrafine inorganic filler “Aerosil R805” and 3.2 parts by mass of the thermoplastic resin powder “PES4100MP” with respect to 100 parts by mass of the epoxy resin. .
次いで乳鉢に、前記混合物１５３．６質量部（２回分）、粒径分布の中心が１０μｍのアルミニウム粉体「フィラー用アルミニウムパウダー（東洋アルミニウム株式会社製）」１０質量部、硬化剤として微粉型ジシアンジアミド「ＤＩＣＹ７」４質量部、及び硬化助剤として２−フェニルイミダゾール粉体「２ＰＩ」２質量部を取って、これらをよく混練した。これをポリエチ瓶に取り、１日間室内で放置してエージングし、その後５℃とした冷蔵庫に保管した。この接着剤の名称を接着剤１０（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）とした。この接着剤の組成を表１に示す（実験例５４）。 Next, 153.6 parts by mass of the mixture (twice), 10 parts by mass of aluminum powder “aluminum powder for filler (manufactured by Toyo Aluminum Co., Ltd.)” having a particle size distribution center of 10 μm, and fine powder dicyandiamide as a curing agent. 4 parts by mass of “DICY7” and 2 parts by mass of 2-phenylimidazole powder “2PI” as a curing aid were taken and kneaded well. This was taken up in a polyethylene bottle, left aged indoors for 1 day, and then stored in a refrigerator at 5 ° C. The name of this adhesive was named Adhesive 10 (MIBK, A, PES, DICY, 2PI). The composition of this adhesive is shown in Table 1 (Experimental Example 54).
［実験例５５］（接着剤１０を使用した接着試験）
接着剤２（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ）に代えて、接着剤１０（ＭＩＢＫ、Ａ、ＰＥＳ、ＤＩＣＹ、２ＰＩ）を使用して実験例１７と同様の実験を行った。その結果を表２に示す（実験例５５）。表２に示すように、せん断破断力（３組の平均値）は常温下で６３．８ＭＰａ、１５０℃下で３７ＭＰａであり、少なくともタルクを使用したもの（接着剤９）と比較して接着力の低下はみられなかった。
[Experimental Example 55] (Adhesion test using adhesive 10)
An experiment similar to Experimental Example 17 was performed using the adhesive 10 (MIBK, A, PES, DICY, 2PI) instead of the adhesive 2 (MIBK, A, PES, DICY). The results are shown in Table 2 (Experimental example 55). As shown in Table 2, the shear breaking strength (average value of 3 sets) is 63.8 MPa at room temperature and 37 MPa at 150 ° C., and the adhesive strength is at least as compared with that using talc (adhesive 9). There was no decline.
３０…接合体
３１…金属合金片
３２…金属合金片
３３…接着範囲
４０…金属合金
４１…セラミック質層
４２…接着剤硬化物層
DESCRIPTION OF SYMBOLS 30 ... Bonded body 31 ... Metal alloy piece 32 ... Metal alloy piece 33 ... Bonding range 40 ... Metal alloy 41 ... Ceramic layer 42 ... Hardened adhesive layer
Claims (12)
前記エポキシ樹脂１００質量部に対してケトン系溶剤を３０質量部以上含み、
硬化剤としてジシアンジアミド粉体を含み、
硬化助剤として２−フェニルイミダゾール、３−（３，４−ジクロルフェニル）−１，１−ジメチルウレア、２−メチルイミダゾール、及びＮ，Ｎ’−ジメチルピペラジンから選択される１種以上を含み、
前記エポキシ樹脂１００質量部に対して粒径分布の中心が５〜２５μｍの無機充填材を１〜１５質量部含み、
前記ジシアンジアミド粉体は、当該溶剤型エポキシ接着剤中に分散されており、かつ粒径５μｍ以下の微粒子となっていることを特徴とする溶剤型エポキシ接着剤。 A solvent-type epoxy adhesive mainly composed of epoxy resin,
30 parts by mass or more of a ketone solvent with respect to 100 parts by mass of the epoxy resin,
Contains dicyandiamide powder as a curing agent,
As a curing aid, contains at least one selected from 2-phenylimidazole, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 2-methylimidazole, and N, N′-dimethylpiperazine ,
Particle size center of distribution of the inorganic filler of 5~25μm viewed 1-15 parts by including with respect to the epoxy resin 100 parts by weight,
The solvent type epoxy adhesive, wherein the dicyandiamide powder is dispersed in the solvent type epoxy adhesive and is a fine particle having a particle diameter of 5 μm or less .
