JP4911979B2 - Water-soluble cleaning agent - Google Patents
Water-soluble cleaning agent Download PDFInfo
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- JP4911979B2 JP4911979B2 JP2006019465A JP2006019465A JP4911979B2 JP 4911979 B2 JP4911979 B2 JP 4911979B2 JP 2006019465 A JP2006019465 A JP 2006019465A JP 2006019465 A JP2006019465 A JP 2006019465A JP 4911979 B2 JP4911979 B2 JP 4911979B2
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- 239000012459 cleaning agent Substances 0.000 title claims description 58
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003599 detergent Substances 0.000 claims description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- 150000004665 fatty acids Chemical class 0.000 claims description 21
- 238000010894 electron beam technology Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- -1 alicyclic amine Chemical class 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 150000003333 secondary alcohols Chemical class 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000003466 welding Methods 0.000 description 68
- 229910052751 metal Inorganic materials 0.000 description 43
- 239000002184 metal Substances 0.000 description 43
- 238000004140 cleaning Methods 0.000 description 36
- 238000002845 discoloration Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 17
- 239000000344 soap Substances 0.000 description 14
- 230000007547 defect Effects 0.000 description 10
- 230000003405 preventing effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000010336 energy treatment Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004649 discoloration prevention Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HHPDFYDITNAMAM-UHFFFAOYSA-N 2-[cyclohexyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C1CCCCC1 HHPDFYDITNAMAM-UHFFFAOYSA-N 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
Description
本発明は、水溶性洗浄剤に関し、特に、電子ビーム溶接等の高エネルギー処理を受けるワークの前処理においてワーク表面に付着した有機物を洗浄、除去するとともに、金属ワーク表面をプロテクトし、電子ビーム溶接等の高エネルギー処理に際してワーク表面の変色を防止するのに好適な水溶性洗浄剤に関する。 The present invention relates to a water-soluble cleaning agent, and in particular, cleans and removes organic substances adhering to a work surface in a pre-treatment of a work subjected to high energy treatment such as electron beam welding, and protects a metal work surface, thereby performing electron beam welding. The present invention relates to a water-soluble cleaning agent suitable for preventing discoloration of the workpiece surface during high energy processing such as.
従来、金属加工油やロジン系フラックス等の汚染物質が付着したアルミニウム合金製精密部品、銅合金製精密部品に対する洗浄剤としては、ＣＦＣ１１３や、１．１．１−トリクロロエタン等が広く使用されていた。 Conventionally, CFC113, 1.1.1-trichloroethane, and the like have been widely used as cleaning agents for aluminum alloy precision parts and copper alloy precision parts to which contaminants such as metalworking oil and rosin flux have adhered. .
しかしながら、これらの洗浄剤は現在、オゾン層破壊物質として認識され、その永続的使用に厳しい制約を受ける状況に到っている。 However, these cleaning agents are now recognized as ozone-depleting substances and have come to severe restrictions on their permanent use.
そこで、これら洗浄剤の代替洗浄剤として、（１）アルコール類や石油系炭化水素類、（２）グリコールエーテル類、界面活性剤類、及び水などを主体とする水系洗浄剤や準水系洗浄剤などが候補として挙げられ、利用検討が進んでいるものの、上記（１）のアルコール類や石油系炭化水素類は可燃性で比較的低い引火点を有し、洗浄現場における取扱い安全性に多大の労力が必要となるばかりでなく、その安全対策投資に多大な経済投資が強いられるので、今日においては、上記した（２）の準水系洗浄剤を含む水系洗浄剤に大きな期待が寄せられている。 Therefore, as an alternative cleaning agent for these cleaning agents, (1) alcohols and petroleum hydrocarbons, (2) glycol ethers, surfactants, water-based cleaning agents and semi-aqueous cleaning agents mainly composed of water, etc. However, the alcohols and petroleum hydrocarbons of (1) are flammable and have a relatively low flash point, which greatly increases the handling safety at the cleaning site. Not only labor is required, but also a great deal of economic investment is required to invest in safety measures. Today, there are high expectations for water-based cleaning agents including the quasi-aqueous cleaning agent (2) described above. .
しかしながら、上記（２）の準水系洗浄剤を含む水系洗浄剤は、洗浄剤自身の液性により、また洗浄対象物質（被洗浄汚染物）が洗浄剤の液性に対して及ぼす影響により、並びに洗浄時洗浄液に含まれる水の存在により、ＣＦＣ１１３や１．１．１−トリクロロエタン、アルコール類や石油系炭化水素類などの非水系洗浄剤類では発現しなかった新たな問題、すなわち構成特定金属成分が変色したり、溶出するという問題が発生し、対象金属部品類の品質維持が困難であった。なお、ベンゾトリアゾール、ベンゾチアゾール等の防錆剤やリン酸根を有すアニオン界面活性剤を使用しても金属部品類における特定金属の溶出抑制効果はある程度期待されるが、その有効効果を発現させるには添加絶対量を多く要し、また、残存成分が安定外観維持や絶縁信頼性などの実用上の問題を惹起する欠点があった。 However, the water-based cleaning agent containing the quasi-aqueous cleaning agent of (2) above is due to the liquidity of the cleaning agent itself, the influence of the substance to be cleaned (contaminated matter to be cleaned) on the liquidity of the cleaning agent, and Due to the presence of water contained in the cleaning solution at the time of cleaning, a new problem that did not appear in non-aqueous cleaning agents such as CFC113, 1.1.1-trichloroethane, alcohols and petroleum hydrocarbons, ie, constituent specific metal components Discoloration or elution occurred, and it was difficult to maintain the quality of the target metal parts. Although the use of rust preventives such as benzotriazole and benzothiazole and anionic surfactants with phosphate radicals is expected to some extent to suppress the elution of specific metals in metal parts, the effectiveness is manifested. In addition, a large amount of the additive is required, and the remaining components have disadvantages that cause practical problems such as stable appearance maintenance and insulation reliability.
