JP2016196693A - Detergent composition for copper, zinc or alloy including these alloys, method for cleaning the obtect to be cleaned made of copper, zinc or alloy including these metals and method for removing fine particles made of copper, zinc or an alloy including these metals - Google Patents
Detergent composition for copper, zinc or alloy including these alloys, method for cleaning the obtect to be cleaned made of copper, zinc or alloy including these metals and method for removing fine particles made of copper, zinc or an alloy including these metals Download PDFInfo
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本発明は、洗浄剤組成物、特に、自動車、機械、精密機器、電気、電子、光学等の各種工業分野において扱われる部品、石油精製プラントや化学プラント等の各種工場の配管や装置、自動車や産業機械等を解体した部品、日常生活で使用される種々の物品であって、銅、亜鉛、またはこれらの金属を含む合金からなる部品の洗浄剤組成物、銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物の洗浄方法、および亜鉛、または銅これらの金属を含む合金からなる微粒子の除去方法に関する。 The present invention relates to a cleaning composition, in particular, parts handled in various industrial fields such as automobiles, machines, precision equipment, electricity, electronics, optics, piping and devices of various factories such as oil refineries and chemical plants, automobiles, Parts disassembled from industrial machinery, etc., and various articles used in daily life, including cleaning compositions for parts made of copper, zinc, or alloys containing these metals, copper, zinc, or these metals The present invention relates to a method for cleaning an object to be cleaned made of an alloy containing zinc, and a method for removing fine particles made of zinc or copper containing an alloy containing these metals.
従来、自動車、機械、精密機器、電気、電子、光学等の各種工業分野において扱われる部品の加工の際、（ｉ）鉱物油等を主体とする不水溶性加工油、（ｉｉ）鉱物油等に界面活性剤を加えて水に乳化させた水溶性加工油、（ｉｉｉ）研磨剤等が使用され、被洗浄物には種々の汚れが付着している。このような汚れ成分が付着した物品を洗浄する場合には、汚れ成分に応じて、水系洗浄剤、水系洗浄剤に水溶性溶剤を配合した準水系洗浄剤、イソプロパノールなどのアルコール系洗浄剤、グリコールエーテル系洗浄剤等が使用されている。 Conventionally, when processing parts handled in various industrial fields such as automobiles, machinery, precision equipment, electricity, electronics, optics, etc., (i) water-insoluble processing oil mainly composed of mineral oil, (ii) mineral oil, etc. A water-soluble processing oil emulsified in water by adding a surfactant, (iii) an abrasive, and the like are used, and various stains are attached to the object to be cleaned. When cleaning such articles with soil components attached, depending on the soil components, water-based cleaning agents, semi-aqueous cleaning agents in which water-soluble solvents are blended with water-based cleaning agents, alcohol-based cleaning agents such as isopropanol, glycol Ether detergents are used.
しかしながら、加工時の熱によって変性して表面に固着した汚れや化学結合した汚れ、あるいは加工時の機械力によって表面に突き刺さった微粒子の洗浄の全般に適したものはなく、酸性またはアルカリ性の水で表面をエッチングして除去する方法がとられているが、部品の材料によっては、酸性またはアルカリ性の水によりダメージを受けやすく、洗浄後にさびが発生し、また、乾燥工程に高いエネルギーを要するという欠点を有していた。 However, none of them is suitable for cleaning dirt that has been modified by heat during processing, soiled and chemically bonded, or fine particles that have been stuck into the surface by mechanical force during processing. The method of removing the surface by etching is taken, but depending on the material of the part, it is easily damaged by acidic or alkaline water, rust is generated after cleaning, and high energy is required for the drying process Had.
