JPH0528276B2 - - Google Patents
Info
- Publication number
- JPH0528276B2 JPH0528276B2 JP60220790A JP22079085A JPH0528276B2 JP H0528276 B2 JPH0528276 B2 JP H0528276B2 JP 60220790 A JP60220790 A JP 60220790A JP 22079085 A JP22079085 A JP 22079085A JP H0528276 B2 JPH0528276 B2 JP H0528276B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- epoxy resin
- rust
- aluminum
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000853 adhesive Substances 0.000 claims description 36
- 230000001070 adhesive effect Effects 0.000 claims description 36
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 claims description 16
- 239000000049 pigment Substances 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 17
- 230000002265 prevention Effects 0.000 description 9
- 238000004070 electrodeposition Methods 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- -1 glycidyl ester Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 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 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 210000003660 reticulum Anatomy 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004825 One-part adhesive Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009957 hemming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
産業上の利用分野
本発明は、新規な構造用接着剤に関し、特に防
錆性に優れる熱硬化性接着剤を提供するものであ
る。ドア、ボンネツト、トランクリツドなどのア
ウターパネルとインナーパネルの端縁部をヘミン
グ固定する場合の接着剤として有用である。
従来の技術
接着剤のうち、特に構造用接着剤は、金属と金
属の接合部分に使用され、その材料が受ける特定
の外力に対し、材料と同等またはそれ以上に耐え
る接着力を有し、あたかも、その接合部位と構造
物とが一体をなすほどの強力な接着性を示すこと
が必要である。このような構造用接着剤は、リベ
ツト止め、ボルト止め、溶接などの従来の工法に
代わつて、あるいはそれらと併用して、近時、航
空機産業、製缶、電気、電子工業分野において広
く採用されている。なかでも、自動車の車体組
立、接合において、例えばサイドドア、ボンネツ
ト、トランクなどプレス成型して得られるアウタ
ーパネル、インナーパネルとを組立、接合するに
際しては、かかる構造用接着剤が汎用されてい
る。ところで、構造用接着剤の要求性能として積
極的な防錆機能が求められるようになつている。
特に自動車業界においては、寒冷地向け輸出車に
対する防錆性が問題となつている。従来、寒冷地
では道路の凍結防止のため、岩塩や塩化カルシウ
ムなどの融雪剤がまかれ、そのために車体鋼板の
腐食を著しく早め、外観を損ない、耐久性を低下
させるので、構造用接着剤に対しても鉛丹やジン
ククロメートのような防錆顔料が配合されてき
た。しかしながら、これらの防錆顔料には重金属
（鉛・クロムなど）が含まれている。その毒性の
ために人畜に対する安全衛生上の危惧がもたれ、
問題点とされてきた。そこで、本発明者らはかか
る問題点の解決のために鋭意検討したところ、エ
ポキシ樹脂接着剤において、特殊なメタリン酸ア
ルミニウム系防錆顔料を配合すれば、接着機能を
阻害することなく、防錆性に優れる構造用接着剤
が得られることを見い出し、本発明を完成するに
至つた。
発明が解決しようとする問題点
自動車車体組立・接合において、インナーパネ
ルの外縁部に対し、アウターパネルの外縁部を車
体内方に向けてヘミング成形し、接着、水密気密
シールする際に、該構造用接着剤をインナーパネ
ル外縁部に線状に塗布したうえ、両外縁部をスポ
ツト溶接などで溶接することにより、インナーパ
ネルとアウターパネルを固着する組立方法が行わ
れている。
従来、この種の目的のために用いられる構造用