今日、多くの水系洗浄剤は各工業分野で幅広く用いられており、その有用性は明らかであるが、一部の素材では洗浄履歴により素材の変色や特定金属成分の溶出による問題が生じていた。 Today, many water-based cleaning agents are widely used in various industrial fields, and their usefulness is clear. However, some materials have problems caused by discoloration of materials and elution of specific metal components due to cleaning history. .
そこで、下記特許文献１には、被洗浄物である金属部品類における金属の溶出を低濃度の使用で最小限に抑え、また被洗浄物の変色を防止して外観変化の問題を解決し得る水系洗浄剤用添加剤によって、金属の溶出並びに変色を抑えることを目的として、金属部品類を洗浄するための水系洗浄液の中にパーフルオロアルキルリン酸エステル系界面活性剤を水系洗浄液に対して０．０１〜１．０重量％添加する発明が開示されている。 Therefore, Patent Document 1 below can solve the problem of appearance change by minimizing the elution of metal in the metal parts that are the object to be cleaned by using a low concentration and preventing the object to be discolored. For the purpose of suppressing metal elution and discoloration with the aqueous detergent additive, a perfluoroalkyl phosphate surfactant is added to the aqueous detergent to wash the metal parts. An invention of adding 0.01 to 1.0% by weight is disclosed.
他方、金属部品の溶接には、電子ビーム溶接、レーザー溶接等の種々の溶接法が用いられる。例えば、電子ビーム溶接では、真空室の中で高速の電子ビームを金属部品に照射して溶接を行う。この際、被溶接物である金属部品の表面に加工油、乳化油等の有機物が付着していると、溶接時の熱により該有機物がガス化する。溶融状態の金属内部からガスが噴出することで、ブローホールやスパッタを生じる。このように、被溶接物の表面に付着した有機物は、溶接不良を引き起こす原因となる。そのため、溶接前には、被溶接物の表面を洗浄することが必要となる。 On the other hand, various welding methods such as electron beam welding and laser welding are used for welding metal parts. For example, in electron beam welding, welding is performed by irradiating a metal part with a high-speed electron beam in a vacuum chamber. At this time, if an organic substance such as processing oil or emulsified oil adheres to the surface of the metal part to be welded, the organic substance is gasified by heat during welding. Blow holes and spatter are generated by gas jetting from inside the molten metal. Thus, the organic matter adhering to the surface of the workpiece is a cause of poor welding. Therefore, it is necessary to clean the surface of the workpiece before welding.
被溶接物の表面洗浄に用いる洗浄剤として、種々の成分のものが提案されている。例えば、下記特許文献２には、所定の構造を有する界面活性剤と、カチオン系油水分離剤であるポリアルキレンポリアミンジシアンアンモニウムクロライドとを含む水溶性洗浄剤が示されている。 Various cleaning agents have been proposed as cleaning agents used for cleaning the surface of the workpiece. For example, Patent Document 2 below discloses a water-soluble cleaning agent containing a surfactant having a predetermined structure and a polyalkylene polyamine dicyanammonium chloride which is a cationic oil-water separator.
特許文献２に示された水溶性洗浄剤は、カチオン系油水分離剤を配合し、洗浄液の油水分離性を向上させている。つまり、被洗浄物表面から加工油を除去するとともに、除去された加工油と界面活性剤とが結合したエマルジョンを洗浄液から分離、除去し易くし、エマルジョンの被洗浄物への再付着を抑制している。 The water-soluble cleaning agent disclosed in Patent Document 2 contains a cationic oil / water separating agent to improve the oil / water separating property of the cleaning liquid. In other words, the processing oil is removed from the surface of the object to be cleaned, and the emulsion in which the removed processing oil and the surfactant are combined is easily separated and removed from the cleaning liquid, and the reattachment of the emulsion to the object to be cleaned is suppressed. ing.
しかし、カチオン系油水分離剤は、被洗浄物である金属材料に吸着し易いため、洗浄後に被洗浄物の表面に残留し易い。残留したカチオン系油水分離剤は、溶接時の熱によりガス化して、ブローホールやスパッタの原因となる。また、燃焼後に煤やヤニ等の燃えかすが残り、それにより溶接不良が引き起こされるおそれもある。 However, since the cationic oil-water separator is easily adsorbed on the metal material that is the object to be cleaned, it tends to remain on the surface of the object to be cleaned after cleaning. The remaining cationic oil-water separating agent is gasified by heat during welding and causes blowholes and spatter. In addition, there is a risk that soot and spear remain after combustion, which may cause poor welding.
電子ビーム溶接の際にスパッタが発生すると、それにより真空室のシール材が劣化して空気漏れが生じる。真空度が低下すると、アーキング（異常放電）を招くおそれがある。加えて、溶接時に煤等が生じると、真空ポンプが汚染され不具合を生じる。 If spatter occurs during electron beam welding, the sealing material in the vacuum chamber deteriorates and air leakage occurs. When the degree of vacuum decreases, there is a risk of causing arcing (abnormal discharge). In addition, if flaws or the like are generated during welding, the vacuum pump is contaminated and causes a malfunction.
このように、洗浄剤の成分により、溶接不良や溶接装置の不具合が引き起こされる場合がある。したがって、溶接前の洗浄に使用する洗浄剤は、溶接不良等の原因となり得る成分をできるだけ含まないことが望ましい。換言すれば、該洗浄剤を、溶接性を阻害し難い成分で構成することが望ましい。 As described above, the components of the cleaning agent may cause poor welding or defects in the welding apparatus. Therefore, it is desirable that the cleaning agent used for cleaning before welding does not contain as much components as possible that may cause welding defects. In other words, it is desirable that the cleaning agent is composed of a component that is difficult to inhibit weldability.