前記エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂単量体のみからなることを特徴とする溶剤型エポキシ接着剤。 The solvent-type epoxy adhesive according to claim 1,
The epoxy resin comprises only a bisphenol A type epoxy resin monomer.
前記硬化助剤として２−フェニルイミダゾールを含むことを特徴とする溶剤型エポキシ接着剤。 The solvent-type epoxy adhesive according to claim 2,
A solvent-type epoxy adhesive comprising 2-phenylimidazole as the curing aid.
前記エポキシ樹脂は、
ビスフェノールＡ型エポキシ樹脂単量体、
分子量１０００〜２０００のビスフェノールＡ型エポキシ樹脂オリゴマー、
３個以上のエポキシ基を有する多官能型であって、かつフェノール樹脂型であるエポキシ樹脂、
及び、３個以上のエポキシ基を有する多官能型であって、フェノール樹脂型ではなく、常温で液状であるエポキシ樹脂
を含むことを特徴とする溶剤型エポキシ接着剤。 The solvent-type epoxy adhesive according to claim 1,
The epoxy resin is
Bisphenol A type epoxy resin monomer,
Bisphenol A type epoxy resin oligomer having a molecular weight of 1000 to 2000,
An epoxy resin which is a polyfunctional type having three or more epoxy groups and is a phenol resin type;
A solvent-type epoxy adhesive comprising a polyfunctional type having three or more epoxy groups, which is not a phenol resin type but an epoxy resin that is liquid at room temperature.
前記エポキシ樹脂は、
ビスフェノールＡ型エポキシ樹脂単量体をａ質量部、
分子量１０００〜２０００のビスフェノールＡ型エポキシ樹脂オリゴマーをｂ質量部、
３個以上のエポキシ基を有する多官能型であって、かつフェノール樹脂型であるエポキシ樹脂をｃ質量部、
３個以上のエポキシ基を有する多官能型であって、フェノール樹脂型ではなく、常温で液状であるエポキシ樹脂をｄ質量部含むものとし、
前記エポキシ樹脂を１００質量部としたときに、ａ＋ｂ＋ｃ＋ｄ＝１００であり、
且つ、９５≧ａ＋ｄ≧６８、３２≧ｃ＋ｄ≧１５、２２≧ｂ≧５、及び、ｄ≧７の全ての条件を満たし、
前記硬化助剤として２−フェニルイミダゾールを含むことを特徴とする溶剤型エポキシ接着剤。 The solvent-type epoxy adhesive according to claim 4,
The epoxy resin is
A mass part of bisphenol A type epoxy resin monomer,
B parts by mass of a bisphenol A type epoxy resin oligomer having a molecular weight of 1000 to 2000,
C parts by mass of an epoxy resin which is a polyfunctional type having three or more epoxy groups and is a phenolic resin type,
It is a polyfunctional type having three or more epoxy groups, and is not a phenol resin type, but contains d parts by mass of an epoxy resin that is liquid at room temperature,
When the epoxy resin is 100 parts by mass, a + b + c + d = 100,
And 95 ≧ a + d ≧ 68, 32 ≧ c + d ≧ 15, 22 ≧ b ≧ 5, and d ≧ 7 are all satisfied,
A solvent-type epoxy adhesive comprising 2-phenylimidazole as the curing aid.
前記エポキシ樹脂１００質量部に対して、前記硬化剤を２．５〜５．５質量部含み、前記硬化助剤として２−フェニルイミダゾールを１．２５〜２．７５質量部含むことを特徴とする溶剤型エポキシ接着剤。 The solvent-type epoxy adhesive according to claim 1 ,
2.5 to 5.5 parts by mass of the curing agent is included with respect to 100 parts by mass of the epoxy resin, and 1.25 to 2.75 parts by mass of 2-phenylimidazole is included as the curing aid. Solvent type epoxy adhesive.