すなわち、酸性またはアルカリ性の水によりダメージを受ける銅等の材質を含む被洗浄物を水系洗浄剤で洗浄する場合、銅、または亜鉛等の金属の洗浄による腐食や変色を防止する技術として、所定炭素数のアルキル基またはアルケニル基を有する第１級アルコールのアルキレンオキシド付加体、所定炭素数のアルキル基またはアルケニル基を有する第２級アルコールのアルキレンオキシド付加体、界面活性剤、およびアルカリ剤を含む水性液体金属洗浄剤が開示されているが（例えば、特許文献１参照）、特許文献１の水性洗浄剤では、金属の腐食や変色を防止できるものの、加工時の熱によって変性して表面に固着した汚れや化学結合した汚れ、あるいは加工時の機械力によって表面に突き刺さった微粒子の洗浄の全般への適合性については記載も示唆もされておらず、また、水によりすすぎを行なうため、その後の乾燥工程に時間もしくは高いエネルギーを要するという欠点を有する。 In other words, when cleaning an object to be cleaned containing copper or other material that is damaged by acidic or alkaline water with an aqueous cleaning agent, as a technique for preventing corrosion or discoloration due to cleaning of a metal such as copper or zinc, predetermined carbon is used. An aqueous solution comprising an alkylene oxide adduct of a primary alcohol having a certain number of alkyl groups or alkenyl groups, an alkylene oxide adduct of a secondary alcohol having an alkyl group or alkenyl group having a predetermined number of carbon atoms, a surfactant, and an alkali agent Although a liquid metal cleaning agent is disclosed (for example, refer to Patent Document 1), the aqueous cleaning material of Patent Document 1 can prevent corrosion and discoloration of the metal, but is modified by heat during processing and fixed to the surface. About the general suitability for cleaning dirt, chemically bonded dirt, or fine particles stuck on the surface by mechanical force during processing. Has not been described or suggested, also, to perform the rinsing with water, it has the disadvantage that the subsequent drying step takes time or higher energy.
また、金属表面に付着した水分や水溶性汚れ、微粒子等を洗浄できる洗浄剤として、炭化水素系溶剤に、脂肪酸アルカノールアミドと、Ｎ−アルキルプロピレンジアミン脂肪酸塩とを配合した洗浄剤組成物（例えば、特許文献２〜４参照）や、脂肪族炭化水素系溶剤に所定炭素数のアミンと所定炭素数の飽和脂肪酸とを配合した水切り用組成物（例えば、特許文献５参照）、炭化水素に、脂肪族モノカルボン酸と脂肪族モノアミンとの塩、ノニオン系界面活性剤、飽和脂肪族アルコールを配合した水切り用溶剤組成物（例えば、特許文献６参照）が開示されているが、特許文献２〜６では、酸性またはアルカリ性の水によりダメージを受ける銅や亜鉛等の材質を有する被洗浄物を、さびを発生せずに洗浄する方法については記載も示唆もされておらず、また、加工時の熱によって変性して表面に固着した汚れや化学結合した汚れ、あるいは加工時の機械力によって表面に突き刺さった微粒子の洗浄の全般への適合性についての記載も示唆もされていない。 Moreover, as a cleaning agent capable of cleaning moisture, water-soluble dirt, fine particles, etc. attached to the metal surface, a cleaning composition comprising a hydrocarbon solvent and a fatty acid alkanolamide and an N-alkylpropylenediamine fatty acid salt (for example, , Refer to Patent Documents 2 to 4), a draining composition prepared by mixing an aliphatic hydrocarbon solvent with an amine having a predetermined carbon number and a saturated fatty acid having a predetermined carbon number (for example, refer to Patent Document 5), A draining solvent composition containing a salt of an aliphatic monocarboxylic acid and an aliphatic monoamine, a nonionic surfactant, and a saturated aliphatic alcohol (for example, see Patent Document 6) is disclosed. 6 describes or suggests a method for cleaning an object to be cleaned having a material such as copper or zinc that is damaged by acidic or alkaline water without causing rust. In addition, there is a description and suggestion about the general suitability of cleaning dirt that has been modified by heat during processing, dirt that has adhered to the surface, chemically bonded dirt, or fine particles that have pierced the surface by mechanical force during processing. It has not been.
本発明は、上記に鑑みてなされたものであって、酸性またはアルカリ性の水によりダメージを受ける銅等を含む被洗浄物に付着した種々の汚れを、被洗浄物の表面をわずかにエッチングすることにより汚れを洗浄しうる銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物、銅、亜鉛、またはこれらの金属を含む合金をからなる被洗浄物の洗浄方法、および銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去方法を提供することを目的とする。 The present invention has been made in view of the above, and slightly etches the surface of an object to be cleaned with various stains attached to the object to be cleaned including copper or the like that is damaged by acidic or alkaline water. A cleaning composition for copper, zinc, or an alloy containing these metals, and a method for cleaning an object to be cleaned comprising copper, zinc, or an alloy containing these metals, and copper, zinc, or It is an object of the present invention to provide a method for removing fine particles made of an alloy containing these metals.