さらに、被洗浄物の表面には、金属石鹸が付着していることが多い。金属石鹸は、金属イオンと脂肪酸との化合物である。金属石鹸は、被洗浄物の切削加工時に用いられる加工油剤に含まれることが多く、それが被洗浄物の表面に付着する。また、水中の金属イオンと洗浄剤中の脂肪酸とから生成される場合もある。溶接時に生成したブローホール内部の気体成分の約９０％は水素であることがわかっている。これより、ブローホールの多くは、被洗浄物の表面に付着した金属石鹸が、溶接時にガス化することで生成されると考えられる。したがって、被洗浄物の表面に金属石鹸が付着している場合には、その金属石鹸を除去することが重要となる。しかし、特許文献２に示された洗浄剤を含めて、従来の水溶性洗浄剤では、被洗浄物の表面に付着した金属石鹸を充分に除去することはできない。 Further, metal soap often adheres to the surface of the object to be cleaned. Metal soap is a compound of metal ions and fatty acids. Metal soap is often contained in a processing oil used when cutting an object to be cleaned, and adheres to the surface of the object to be cleaned. Moreover, it may be produced | generated from the metal ion in water and the fatty acid in a cleaning agent. It has been found that about 90% of the gas component inside the blowhole produced during welding is hydrogen. From this, it is considered that many blow holes are generated by gasifying the metal soap attached to the surface of the object to be cleaned during welding. Therefore, when metal soap adheres to the surface of the object to be cleaned, it is important to remove the metal soap. However, conventional water-soluble cleaning agents including the cleaning agent disclosed in Patent Document 2 cannot sufficiently remove metal soap adhered to the surface of the object to be cleaned.
そこで、先に本発明者らは、溶接前の洗浄に使用しても、溶接不良や溶接装置の不具合を引き起こし難く、被洗浄物の表面に付着した金属石鹸をも除去することのできる水溶性洗浄剤として、脂環式アミンと、液状脂肪酸と、非イオン界面活性剤とを主剤とし、粉末脂肪酸を含まないことを特徴とする水溶性洗浄剤を発明した（下記特許文献３）。該水溶性洗浄剤は、洗浄成分として非イオン界面活性剤を含み、被洗浄物表面の有機物を効果的に除去するとともに、脂環式アミンと液状脂肪酸とを含むため、被洗浄物表面の錆止め作用をも有する。すなわち、該水溶性洗浄剤で洗浄すると、脂環式アミンと液状脂肪酸との中和塩からなる皮膜が被洗浄物の表面に形成される結果、被洗浄物表面における錆の発生が効果的に抑制される。 Therefore, the inventors of the present invention are water-soluble that can easily remove metal soap adhered to the surface of the object to be cleaned, even if it is used for cleaning before welding, which is difficult to cause welding failure and welding apparatus failure. As a cleaning agent, a water-soluble cleaning agent was invented which is mainly composed of an alicyclic amine, a liquid fatty acid, and a nonionic surfactant and does not contain powdered fatty acid (Patent Document 3 below). The water-soluble cleaning agent contains a nonionic surfactant as a cleaning component, effectively removes organic substances on the surface of the object to be cleaned, and contains an alicyclic amine and a liquid fatty acid. Also has an effect. That is, when washed with the water-soluble detergent, a film composed of a neutralized salt of an alicyclic amine and a liquid fatty acid is formed on the surface of the object to be cleaned, so that rust is effectively generated on the surface of the object to be cleaned. It is suppressed.
電子ビーム溶接やレーザービーム溶接を行う場合、溶接中に金属蒸気が発生してワークに付着し、ワーク表面が黒や青に変色する。これにより、見た目品質がよくない事や、変色した部分の塗装がし難いといった問題がある。 When performing electron beam welding or laser beam welding, metal vapor is generated during welding and adheres to the workpiece, and the workpiece surface changes to black or blue. As a result, there are problems such as poor appearance quality and difficulty in painting discolored portions.
特許文献３に開示された水溶性洗浄剤は、溶接性を阻害し難い成分で構成されるため、溶接前の洗浄に使用しても、溶接不良や溶接装置の不具合を引き起こし難く、さらにキレート剤を配合することにより、被洗浄物表面に付着した金属石鹸を効果的に除去することができる結果、洗浄後の溶接における溶接不良や溶接装置の不具合の発生を抑制することができるものではあったが、上述のような、溶接中に金属蒸気が発生してワークに付着し、ワーク表面が黒や青に変色することに対しては抑制作用がなかった。 Since the water-soluble cleaning agent disclosed in Patent Document 3 is composed of components that are difficult to inhibit weldability, even if used for cleaning before welding, it is difficult to cause poor welding and failure of the welding apparatus. As a result of being able to effectively remove the metal soap adhering to the surface of the object to be cleaned, it was possible to suppress the occurrence of welding defects and welding apparatus failures after cleaning. However, there was no inhibitory action against the occurrence of metal vapor generated during welding and adhering to the workpiece as described above, and the workpiece surface changing to black or blue.
そこで、本発明は、電子ビーム溶接等の高エネルギー処理における、処理前の洗浄において、溶接阻害性が少なく、金属吸着性がある成分を洗浄液に添加して金属表面をプロテクトし、ワーク表面の変色を防止することを目的とする。 Accordingly, the present invention protects the metal surface by adding a component having a low metal barrier property to the cleaning liquid in the cleaning before the treatment in the high energy processing such as electron beam welding, thereby discoloring the workpiece surface. The purpose is to prevent.