接着剤としては、防錆顔料およびスポツト溶接と
電着塗装ができるようにいくらか通電性を持たせ
るため、アルミニウムなどの金属粉を配合した一
液性加熱硬化型エポキシ樹脂系の構造用接着剤が
提案されている。しかしながら、この場合には、
後工程の電着塗装工程において、接着剤塗布面お
よび塗布周縁に対する電着塗料の塗着が悪く、し
かも、アルミニウムなど金属粉の電極反応により
水素ガスが発生するので、接着剤に多数ピンホー
ルが起こる。その結果、塩水噴霧装置による発錆
試験をすれば、24時間以内に接着剤塗布周縁界面
から発錆するなどの欠点がある。この点は、特に
自動車の軽量化に伴う薄肉鋼板の使用と相まつ
て、さらに重要な問題となつており、電着塗装も
可能で、防錆性に優れた改良された構造用接着剤
の開発がきわめて重大な課題となつている。かか
る観点から接着剤に防錆性を付与する検討、ある
いは電着塗装が可能なように通電性を付与する検
討など、多くの研究がなされているが、未だ満足
すべき金属構造用接着剤は実用化されていない。
かかる事情のもとに、本発明者らは、所望の構造
用接着剤を得るべく研究を重ねた結果、メタリン
酸アルミニウム亜鉛化合物および／またはアルカ
リ土類金属化合物とからなる防錆顔料を熱硬化性
エポキシ樹脂系接着剤成分とすることによつて、
従来品にくらべて、格段に防錆性能に優れた接着
剤を見い出し、本発明を完成するに至つた。
問題を解決するための手段
本発明は、(a)エポキシ当量150〜300のエポキシ
樹脂と、(b)ジシアンジアミド、４，4′−ジアミノ
ジフエニルスルホン、イミダゾール誘導体、Ｎ，
N′−ジアルキル尿素誘導体およびＮ，N′−ジア
ルキルチオ尿素誘導体より選ばれた少なくとも１
種の硬化剤と、(c)メタリン酸アルミニウムおよび
酸化亜鉛からなる防錆顔料を含むことを特徴とす
る無溶剤型熱硬化性エポキシ樹脂系構造用接着剤
を提供するものである。
本発明のエポキシ樹脂としては、通常のグリシ
ジルエーテル型、グリシジルエステル型、グリシ
ジルアミン型、線状脂肪族エポキサイド型、脂環
族エポキサイド型などから選ばれるエポキシ樹脂
が挙げられ、エポキシ当量150〜300の範囲のもの
である。これらのエポキシ樹脂は、所望の物性に
応じてその１種を単独で用いるか、あるいは２種
以上を組み合わせて使用する。特にウレタン変性
のエポキシ樹脂との併用が望ましい。通常のエポ
キシ樹脂とウレタン変性エポキシ樹脂との割合
は、硬化物の所望の強靭性の付与のために0.2：
0.8から、0.7：0.3の範囲とする。その硬化剤とし
ては、ジシアンジアミド、４，4′−ジアミノジフ
エニルスルホン、２−ｎ−ヘプタデシルイミダゾ
ールのようなイミダゾール誘導体、イソフタル酸
ジヒドラジド、Ｎ，N′−ジアルキル尿素誘導体、
Ｎ，N′−ジアルキルチオ尿素誘導体から選ばれ
る。
これらは、所望の硬化状態に応じて適宜組成物
中に配合されるが通常、エポキシ樹脂100部（重
量部、以下同じ）に対して１〜15部の範囲で好ま
しく用いられる。
本発明における防錆顔料は、メタリン酸アルミ
ニウムとしては、メタリン酸アルミニウムを含有
している物質であれば特に制限はない。
メタリン酸アルミニウムの結晶型としては、Ａ
型、Ｂ型、Ｃ型、Ｄ型等が知られている。
メタリン酸アルミニウムは、例えばアルミニウ
ム化合物とリン化合物をＰ／Al＝1.1〜３になる
ように反応させ、それを100〜200℃で乾燥させた
後、250〜450℃で焼成し、次いで、450〜900℃で
さらに焼成し、粉砕することによつて得られる。
また、市販のトリポリリン酸二水素アルミニウ
ムを、400〜900℃で焼成することによつても製造
できる。メタリン酸アルミニウムと酸化亜鉛は、
単なる乾式混合または水中で湿式混合したものを
脱水乾燥して樹脂へ添加してもよいし、別々に添
加することも可能である。
メタリン酸アルミニウムと酸化亜鉛の配合割合
はPHが４〜10の範囲になるようなものであれば、
特に制限はない。特にメタリン酸アルミニウムと
酸化亜鉛を配合したものは、PH５〜８であり、優
れた防錆性を示し、樹脂選択性も少ない。
本発明の防錆顔料は、特に接着剤に使用される
場合に低温遊離の結晶水を持たないため、接着膜
が発泡を起こす心配がなく、優れた防錆性を示
す。
次に、エポキシ樹脂に混合して接着剤とすると
きの混合比率は、エポキシ樹脂100部に対して５
〜50部の範囲とするのが望ましい。５部未満であ
れば所望の樹脂組成物の防錆性が得られない。ま
た50部以上となれば、樹脂組成物の硬化物の物性
が脆弱となる傾向にあり、接着剤としての用途に
は望ましくない。
鋼板の防錆性を向上させるためには、本発明の
樹脂組成物の硬化物の表面に電着塗装ができるよ
うにするため、カーボンブラツク、金属粉（銀、
銅、ニツケルなど）、フエライトなどの導電性物
質を配合するのが望ましい。使用量はエポキシ樹
脂100部に対して１〜30部の範囲で選定する。
実施例
本発明をさらに詳細に説明するため、以下に試
作例、実施例を示す。
メタリン酸アルミニウムの試作例
(1) 85％リン酸216.0ｇと、水酸化アルミニウ
ム（Al2O3として59％のもの）58.0ｇとをビ
ーカーで反応させ、これを200℃で乾燥させ
た後、300℃で２時間、ついで900℃で２時間
焼成し、粉砕することによつてサンプル
（）を得た。
このメタリン酸アルミニウムは、主成分は