本出願人らは、酸性またはアルカリ性の水によりダメージを受ける銅等を含む被洗浄物に付着した種々の汚れを、被洗浄物である銅、亜鉛、またはこれらの金属を含む合金の表面を水を使うことなく本発明の洗浄剤組成物によってわずかにエッチングすることにより洗浄できるとともに、エッチング後の被洗浄物のさび発生を抑制することを見出し、本発明を完成するに至った。 The present applicants apply various stains attached to an object to be cleaned including copper or the like damaged by acidic or alkaline water, and water the surface of copper, zinc, or an alloy including these metals as an object to be cleaned. The present invention has been completed by finding that it can be cleaned by slightly etching with the cleaning composition of the present invention without using, and that rusting of the object to be cleaned after etching is suppressed.
上述した課題を解決し、目的を達成するために、本発明の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物は、炭化水素系溶剤（Ａ）と、下記一般式（１）で表されるＮ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）、
Ｒ１−ＮＨ（ＣＨ２）３ＮＨ２・２Ｒ２−ＣＯＯＨ ・・・（１）
（式（１）において、Ｒ１およびＲ２は、炭素数７〜２２のアルキル基である）
下記一般式（２）で表されるサルコシン類（Ｂ−２）、
Ｒ３−Ｃ（Ｏ）−Ｎ（ＣＨ３）−ＣＨ２−ＣＯＯＨ ・・・（２）
（式（２）において、Ｒ３は、炭素数７〜２１のアルキル基である）、および炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとの混合物（Ｂ−３）からなる群から選ばれる少なくとも１種の化合物または混合物（Ｂ）と、を含み、前記炭化水素系溶剤（Ａ）を６０．０〜９９．７質量％、前記化合物または混合物（Ｂ）を０．３〜３０．０量％含有することを特徴とする。
In order to solve the above-described problems and achieve the object, a cleaning composition for an alloy containing copper, zinc, or these metals of the present invention comprises a hydrocarbon solvent (A) and the following general formula (1). N-alkylpropylenediamine fatty acid salt (B-1) represented by
R 1 —NH (CH 2 ) 3 NH 2 .2R 2 —COOH (1)
(In formula (1), R 1 and R 2 are alkyl groups having 7 to 22 carbon atoms)
Sarcosines (B-2) represented by the following general formula (2),
R 3 —C (O) —N (CH 3 ) —CH 2 —COOH (2)
(In formula (2), R 3 is an alkyl group having 7 to 21 carbon atoms), and a group (B-3) of a mixture of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms At least one compound or mixture (B) selected from the group consisting of 60.0 to 99.7% by mass of the hydrocarbon solvent (A) and 0.3 to 30 of the compound or mixture (B). It is characterized by containing 0.0% by weight.
また、本発明の銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物の洗浄方法は、銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物の洗浄方法であって、上記のいずれか一つに記載の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物に前記被洗浄物を浸漬し洗浄する洗浄工程と、前記洗浄工程後、前記被洗浄物を前記炭化水素系溶剤（Ａ）に浸漬するすすぎ工程と、を有し、前記洗浄工程において、銅、亜鉛、またはこれらの金属を含む合金からなる前記被洗浄物の銅、亜鉛、またはこれらの金属を含む合金の表面をエッチングすることにより被洗浄物の表面に付着する汚れを洗浄することを特徴とする。 Further, the method for cleaning an object to be cleaned made of copper, zinc, or an alloy containing these metals according to the present invention is a method for cleaning an object to be cleaned made of copper, zinc, or an alloy containing these metals, A cleaning process of immersing and cleaning the object to be cleaned in a cleaning composition for copper, zinc, or an alloy containing any of these metals, and after the cleaning process, the object to be cleaned is carbonized. A rinsing step of immersing in a hydrogen-based solvent (A), and in the cleaning step, the object to be cleaned made of copper, zinc, or an alloy containing these metals contains copper, zinc, or these metals It is characterized in that dirt adhering to the surface of the object to be cleaned is cleaned by etching the surface of the alloy.
また、本発明の銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去方法は、銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去方法であって、上記のいずれか一つに記載の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物に前記微粒子が付着した被洗浄物を浸漬し前記微粒子を除去する除去工程と、前記除去工程後、前記被洗浄物を前記炭化水素系溶剤（Ａ）に浸漬するすすぎ工程と、を有し、前記除去工程において、銅、亜鉛、またはこれらの金属を含む合金からなる前記微粒子の表面をエッチングすることにより被洗浄物の表面から前記微粒子を除去することを特徴とする。 Further, the method for removing fine particles comprising copper, zinc, or an alloy containing these metals according to the present invention is a method for removing fine particles comprising copper, zinc, or an alloy containing these metals. A removing step of removing the fine particles by immersing the fine material adhered to the cleaning composition for copper, zinc, or an alloy containing these metals, and after the removing step, the washed object A rinsing step of immersing the substrate in the hydrocarbon solvent (A), and in the removing step, the surface of the fine particles made of copper, zinc, or an alloy containing these metals is etched to be cleaned. The fine particles are removed from the surface of the film.