本発明者らは、金属蒸着抑制剤として特定の成分を洗浄液に添加することで上記課題が解決されることを見出し、本発明に到達した。 The present inventors have found that the above problem can be solved by adding a specific component as a metal deposition inhibitor to the cleaning liquid, and have reached the present invention.
第１に、本発明は、水溶性洗浄剤の発明であり、脂環式アミン０．０００１〜０．０１２ｗｔ％と、液状脂肪酸０．０００１〜０．００６ｗｔ％と、非イオン界面活性剤０．０００１〜０．００１５ｗｔ％とを主剤として含有し、更に高分子多価カルボン酸モルホリン中和剤を０．０００１〜０．００５ｗｔ％含むことを特徴とする。 1stly, this invention is invention of a water-soluble detergent, 0.0001-0.012 wt% of alicyclic amine, 0.0001-0.006 wt% of liquid fatty acids, nonionic surfactant 0. It is characterized by containing 0001 to 0.0015 wt% as a main agent and further containing 0.0001 to 0.005 wt% of a polymer polyvalent carboxylic acid morpholine neutralizing agent.
本発明の水溶性洗浄剤は、主として金属ワークの前処理剤として用いられ、該金属ワークの表面の汚れを洗浄・除去するとともに、金属ワーク表面をプロテクトし、電子ビーム溶接等の高エネルギー処理に際してワーク表面の変色を防止する。 The water-soluble cleaning agent of the present invention is mainly used as a pretreatment agent for metal workpieces, cleans and removes dirt on the surface of the metal workpiece, protects the surface of the metal workpiece, and performs high energy processing such as electron beam welding. Prevent discoloration of the workpiece surface.
高分子多価カルボン酸モルホリン中和剤の添加量が、高分子多価カルボン酸モルホリン中和剤として、モルホリンを０．０００８ｗｔ％以上、高分子多価カルボン酸を０．０００４ｗｔ％以上であることが変色防止効果が顕著で好ましい。 The addition amount of the polymeric polycarboxylic acid morpholine neutralizing agent should be 0.0008 wt% or more of morpholine and 0.0004 wt% or more of the polymeric polycarboxylic acid as the polymeric polycarboxylic acid morpholine neutralizing agent. However, the effect of preventing discoloration is remarkable and preferable.
本発明の水溶性洗浄剤の主剤の１つである「脂環式アミン」は、エタノールアミン等と比較して、ヤニの生成が無く、燃焼性も良好である。また、「液状脂肪酸」も、粉末脂肪酸と比較して、煤およびヤニの生成が少なく、燃焼性も良好である。つまり、脂環式アミンおよび液状脂肪酸は、洗浄後に被洗浄物の表面に残存しても、溶接不良等を引き起こし難いといえる。これに対して粉末脂肪酸は、燃えかすが多く、燃焼性も悪いので、被洗浄物の表面に残存すると溶接不良等を引き起こす原因となる。 The “alicyclic amine”, which is one of the main components of the water-soluble detergent of the present invention, does not generate spears and has good combustibility compared to ethanolamine and the like. In addition, “liquid fatty acid” produces less soot and spear and has good combustibility compared with powdered fatty acid. That is, it can be said that even if the alicyclic amine and the liquid fatty acid remain on the surface of the object to be cleaned after cleaning, it is difficult to cause poor welding or the like. On the other hand, powdered fatty acids often burn and have poor flammability, and if they remain on the surface of the object to be cleaned, they cause poor welding and the like.
本発明の水溶性洗浄剤の主剤の１つである「非イオン界面活性剤」としては、種々のものを用いることができる。その中で、高級アルコールエトキシレート、脂肪酸ポリエーテル、２級アルコールエトキシレートから選ばれる一種以上が好ましく例示される。 As the “nonionic surfactant” which is one of the main components of the water-soluble detergent of the present invention, various types can be used. Among them, one or more selected from higher alcohol ethoxylates, fatty acid polyethers, and secondary alcohol ethoxylates are preferably exemplified.
本発明の水溶性洗浄剤には、ＥＤＴＡ有機中和塩及び／又はＤＴＰＡ有機中和塩に代表されるキレート剤を含むことが好ましい。被洗浄物の表面には、金属石鹸が付着していることが多い。キレート剤を配合することで、金属石鹸を錯化合物として効果的に除去することができる。したがって、キレート剤を含む態様の本発明の水溶性洗浄剤を用いて洗浄すれば、溶接不良や溶接装置の不具合の発生をより低減することができる。 The water-soluble detergent of the present invention preferably contains a chelating agent typified by an EDTA organic neutralized salt and / or a DTPA organic neutralized salt. Metal soap is often attached to the surface of the object to be cleaned. By blending the chelating agent, the metal soap can be effectively removed as a complex compound. Therefore, if it wash | cleans using the water-soluble cleaning agent of this invention of the aspect containing a chelating agent, generation | occurrence | production of the welding defect and the malfunction of a welding apparatus can be reduced more.
また、本発明の水溶性洗浄剤には、アルコール系消泡剤に代表される消泡剤を含むことが好ましい。 Moreover, it is preferable that the water-soluble cleaning agent of the present invention contains an antifoaming agent represented by an alcohol-based antifoaming agent.
第２に、本発明は、上記洗浄剤からなる電子ビーム処理部品用水溶性洗浄剤である。又、本発明は、上記洗浄剤からなるレーザービーム処理部品用水溶性洗浄剤である。 Second, the present invention is a water-soluble cleaning agent for electron beam processing parts comprising the above-described cleaning agent. Moreover, this invention is a water-soluble cleaning agent for laser beam processing parts which consists of said cleaning agent.