Ａ型で、少量のＢ型を含むものであり、結晶
水量は、0.28％であつた。
(2) 市販のトリポリリン酸二水素アルミニウム
（帝国化工製、Ｋ−フレツシユ＃100P）を
900℃で２時間焼成してサンプル（）を得
た。このメタリン酸アルミニウムは、Ａ型と
少量のＢ型とが混在するものであり、結晶水
量は0.33％であつた。
防錆顔料の試作例
(1) サンプル（）およびサンプル（）それ
ぞれに、酸化亜鉛を重量比で10：４になるよ
うに乾式混合し、防錆顔料ａおよびｂを得
た。
これらの顔料のPHは、ａが7.1、ｂが6.9で
あつた。
(2) 市販のトリポリリン酸二水素アルミニウム
（帝国化工製、Ｋ−フレツシユ＃100P）に、
酸化亜鉛を重量比で10：２になるように乾式
混合し、防錆顔料ｃを得た。この顔料のPHは
6.3であつた。
実施例１〜５、比較例１、２
表１に示す部数の成分をニーダーで混練したの
ち、三本ロールに２回通し、再びニーダーにて脱
泡撹拌を行い、樹脂組成物を調製した。なお、比
較例も同様にして樹脂組成物を得た。
INDUSTRIAL APPLICATION FIELD The present invention relates to a novel structural adhesive, and in particular provides a thermosetting adhesive with excellent rust prevention properties. It is useful as an adhesive for hemming and fixing the edges of outer and inner panels of doors, bonnets, trunk lids, etc. BACKGROUND ART Among adhesives, structural adhesives in particular are used for joints between metals, and have adhesive strength that is equal to or greater than the specific external force that the material is subjected to. , it is necessary to exhibit such strong adhesion that the joint portion and the structure become integral. These structural adhesives have recently been widely adopted in the aircraft industry, can manufacturing, electrical and electronics industries, instead of or in combination with traditional construction methods such as riveting, bolting, and welding. ing. Among these, such structural adhesives are widely used in assembling and joining automobile bodies, for example, when assembling and joining outer panels and inner panels obtained by press molding such as side doors, bonnets, and trunks. Incidentally, as a required performance of structural adhesives, active anti-corrosion function is now required.
Particularly in the automobile industry, rust prevention for cars exported to cold regions has become a problem. Traditionally, snow-melting agents such as rock salt and calcium chloride are sprinkled on roads in cold regions to prevent them from freezing. This significantly accelerates the corrosion of car body steel plates, impairs their appearance, and reduces their durability. Anti-rust pigments such as red lead and zinc chromate have also been added to these materials. However, these anti-rust pigments contain heavy metals (lead, chromium, etc.). Due to its toxicity, there are health and safety concerns for humans and livestock.