本発明にかかる銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物は、銅、亜鉛、またはこれらの金属を含む合金に対してエッチング性を有する化合物または混合物（Ｂ）を、所定の割合で炭化水素系溶剤（Ａ）に配合することにより、汚れが付着した被洗浄物の表面をわずかにエッチングすることができるため、汚れの種類や、汚れの被洗浄物への付着の機構にかかわらずに洗浄することができる。 The cleaning composition for an alloy containing copper, zinc, or a metal thereof according to the present invention comprises a compound or a mixture (B) having an etching property with respect to copper, zinc, or an alloy containing these metals. By blending with the hydrocarbon solvent (A) at a ratio, the surface of the object to be cleaned can be slightly etched, so that the type of dirt and the mechanism of adhesion of the dirt to the object to be cleaned can be used. Can be washed regardless.
以下に、本発明にかかる銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物、銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物の洗浄方法、および銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去方法について詳細に説明する。 Hereinafter, a cleaning composition for copper, zinc, or an alloy containing these metals according to the present invention, a method for cleaning an object to be cleaned comprising copper, zinc, or an alloy containing these metals, and copper, zinc, or A method for removing fine particles made of an alloy containing these metals will be described in detail.
本発明の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物は、炭化水素系溶剤（Ａ）と、下記一般式（１）で表されるＮ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）、
Ｒ１−ＮＨ（ＣＨ２）３ＮＨ２・２Ｒ２−ＣＯＯＨ ・・・（１）
（式（１）において、Ｒ１およびＲ２は、炭素数７〜２２のアルキル基である）
下記一般式（２）で表されるサルコシン類（Ｂ−２）、
Ｒ３−Ｃ（Ｏ）−Ｎ（ＣＨ３）−ＣＨ２−ＣＯＯＨ ・・・（２）
（式（２）において、Ｒ３は、炭素数７〜２１のアルキル基である）および炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとの混合物（Ｂ−３）からなる群から選ばれる少なくとも１種の化合物または混合物（Ｂ）と、を含み、炭化水素系溶剤（Ａ）を６０．０〜９９．７質量％、化合物または混合物（Ｂ）を０．３〜３０．０量％含有する。
The cleaning composition for an alloy containing copper, zinc, or these metals of the present invention comprises a hydrocarbon solvent (A) and an N-alkylpropylenediamine fatty acid salt (B-) represented by the following general formula (1). 1),
R 1 —NH (CH 2 ) 3 NH 2 .2R 2 —COOH (1)
(In formula (1), R 1 and R 2 are alkyl groups having 7 to 22 carbon atoms)
Sarcosines (B-2) represented by the following general formula (2),
R 3 —C (O) —N (CH 3 ) —CH 2 —COOH (2)
(In formula (2), R 3 is an alkyl group having 7 to 21 carbon atoms) and a group consisting of a mixture of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms (B-3) At least one selected compound or mixture (B), 60.0 to 99.7% by mass of the hydrocarbon solvent (A), and 0.3 to 30.0 amount of the compound or mixture (B). %contains.
本発明で使用する炭化水素系溶剤（Ａ）は、市販の炭化水素系溶剤が使用でき、特に制限はないが、環境汚染の少ないものを選択するのが望ましい。このような溶剤としては、炭素数が５〜２０、好ましくは炭素数７〜１６、特に好ましくは炭素数９〜１５の範囲のものを主成分としたものが使用できる。炭素数５未満のものは、引火点が低いため作業中に火災や爆発の危険が大きく安全面に問題がある。また、炭素数２０を越えると、乾燥性が悪くなる上、洗浄剤組成物の粘性が増加するため、被洗浄物に付着している汚れの除去性能が低下し、好ましくない。さらに、良好な乾燥性が要求される場合は、実質的に炭素数が同一の炭化水素、或いは炭素数が１つ異なる２種の炭素数からなる炭化水素の混合物を用いることが望ましい。このような炭化水素系溶剤としては、炭素数５〜１７のノルマルパラフィン系溶剤や、炭素数３または４のオレフィンを重合して得られる炭素数６〜２０のイソパラフィン系溶剤、炭素数５〜２０の混合ナフテン系溶剤、炭素数５〜２０の芳香族系溶剤、灯油等がある。 As the hydrocarbon solvent (A) used in the present invention, a commercially available hydrocarbon solvent can be used, and there is no particular limitation, but it is desirable to select a solvent with less environmental pollution. As such a solvent, a solvent having 5 to 20 carbon atoms, preferably 7 to 16 carbon atoms, particularly preferably 9 to 15 carbon atoms as a main component can be used. Those having less than 5 carbon atoms have a low flash point, and there is a large risk of fire and explosion during work, which is a problem in safety. On the other hand, when the number of carbon atoms exceeds 20, the drying property is deteriorated and the viscosity of the cleaning composition is increased, so that the performance of removing dirt adhering to the object to be cleaned is lowered, which is not preferable. Furthermore, when good drying properties are required, it is desirable to use a hydrocarbon having substantially the same carbon number or a mixture of hydrocarbons having two different carbon numbers. Examples of such hydrocarbon solvents include normal paraffin solvents having 5 to 17 carbon atoms, isoparaffin solvents having 6 to 20 carbon atoms obtained by polymerizing olefins having 3 or 4 carbon atoms, and 5 to 20 carbon atoms. Mixed naphthenic solvents, aromatic solvents having 5 to 20 carbon atoms, kerosene and the like.