本発明の水溶性洗浄剤は、電子ビーム処理やレーザービーム処理に代表される高エネルギー処理の前処理剤として好適に用いられる。ここで、具体的な高エネルギー処理としては、溶接、切断、穿孔、表面処理、表面硬化などが好ましく例示される。又、高エネルギー処理を受ける被処理物としては、金属の他、セラミックスや樹脂成形物が好ましく例示される。 The water-soluble cleaning agent of the present invention is suitably used as a pretreatment agent for high energy processing typified by electron beam processing or laser beam processing. Here, specific examples of the high energy treatment include welding, cutting, drilling, surface treatment, surface hardening, and the like. Moreover, as a to-be-processed object which receives a high energy process, ceramics and a resin molding other than a metal are illustrated preferably.
本発明の水溶性洗浄剤は、金属ワークの前処理剤として用いられ、該金属ワークの表面の汚れを洗浄・除去するとともに、金属ワーク表面をプロテクトし、電子ビーム溶接等の高エネルギー処理に際してワーク表面の変色を防止する。本発明の水溶性洗浄剤は、溶接性を阻害し難い成分で構成されるため、溶接前の洗浄に使用しても、溶接不良や溶接装置の不具合を引き起こし難い上に、ポリカルボン酸モルホリン中和剤が皮膜となって、高エネルギー処理時のワーク表面の変色の防止に効果がある。 The water-soluble cleaning agent of the present invention is used as a pretreatment agent for metal workpieces, cleans and removes dirt on the surface of the metal workpiece, protects the surface of the metal workpiece, and protects the workpiece during high energy processing such as electron beam welding. Prevent surface discoloration. Since the water-soluble cleaning agent of the present invention is composed of components that do not easily impair weldability, even when used for cleaning before welding, it is difficult to cause poor welding or failure of the welding apparatus, and in the polycarboxylic acid morpholine. The additive becomes a film and is effective in preventing discoloration of the workpiece surface during high energy treatment.
また、さらにキレート剤を配合することにより、被洗浄物表面に付着した金属石鹸を効果的に除去することができる。その結果、洗浄後の溶接における溶接不良や溶接装置の不具合の発生を、より抑制することができる。 Moreover, the metal soap adhering to the to-be-washed | cleaned object surface can be effectively removed by mix | blending a chelating agent further. As a result, it is possible to further suppress the occurrence of defective welding and defects in the welding apparatus in the weld after cleaning.
便宜上、以下の説明では、本発明の水溶性洗浄剤（原液）を水で１％以上３％以下の濃度に希釈して使用することを前提として、各成分の好適な含有割合を示す。したがって、使用する際の希釈率が上記範囲と異なる場合には、希釈率に応じて、各成分の含有割合を適宜調整すればよい。 For convenience, in the following description, the preferable content ratio of each component is shown on the assumption that the water-soluble detergent (stock solution) of the present invention is diluted with water to a concentration of 1% or more and 3% or less. Therefore, when the dilution rate at the time of use differs from the said range, what is necessary is just to adjust the content rate of each component suitably according to a dilution rate.
本発明の水溶性洗浄剤の主剤の１つである「脂環式アミン」は、水溶性のものであればその種類が特に限定されるものではない。例えば、モルホリン、Ｎ−シクロヘキシルジエタノールアミン、シクロヘキシルアミン等が挙げられる。これら脂環式アミンの一種を単独で、また二種以上を混合して用いればよい。なかでも、分子内に酸素原子を含む化合物は、鉄が溶融する前にガス化し易く、燃焼性が良好であるため好適である。 The “alicyclic amine” which is one of the main components of the water-soluble detergent of the present invention is not particularly limited as long as it is water-soluble. For example, morpholine, N-cyclohexyldiethanolamine, cyclohexylamine and the like can be mentioned. These alicyclic amines may be used alone or in combination of two or more. Especially, the compound which contains an oxygen atom in a molecule | numerator is suitable since it is easy to gasify before iron melt | dissolves and combustibility is favorable.
本発明の水溶性洗浄剤（原液）における脂環式アミンの含有割合は、特に限定されるものではない。防錆効果を効果的に発揮させるという観点から、脂環式アミンの含有割合を１ｗｔ％以上とすることが望ましい。防錆効果を高くしたい場合には、脂環式アミンの含有割合を高くすればよい。しかし、コスト等の実用性を考慮すれば、脂環式アミンの含有割合を４０ｗｔ％以下とすることが望ましい。特に、溶接不良等をより少なくするという観点からは、２５ｗｔ％以下とすることが望ましい。１０ｗｔ％以下とするとより好適である。 The content ratio of the alicyclic amine in the water-soluble detergent (stock solution) of the present invention is not particularly limited. From the viewpoint of effectively exhibiting the rust prevention effect, the content of the alicyclic amine is preferably 1 wt% or more. In order to increase the rust prevention effect, the content of the alicyclic amine may be increased. However, in consideration of practicality such as cost, it is desirable that the content of the alicyclic amine is 40 wt% or less. In particular, from the viewpoint of reducing welding defects and the like, it is desirable that the content be 25 wt% or less. More preferably, it is 10 wt% or less.
本発明の水溶性洗浄剤の主剤の１つである「液状脂肪酸」の種類は、特に限定されるものではない。例えば、炭素数が９以下のカプリル酸、イソノナン酸等が挙げられる。これら液状脂肪酸の一種を単独で、また二種以上を混合して用いればよい。 The kind of “liquid fatty acid” which is one of the main ingredients of the water-soluble detergent of the present invention is not particularly limited. Examples thereof include caprylic acid having 9 or less carbon atoms and isononanoic acid. These liquid fatty acids may be used alone or in combination of two or more.