It has been considered a problem. Therefore, the inventors of the present invention conducted extensive studies to solve this problem, and found that if a special aluminum metaphosphate rust-preventing pigment is added to the epoxy resin adhesive, it will prevent rust without impairing the adhesive function. The inventors have discovered that a structural adhesive with excellent properties can be obtained, and have completed the present invention. Problems to be Solved by the Invention In assembling and joining automobile bodies, when the outer edge of the outer panel is hemmed toward the inner edge of the inner panel to form an adhesive and watertight seal, the structure An assembly method is used in which the inner panel and the outer panel are fixed by applying a linear adhesive to the outer edge of the inner panel and then welding both outer edges by spot welding or the like. Traditionally, structural adhesives used for this type of purpose are one-part adhesives containing anti-rust pigments and metal powders such as aluminum to provide some electrical conductivity for spot welding and electrodeposition coating. Structural adhesives based on thermosetting epoxy resins have been proposed. However, in this case,
In the post-electrodeposition coating process, the electrodeposition paint does not adhere well to the adhesive coating surface and the coating periphery, and hydrogen gas is generated due to the electrode reaction of metal powder such as aluminum, resulting in many pinholes in the adhesive. happen. As a result, if a rusting test is conducted using a salt spray device, there are drawbacks such as rusting from the adhesive application peripheral interface within 24 hours. This has become an even more important issue, especially with the use of thinner steel sheets to reduce the weight of automobiles, and the development of improved structural adhesives that can be electroplated and have excellent rust prevention properties. has become an extremely important issue. From this point of view, many studies have been carried out, including studies on imparting rust prevention properties to adhesives and studies on imparting electrical conductivity to enable electrodeposition coating, but there are still no satisfactory adhesives for metal structures. Not put into practical use.
Under these circumstances, the present inventors conducted repeated research to obtain a desired structural adhesive. As a result, the present inventors developed a heat-curable rust preventive pigment consisting of an aluminum zinc metaphosphate compound and/or an alkaline earth metal compound. By using a polyester epoxy resin adhesive component,
We have discovered an adhesive with significantly superior anti-rust performance compared to conventional products, and have completed the present invention. Means for Solving the Problem The present invention comprises (a) an epoxy resin having an epoxy equivalent of 150 to 300, (b) dicyandiamide, 4,4'-diaminodiphenylsulfone, an imidazole derivative, N,
At least one selected from N'-dialkyl urea derivatives and N,N'-dialkylthiourea derivatives
The present invention provides a solvent-free thermosetting epoxy resin structural adhesive characterized by containing a seed curing agent and (c) an anticorrosive pigment consisting of aluminum metaphosphate and zinc oxide. The epoxy resin of the present invention includes epoxy resins selected from ordinary glycidyl ether type, glycidyl ester type, glycidyl amine type, linear aliphatic epoxide type, alicyclic epoxide type, etc., and has an epoxy equivalent of 150 to 300. It's a range of things. These epoxy resins may be used singly or in combination of two or more depending on the desired physical properties. In particular, it is desirable to use it in combination with a urethane-modified epoxy resin. The ratio of normal epoxy resin to urethane-modified epoxy resin is 0.2 in order to impart the desired toughness to the cured product.