前記ケトン系溶剤はメチルイソブチルケトンであることを特徴とする溶剤型エポキシ接着剤。 The solvent-type epoxy adhesive according to claim 1 ,
The solvent type epoxy adhesive, wherein the ketone solvent is methyl isobutyl ketone.
金属合金の表面に、輪郭曲線要素の平均長さ（ＲＳｍ）が０．８〜１０μｍ、最大高さ（Ｒｚ）が０．２〜５μｍであるミクロンオーダーの粗度を生じさせ、且つ、その粗度を有する面内に、５〜５００ｎｍ周期の超微細凹凸を形成し、且つ、表層を金属酸化物又は金属リン酸化物の薄層とするための表面処理を行う表面処理工程と、
前記表面処理工程を経た金属合金の表面に、前記溶剤型エポキシ接着剤を噴霧器によって噴霧する噴霧工程と、
前記噴霧工程を経た金属合金表面の溶剤成分を揮発させる揮発工程と、
前記揮発工程を経た金属合金の前記溶剤型エポキシ接着剤が噴霧された範囲と、当該金属合金と接着させる被着材を密着させた状態で固定し、前記エポキシ樹脂を硬化させることで両者を一体化する硬化工程と、
を含むことを特徴とする金属合金と被着材の接着方法。 A bonding method using the solvent-type epoxy adhesive according to claim 1 ,
On the surface of the metal alloy, a roughness on the order of microns having an average length (RSm) of the contour curve element of 0.8 to 10 μm and a maximum height (Rz) of 0.2 to 5 μm is generated, and the roughness A surface treatment step of performing surface treatment for forming ultrafine irregularities with a period of 5 to 500 nm in a plane having a degree and forming a surface layer as a thin layer of metal oxide or metal phosphate;
A spraying step of spraying the solvent-type epoxy adhesive onto the surface of the metal alloy that has undergone the surface treatment step with a sprayer;
A volatilization step for volatilizing the solvent component on the surface of the metal alloy that has undergone the spraying step;
The solvent-type epoxy adhesive of the metal alloy that has undergone the volatilization step is fixed in a state in which the solvent-type epoxy adhesive is sprayed and the adherend to be bonded to the metal alloy are in close contact, and the epoxy resin is cured to integrate both A curing step to become,
A method for adhering a metal alloy and an adherend, characterized by comprising:
前記金属合金は、アルミニウム合金、マグネシウム合金、銅合金、チタン合金、ステンレス鋼、及び鉄鋼材から選択されるいずれか１種であることを特徴とする接着方法。 The bonding method according to claim 8 ,
The metal alloy is any one selected from an aluminum alloy, a magnesium alloy, a copper alloy, a titanium alloy, stainless steel, and a steel material.
前記揮発工程を経た金属合金を密閉容器に封じて、その密閉容器内を一旦減圧後に昇圧する染み込まし工程をさらに含み、
当該染み込まし工程後に前記硬化工程を行うことを特徴とする接着方法。 The bonding method according to claim 9 ,
The metal alloy that has undergone the volatilization process is sealed in a sealed container, and further includes a step of soaking that the inside of the sealed container is once pressurized after being depressurized,
An adhesion method comprising performing the curing step after the soaking step.
前記噴霧工程を経た金属合金を密閉容器に封じて、その密閉容器内を一旦減圧後に昇圧する染み込まし工程をさらに含み、
当該染み込まし工程後に前記揮発工程を行うことを特徴とする接着方法。 The bonding method according to claim 9 ,
The metal alloy that has undergone the spraying step is sealed in a sealed container, and further includes a soaking step that pressurizes the inside of the sealed container once after decompression,
An adhesion method comprising performing the volatilization step after the soaking step.
前記揮発工程を行う際に、前記金属合金を加熱して当該金属合金表面に噴霧された溶剤型エポキシ接着剤の粘度を低下させ、その溶剤成分を揮発させると共に、そのエポキシ接着剤成分を前記超微細凹凸に侵入させることを特徴とする接着方法。
The bonding method according to claim 9 ,
In performing the volatilization step, the metal alloy is heated to reduce the viscosity of the solvent-type epoxy adhesive sprayed on the surface of the metal alloy, volatilizes the solvent component, and the epoxy adhesive component is A bonding method characterized in that it penetrates into fine irregularities.
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