本発明の水溶性洗浄剤（原液）における液状脂肪酸の含有割合は、特に限定されるものではない。防錆効果を効果的に発揮させるという観点から、液状脂肪酸の含有割合を１ｗｔ％以上とすることが望ましい。一方、コスト等の実用性を考慮すれば、液状脂肪酸の含有割合を２０ｗｔ％以下とすることが望ましい。特に、溶接不良等をより少なくするという観点からは、１０ｗｔ％以下とすることが望ましい。５ｗｔ％以下とするとより好適である。 The content ratio of the liquid fatty acid in the water-soluble detergent (stock solution) of the present invention is not particularly limited. From the viewpoint of effectively exhibiting the rust prevention effect, the content ratio of the liquid fatty acid is preferably 1 wt% or more. On the other hand, in view of practicality such as cost, it is desirable that the content ratio of the liquid fatty acid is 20 wt% or less. In particular, from the viewpoint of reducing welding defects and the like, it is desirable that the content be 10 wt% or less. More preferably, it is 5 wt% or less.
本発明の水溶性洗浄剤の主剤の１つである「非イオン系界面活性剤」は、公知の活性剤を用いることができる。例えば、高級アルコールエトキシレート、プルロニックタイプ、テトロニックタイプ、脂肪族アミンエトキシレート、ソルビタン脂肪酸エステルエトキシレート、脂肪酸ポリエーテル、セカンダリアルコールエトキシレート等が好ましく挙げられる。これら非イオン系界面活性剤の一種を単独で、また二種以上を混合して用いればよい。 As the “nonionic surfactant” which is one of the main components of the water-soluble detergent of the present invention, a known activator can be used. For example, higher alcohol ethoxylate, pluronic type, tetronic type, aliphatic amine ethoxylate, sorbitan fatty acid ester ethoxylate, fatty acid polyether, secondary alcohol ethoxylate and the like are preferable. One kind of these nonionic surfactants may be used alone, or two or more kinds may be mixed and used.
本発明の水溶性洗浄剤における非イオン界面活性剤の含有割合は、特に限定されるものではない。実用上の洗浄効果を発揮させるという観点から、非イオン界面活性剤の含有割合を１ｗｔ％以上とすることが望ましい。一方、コスト等の実用性を考慮すれば、物理的な洗浄力に長けたスプレー洗浄等の場合、非イオン界面活性剤の含有割合を５ｗｔ％以下とすることが望ましい。特に、３ｗｔ％程度が好適である。 The content ratio of the nonionic surfactant in the water-soluble detergent of the present invention is not particularly limited. From the viewpoint of exerting a practical cleaning effect, the content ratio of the nonionic surfactant is preferably 1 wt% or more. On the other hand, if practicality such as cost is taken into consideration, it is desirable that the content ratio of the nonionic surfactant is 5 wt% or less in the case of spray cleaning or the like that has excellent physical detergency. In particular, about 3 wt% is preferable.
本発明の水溶性洗浄剤は、上記主剤に加え、さらに「キレート剤」を含んで構成すると好適である。この場合、被洗浄物の表面に付着した金属石鹸を、効果的に除去することができる。使用するキレート剤の種類は、特に限定されるものではない。例えば、ＥＤＴＡ（エチレンジアミン四酢酸）無機中和塩、ＥＤＴＡ有機中和塩、ＤＴＰＡ（ジエチレントリアミン五酢酸）無機中和塩、ＤＴＰＡ有機中和塩、ポリカルボン酸無機中和塩、ポリカルボン酸有機中和塩等が挙げられる。これらキレート剤の一種を単独で、また二種以上を混合して用いればよい。なかでも、ＥＤＴＡ有機中和塩およびＤＴＰＡ有機中和塩は、他のものと比べて燃えかすが少なく、燃焼性が良好であるため好適である。 It is preferable that the water-soluble cleaning agent of the present invention further includes a “chelating agent” in addition to the above main agent. In this case, the metal soap adhering to the surface of the object to be cleaned can be effectively removed. The kind of chelating agent to be used is not particularly limited. For example, EDTA (ethylenediaminetetraacetic acid) inorganic neutralized salt, EDTA organic neutralized salt, DTPA (diethylenetriaminepentaacetic acid) inorganic neutralized salt, DTPA organic neutralized salt, polycarboxylic acid inorganic neutralized salt, polycarboxylic acid organic neutralized salt Examples include salts. One kind of these chelating agents may be used alone, or two or more kinds may be mixed and used. Among these, the EDTA organic neutralized salt and the DTPA organic neutralized salt are preferable because they are less combustible than other materials and have good combustibility.
本発明の水溶性洗浄剤（原液）におけるキレート剤の含有割合は、特に限定されるものではない。金属石鹸の除去効果を効果的に発揮させるという観点から、キレート剤の含有割合を１ｗｔ％以上とすることが望ましい。一方、コスト等の実用性を考慮すれば、キレート剤の含有割合を２０ｗｔ％以下とすることが望ましい。特に、溶接不良等をより少なくするという観点からは、１０ｗｔ％以下とすることが望ましい。５ｗｔ％以下とするとより好適である。 The content ratio of the chelating agent in the water-soluble detergent (stock solution) of the present invention is not particularly limited. From the viewpoint of effectively exhibiting the effect of removing the metal soap, the content of the chelating agent is preferably 1 wt% or more. On the other hand, in view of practicality such as cost, it is desirable that the content of the chelating agent is 20 wt% or less. In particular, from the viewpoint of reducing welding defects and the like, it is desirable that the content be 10 wt% or less. More preferably, it is 5 wt% or less.