The range is from 0.8 to 0.7:0.3. The curing agents include dicyandiamide, 4,4'-diaminodiphenylsulfone, imidazole derivatives such as 2-n-heptadecyl imidazole, isophthalic acid dihydrazide, N,N'-dialkyl urea derivatives,
selected from N,N'-dialkylthiourea derivatives. These are appropriately blended into the composition depending on the desired cured state, but are usually preferably used in an amount of 1 to 15 parts per 100 parts (parts by weight, same hereinafter) of the epoxy resin. The anticorrosive pigment in the present invention is not particularly limited as long as the aluminum metaphosphate is a substance containing aluminum metaphosphate. The crystal form of aluminum metaphosphate is A
Types such as type, B type, C type, and D type are known. Aluminum metaphosphate is produced by, for example, reacting an aluminum compound and a phosphorus compound so that P/Al=1.1 to 3, drying it at 100 to 200°C, calcining it at 250 to 450°C, and then Obtained by further firing at 900°C and pulverizing. It can also be produced by firing commercially available aluminum dihydrogen tripolyphosphate at 400 to 900°C. Aluminum metaphosphate and zinc oxide are
They may be simply dry mixed or wet mixed in water, dehydrated and then added to the resin, or they may be added separately. If the mixing ratio of aluminum metaphosphate and zinc oxide is such that the pH is in the range of 4 to 10,
There are no particular restrictions. In particular, those containing aluminum metaphosphate and zinc oxide have a pH of 5 to 8, exhibit excellent rust prevention properties, and have low resin selectivity. The rust-preventing pigment of the present invention, especially when used in adhesives, does not have low-temperature free crystal water, so there is no fear that the adhesive film will foam, and it exhibits excellent rust-preventing properties. Next, when mixing with epoxy resin to make an adhesive, the mixing ratio is 5 parts to 100 parts of epoxy resin.
Preferably, the amount is in the range of ~50 parts. If the amount is less than 5 parts, the desired rust prevention properties of the resin composition cannot be obtained. Further, if the amount exceeds 50 parts, the physical properties of the cured resin composition tend to become weak, which is not desirable for use as an adhesive. In order to improve the rust prevention properties of steel sheets, carbon black, metal powder (silver,
It is desirable to incorporate conductive substances such as copper, nickel, etc.) and ferrite. The amount used is selected in the range of 1 to 30 parts per 100 parts of epoxy resin. Examples In order to explain the present invention in more detail, prototype examples and examples are shown below. Prototype example of aluminum metaphosphate (1) 216.0 g of 85% phosphoric acid and 58.0 g of aluminum hydroxide (59% Al 2 O 3 ) were reacted in a beaker, and after drying at 200°C, A sample () was obtained by firing at 300°C for 2 hours, then at 900°C for 2 hours, and pulverizing. The main component of this aluminum metaphosphate was type A and a small amount of type B, and the amount of crystallization water was 0.28%. (2) Commercially available aluminum dihydrogen tripolyphosphate (manufactured by Teikoku Kako, K-Freshyu #100P)
A sample () was obtained by firing at 900°C for 2 hours. This aluminum metaphosphate contained a mixture of type A and a small amount of type B, and the amount of water of crystallization was 0.33%. Prototype Example of Rust-preventing Pigment (1) Sample () and Sample () were dry-mixed with zinc oxide at a weight ratio of 10:4 to obtain rust-preventing pigments a and b. The pH of these pigments was 7.1 for a and 6.9 for b. (2) Commercially available aluminum dihydrogen tripolyphosphate (manufactured by Teikoku Kako, K-Freshyu #100P),
Zinc oxide was dry mixed at a weight ratio of 10:2 to obtain antirust pigment c. The pH of this pigment is
It was 6.3. Examples 1 to 5, Comparative Examples 1 and 2 After kneading the components in the parts shown in Table 1 using a kneader, the mixture was passed through a three-roll roll twice and defoamed and stirred using the kneader again to prepare a resin composition. In addition, a resin composition was obtained in the same manner as a comparative example.