更に、本発明の水溶性洗浄剤は、必要に応じて上記以外の種々の添加剤を含めることができる。例えば、消泡剤等を含めることができる。ここで、消泡剤には、シリコン系消泡剤、アルコール系消泡剤等が挙げられる。しかし、シリコン系消泡剤の燃焼性は悪く、溶接時には燃えかすが多く残存する。そのため、溶接性を考慮した場合には、燃えかすが残らず、かつ燃焼性が良好なアルコール系消泡剤を用いることが望ましい。消泡剤を添加する場合、その含有割合は特に限定されるものではない。消泡効果を発揮させるには、１ｗｔ％以下で充分である。０．５ｗｔ％程度とすると好適である。 Furthermore, the water-soluble cleaning agent of the present invention can contain various additives other than those described above as necessary. For example, an antifoaming agent etc. can be included. Here, examples of the antifoaming agent include a silicon-based antifoaming agent and an alcohol-based antifoaming agent. However, the flammability of the silicon-based antifoaming agent is poor, and many burnouts remain during welding. Therefore, in consideration of weldability, it is desirable to use an alcohol-based antifoaming agent that does not leave flaming and has good flammability. When adding an antifoamer, the content rate is not specifically limited. In order to exhibit the defoaming effect, 1 wt% or less is sufficient. About 0.5 wt% is preferable.
本発明の水溶性洗浄剤は、上記所定の成分と、溶媒である水とを混合して調製される。そして、必要に応じて水で希釈して使用する。希釈率は、所望の効果が得られる範囲で適宜設定することができる。例えば、本発明の水溶性洗浄剤（原液）を水で１％以上３％以下の濃度に希釈して使用すればよい。 The water-soluble cleaning agent of the present invention is prepared by mixing the predetermined component and water as a solvent. And it dilutes with water as needed and uses it. The dilution rate can be appropriately set as long as a desired effect is obtained. For example, the water-soluble detergent (stock solution) of the present invention may be diluted with water to a concentration of 1% or more and 3% or less.
本発明の水溶性洗浄剤は、超音波洗浄、浸漬洗浄、水中噴霧法、気中噴霧法（スプレー洗浄）等、種々の洗浄方法に用いることができる。その洗浄液は洗浄の際に、４０〜７０℃に加温されて使用されることが好ましい。このようにして洗浄された部品は仕上げ処理として温水によるすすぎが行われ、部品表面が清浄される。 The water-soluble cleaning agent of the present invention can be used in various cleaning methods such as ultrasonic cleaning, immersion cleaning, underwater spray method, and air spray method (spray cleaning). The cleaning liquid is preferably used after being heated to 40 to 70 ° C. during the cleaning. The parts cleaned in this way are rinsed with warm water as a finishing process, and the surface of the parts is cleaned.
特に、本発明の水溶性洗浄剤は、電子ビーム溶接、レーザー溶接等の種々の溶接の前洗浄に好適である。 In particular, the water-soluble cleaning agent of the present invention is suitable for pre-cleaning of various welding such as electron beam welding and laser welding.
以下、本発明の水溶性洗浄剤の各成分が奏する本発明の特徴である、（１）変色防止効果、（２）溶接阻害性、（３）好適な添加量、について検討した。検討の結果、電子ビーム溶接時のワーク表面の変色物質は、ＥＰＭＡ分析からＦｅ、Ｍｎ等母材に存在する物質であり、（１）変色物質は溶接時に発生した金属蒸気が付着したものであること、（２）洗浄液の基本構成物質である脂肪酸、活性剤、アミン類、キレート剤の中から、変色防止効果があり、溶接阻害性の無い物質を選択し、最小で最大の効果のある添加量を確認した。 Hereinafter, (1) discoloration prevention effect, (2) welding inhibition, and (3) suitable addition amount, which are the characteristics of the present invention exhibited by each component of the water-soluble detergent of the present invention, were examined. As a result of the examination, the discoloration material on the workpiece surface during electron beam welding is a material present in the base material such as Fe and Mn from EPMA analysis, and (1) the discoloration material is a metal vapor generated during welding attached. (2) From the fatty acid, activator, amines, and chelating agents that are the basic constituents of the cleaning solution, select a substance that has the effect of preventing discoloration and has no welding inhibition, and has the minimum and maximum effect. Check the amount.
（１）変色防止効果
テストピースを完全脱脂処理を行い、ワークに添加剤を刷け塗りして溶接し、ワーク表面の変色防止効果を確認した。その結果、を下記表１に示す。
(1) Discoloration prevention effect The test piece was completely degreased, the additive was applied to the workpiece and welded, and the workpiece surface discoloration prevention effect was confirmed. The results are shown in Table 1 below.
表１の結果、活性剤である高級エトキシレート、２級アルコールエトキシレートは変色防止に若干効果があるが、キレート剤であるポリカルボン酸モルホリン中和塩は特に変色防止効果を有することが分かる。 As a result of Table 1, it can be seen that the higher ethoxylate as the activator and the secondary alcohol ethoxylate are slightly effective in preventing discoloration, but the polycarboxylic acid morpholine neutralized salt as the chelating agent has a discoloration preventing effect.
（２）溶接阻害性
煤・ヤニ（燃えカス発生の有無）、燃焼性（鉄が燃焼する前に洗浄成分が気化して無くなり易いかどうか）から、ポリカルボン酸モルホリン中和塩が溶接性に与える影響を検討した。結果を下記表２に示す。
(2) Welding inhibition 煤 / spotting (whether burn residue is generated) and flammability (whether the cleaning component is easily vaporized before iron burns) The effect was examined. The results are shown in Table 2 below.
表２の結果より、煤、ヤニ、燃焼性から総合判断して、高分子多価カルボン酸モルホリン中和塩に溶接阻害性はなかった。 From the results shown in Table 2, the polymer polyvalent carboxylic acid morpholine neutralized salt was not weld-inhibiting based on comprehensive judgment from soot, spear, and flammability.