【表】
エポキシ樹脂：油化シエル(株)製、エピコート
807
エポキシ樹脂：ポリテトラメチレンエーテルグ
リコール（分子量1000）100部とトリレンジイ
ソシアネート35部を窒素置換したフラスコ中に
て混合し、80℃まで昇温し、３時間撹拌しなが
ら反応して末端NCO基を有するウレタンポリ
マーを得る。次いで、このウレタンポリマー45
部にビスフエノールＡのジグリシジルエーテル
（エポキシ当量215、水酸基当量900）250部を加
え、95℃で７時間反応させたエポキシ当量200
のエポキシ樹脂
イミダゾール：四国化成工業(株)製、2MZ−
AZINE
カーボンブロツク：アクゾ社製、ケツチエンブ
ラツクEC
評価方法と評価結果
（発錆性の評価）
トルエン脱脂した鋼板（70×100×0.8mm）に実
施例１〜５および比較例１、２で調整した樹脂
組成物を30巾mmで厚さを５mmから0.5mmに徐々
に薄く傾斜をつけて塗布した後、200ボルト、
0.5アンペアで加電した状態で電着塗装を行う。
（電着塗料としては関西ペイント(株)性、カチオ
ン電着塗料を使用）その後水洗し、170℃で30
分間加熱硬化する。この試験体を次のような発
錆性試験条件で発錆性の評価を行つた。
発錆性試験条件：35℃、５％の塩水霧試験1000
時間
発錆性試験条件：湿潤条件（50℃、95％RH）
16時間
乾燥条件（70℃）４時間
塩水噴霧条件（35℃、５％水）４時間
上記３条件を60サイクル
発錆性試験条件：湿潤条件（同上）６時間
乾燥条件（60℃）２時間
冷寒条件（−40℃）２時間
乾燥条件（20℃）２時間
上記条件を100サイクル
（接着性の評価）
トルエン脱脂した鋼板（100×25×1.6mm）を接
着ラツプが12.5mmとなるように樹脂組成物を塗布
し、一方の鋼板を張り合わせてせん断接着試験体
を作成し、170℃で30分間加熱硬化した後、室温
で24時間放置後、せん断接着強度を測定する。
（評価結果）
表２に発錆性と接着強度の評価結果を示す。[Table] Epoxy resin: Manufactured by Yuka Ciel Co., Ltd., Epicoat
807 Epoxy resin: 100 parts of polytetramethylene ether glycol (molecular weight 1000) and 35 parts of tolylene diisocyanate are mixed in a flask purged with nitrogen, heated to 80°C, and reacted with stirring for 3 hours to form terminal NCO groups. A urethane polymer having the following properties is obtained. Next, this urethane polymer 45
250 parts of diglycidyl ether of bisphenol A (epoxy equivalent: 215, hydroxyl equivalent: 900) was added to 1 part, and the mixture was reacted at 95°C for 7 hours to obtain an epoxy equivalent of 200.
Epoxy resin imidazole: manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MZ-
AZINE Carbon block: manufactured by Akzo Co., Ltd., KETSUTIEN BLACK EC Evaluation method and evaluation results (rusting property evaluation) Prepared according to Examples 1 to 5 and Comparative Examples 1 and 2 on a toluene-degreased steel plate (70 x 100 x 0.8 mm) After applying the resin composition to a width of 30 mm and gradually increasing the thickness from 5 mm to 0.5 mm, 200 volts was applied.
Electrodeposition painting is performed with a current of 0.5 ampere applied.
(The electrodeposition paint used was Kansai Paint Co., Ltd.'s cationic electrodeposition paint.) After that, it was washed with water and heated to 170℃ for 30 minutes.
Heat and cure for minutes. The rusting properties of this test specimen were evaluated under the following rusting test conditions. Rustability test conditions: 35℃, 5% salt fog test 1000
Time rusting test conditions: Humid conditions (50℃, 95%RH)
16 hours Dry conditions (70℃) 4 hours Salt water spray conditions (35℃, 5% water) 4 hours 60 cycles of the above three conditions Rust development test conditions: Wet conditions (same as above) 6 hours Dry conditions (60℃) 2 hours Cold condition (-40℃) 2 hours Dry condition (20℃) 2 hours 100 cycles of the above conditions (adhesion evaluation) Toluene-degreased steel plate (100 x 25 x 1.6 mm) so that the adhesive lap is 12.5 mm A shear adhesion test specimen was prepared by applying a resin composition to the resin composition and pasting one steel plate together. After curing by heating at 170°C for 30 minutes, and standing at room temperature for 24 hours, the shear adhesion strength was measured. (Evaluation Results) Table 2 shows the evaluation results of rust resistance and adhesive strength.
【表】
発明の効果
本発明は、従来の構造用接着剤が抱えている防
錆機能の問題を解決し、かつ優れた接着力を発揮
するものである。
すなわち、本発明の構造用接着剤は、エポキシ
樹脂系バインダーとメタリン酸アルミニウム、酸
化亜鉛からなる防錆顔料との相乗効果によつて、
格段の接着性と防錆性とを与えるものである。[Table] Effects of the Invention The present invention solves the problem of rust prevention function that conventional structural adhesives have and exhibits excellent adhesive strength. That is, the structural adhesive of the present invention has a synergistic effect between the epoxy resin binder and the rust-preventing pigment consisting of aluminum metaphosphate and zinc oxide.