（３）添加量
高分子多価カルボン酸モルホリン中和塩を洗浄液に配合する割合を変化させ、変色防止効果を確認した。配合する割合を多くするほど、コストアップになる事から、最も少ない量で最大の効果が得られる濃度を確認した。結果を下記表３に示す。
(3) Addition amount The ratio of blending the polymer polyvalent carboxylic acid morpholine neutralized salt with the cleaning liquid was changed to confirm the effect of preventing discoloration. The higher the proportion, the higher the cost. Therefore, the concentration at which the maximum effect was obtained with the smallest amount was confirmed. The results are shown in Table 3 below.
表３の結果より、洗浄剤投入量に対し、モルホリン１０％以上、高分子多価カルボン酸５％以上配合した時に、充分な変色防止効果が得られることが分かった。 From the results shown in Table 3, it was found that a sufficient discoloration preventing effect was obtained when 10% or more of morpholine and 5% or more of the polymer polyvalent carboxylic acid were blended with respect to the amount of the detergent.
以上の結果より、高分子多価カルボン酸モルホリン中和塩は変色防止効果を有し、かつ溶接阻害性を有しないことが明らかとなった。 From the above results, it has been clarified that the polymer polyvalent carboxylic acid morpholine neutralized salt has the effect of preventing discoloration and does not have welding inhibition.
本発明の水溶性洗浄剤を調製した。調製した水溶性洗浄剤を用いて、電子ビーム溶接の前洗浄を行い、その後の溶接における溶接不良および溶接装置の不具合の発生を調査した。以下、順に説明する。 A water-soluble detergent of the present invention was prepared. Using the prepared water-soluble cleaning agent, pre-cleaning of electron beam welding was performed, and the occurrence of welding defects and defects in the welding apparatus in subsequent welding was investigated. Hereinafter, it demonstrates in order.
（１）水溶性洗浄剤の調製
以下の組成および含有割合の水溶性洗浄剤を調製した。
Ｎ−シクロヘキシルジエタノールアミン：２．５ｗｔ％
モルホリン ：２．５ｗｔ％
カプリル酸 ：３ｗｔ％
高級アルコールエトキシレート ：３ｗｔ％
ＥＤＴＡ有機中和塩 ：３ｗｔ％
アルコール系消泡剤 ：０．５ｗｔ％
水 ：残部
上記組成を有する水溶性洗浄液（島田化成製ケミーライトＬＥ−２０００ １％希釈液）に
モルホリン：１０％
ポリカルボン酸：５％
水：８５％
からなる配合品を、１％分添加して希釈洗浄剤とした。
(1) Preparation of water-soluble detergent A water-soluble detergent having the following composition and content ratio was prepared.
N-cyclohexyldiethanolamine: 2.5 wt%
Morpholine: 2.5 wt%
Caprylic acid: 3wt%
Higher alcohol ethoxylate: 3wt%
EDTA organic neutralized salt: 3wt%
Alcohol-based antifoaming agent: 0.5 wt%
Water: balance Morpholine: 10% in water-soluble cleaning solution having the above composition (Chemicalite LE-2000 1% diluted solution manufactured by Shimada Kasei)
Polycarboxylic acid: 5%
Water: 85%
A blended product consisting of 1% was added to make a diluted detergent.
（２）洗浄
上記希釈洗浄剤を加温（６０℃から８０℃）して、スプレー洗浄装置にて、鉄製のデフケースを洗浄した。洗浄条件は、希釈洗浄剤温度６０〜８０℃、スプレー圧力０．３ＭＰａ、洗浄時間２５秒とした。
(2) Washing The diluted detergent was heated (60 ° C. to 80 ° C.), and the iron differential case was washed with a spray cleaning device. The cleaning conditions were a diluted cleaning agent temperature of 60 to 80 ° C., a spray pressure of 0.3 MPa, and a cleaning time of 25 seconds.
（３）溶接性の評価
上記洗浄後のデフケースを電子ビーム溶接した。その結果、電子ビーム溶接後のワーク表面の変色は発生しなかった。また、溶接時にガス化してブローホールやスパッタ等の溶接不良の発生はなかった。
(3) Evaluation of weldability The differential case after the cleaning was electron beam welded. As a result, discoloration of the workpiece surface after electron beam welding did not occur. Further, gasification occurred during welding, and there was no occurrence of poor welding such as blow holes or spatter.
以上より、本発明の水溶性洗浄剤を用いて洗浄することにより、ワーク表面の変色は発生を低減できることが確認された。 From the above, it was confirmed that discoloration of the workpiece surface can be reduced by washing with the water-soluble detergent of the present invention.
本発明の水溶性洗浄剤は、金属ワークの前処理剤として用いられて、該金属ワークの表面の汚れを洗浄・除去するとともに、金属ワーク表面をプロテクトし、電子ビーム溶接等の高エネルギー処理に際してワーク表面の変色を防止する。この結果、本発明の水溶性洗浄剤は、電子ビーム処理やレーザービーム処理に代表される高エネルギー処理の前処理剤として好適に用いられる。高エネルギー処理による、溶接、切断、穿孔、表面処理、表面硬化などの実用化と普及に貢献する。 The water-soluble cleaning agent of the present invention is used as a pretreatment agent for metal workpieces to clean and remove the surface of the metal workpiece, protect the metal workpiece surface, and perform high energy processing such as electron beam welding. Prevent discoloration of the workpiece surface. As a result, the water-soluble cleaning agent of the present invention is suitably used as a pretreatment agent for high energy processing typified by electron beam processing and laser beam processing. It contributes to the practical application and spread of welding, cutting, drilling, surface treatment, surface hardening, etc. by high energy treatment.
Claims (7)
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