It provides outstanding adhesion and rust prevention properties.
Claims (1)
(b)ジシアンジアミド、４，4′−ジアミノジフエニ
ルスルホン、イミダゾール誘導体、イソフタル酸
ジヒドラジド、Ｎ，N′−ジアルキル尿素誘導体
およびＮ，N′−ジアルキルチオ尿素誘導体より
選ばれる少なくとも１種の硬化剤と、(c)メタリン
酸アルミニウムおよび酸化亜鉛からなる防錆顔料
を含むことを特徴とする無溶剤型熱硬化性エポキ
シ樹脂系構造用接着剤。 ２ メタリン酸アルミニウムの50％以上がＡ型で
ある特許請求の範囲第１項の接着剤。[Claims] 1. (a) an epoxy resin having an epoxy equivalent of 150 to 300;
(b) at least one curing agent selected from dicyandiamide, 4,4'-diaminodiphenylsulfone, imidazole derivatives, isophthalic acid dihydrazide, N,N'-dialkyl urea derivatives and N,N'-dialkylthiourea derivatives; , (c) A solvent-free thermosetting epoxy resin structural adhesive characterized by containing a rust-preventing pigment consisting of aluminum metaphosphate and zinc oxide. 2. The adhesive according to claim 1, wherein 50% or more of the aluminum metaphosphate is type A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22079085A JPS6279282A (en) | 1985-10-02 | 1985-10-02 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22079085A JPS6279282A (en) | 1985-10-02 | 1985-10-02 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6279282A JPS6279282A (en) | 1987-04-11 |
| JPH0528276B2 true JPH0528276B2 (en) | 1993-04-23 |
Family
ID=16756605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22079085A Granted JPS6279282A (en) | 1985-10-02 | 1985-10-02 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6279282A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0726080B2 (en) * | 1987-11-30 | 1995-03-22 | サンスター技研株式会社 | Structural adhesive with high corrosion resistance |
| JP2694979B2 (en) * | 1988-11-15 | 1997-12-24 | サンスター技研株式会社 | Adhesive composition |
| JPH10152664A (en) * | 1996-11-26 | 1998-06-09 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor system prepared by using the same |
| JPH11116856A (en) * | 1997-10-14 | 1999-04-27 | Kobe Paint Kk | Rustproofing coating composition |
| CN111269676A (en) * | 2018-12-04 | 2020-06-12 | 北京航天试验技术研究所 | Strong acid resistant and fast-curing phosphate-based composite plugging agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930280A (en) * | 1972-07-19 | 1974-03-18 | ||
| JPS5688452A (en) * | 1979-12-21 | 1981-07-17 | Toshiba Corp | Epoxy resin-based molding material |
| JPS56129284A (en) * | 1980-03-17 | 1981-10-09 | Akebono Brake Ind Co Ltd | Friction material |
| JPS56131671A (en) * | 1980-03-19 | 1981-10-15 | Kansai Paint Co Ltd | Coating composition for metal container |
| JPS60220791A (en) * | 1984-04-18 | 1985-11-05 | Seiko Epson Corp | Printing system |
-
1985
- 1985-10-02 JP JP22079085A patent/JPS6279282A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930280A (en) * | 1972-07-19 | 1974-03-18 | ||
| JPS5688452A (en) * | 1979-12-21 | 1981-07-17 | Toshiba Corp | Epoxy resin-based molding material |
| JPS56129284A (en) * | 1980-03-17 | 1981-10-09 | Akebono Brake Ind Co Ltd | Friction material |
| JPS56131671A (en) * | 1980-03-19 | 1981-10-15 | Kansai Paint Co Ltd | Coating composition for metal container |
| JPS60220791A (en) * | 1984-04-18 | 1985-11-05 | Seiko Epson Corp | Printing system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6279282A (en) | 1987-04-11 |
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