ノルマルパラフィン系溶剤は、炭素数が５〜１７、好ましくは炭素数７〜１４、特に好ましくは炭素数９〜１３の範囲のものが使用できる。１７を超えると、乾燥性が悪くなる上、洗浄剤組成物の粘性が増加するため、被洗浄物に付着している汚れの除去性能が低下し好ましくない。さらに、沸点が高すぎて蒸留回収が困難であったり、加温しないと溶液状態にならないものがあったりする。 As the normal paraffin solvent, those having 5 to 17, preferably 7 to 14, and particularly preferably 9 to 13 carbon atoms can be used. If it exceeds 17, the drying property is deteriorated and the viscosity of the cleaning composition is increased, so that the removal performance of dirt adhering to the object to be cleaned is lowered, which is not preferable. Furthermore, the boiling point is too high, making it difficult to recover by distillation, or there are some that do not become a solution unless heated.
イソパラフィン系溶剤は、炭素数５〜２０、好ましくは８〜１６、特に好ましくは８〜１２の範囲のものが使用できるが、合成のし易さから通常は、炭素数６、８、９、１２及び１６から適当なものを選択するのが実際的である。この場合において、炭素数が１異なる溶剤と混合するときは、８と９の組合せにするか、ノルマルパラフィンと組合せて使用する。 As the isoparaffinic solvent, those having 5 to 20 carbon atoms, preferably 8 to 16 carbon atoms, particularly preferably 8 to 12 carbon atoms can be used, but usually 6, 8, 9, and 12 carbon atoms because of ease of synthesis. And 16 is practical. In this case, when mixing with a solvent having one different carbon number, it is used in combination with 8 or 9 or in combination with normal paraffin.
銅、亜鉛、またはこれらの金属を含む合金の表面をわずかにエッチングする化合物または混合物（Ｂ）としては、Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）、サルコシン類（Ｂ−２）、および炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとの混合物（Ｂ−３）からなる群から選ばれる少なくとも１種である。本発明の洗浄剤組成物は、銅、亜鉛、またはこれらの金属を含む合金に対し腐食性が低い炭化水素系溶剤（Ａ）と、銅、亜鉛、またはこれらの金属を含む合金の表面をわずかにエッチングする化合物または混合物（Ｂ）とを、所定の割合で配合することにより、被洗浄物の表面をエッチングして被洗浄物表面に付着する汚れを除去するとともに、洗浄後、被洗浄物にさびを発生することがない。また、表面のエッチングにより汚れを洗浄するため、洗浄しにくい汚れ、例えば、加工時の熱によって変性して表面に固着した汚れや化学結合した汚れ、あるいは加工時の機械力によって表面に突き刺さった微粒子の洗浄を行うことができる。 Compounds or mixtures (B) that slightly etch the surface of copper, zinc, or alloys containing these metals include N-alkylpropylenediamine fatty acid salts (B-1), sarcosines (B-2), and carbon It is at least one selected from the group consisting of a mixture (B-3) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms. The cleaning composition of the present invention has a hydrocarbon solvent (A) that is less corrosive to copper, zinc, or an alloy containing these metals, and a surface of the alloy containing copper, zinc, or these metals. The compound or mixture (B) to be etched is blended at a predetermined ratio to etch the surface of the object to be cleaned to remove the dirt adhering to the surface of the object to be cleaned. Does not generate rust. Also, since dirt is cleaned by etching the surface, dirt that is difficult to clean, such as dirt that has been modified by heat during processing, dirt that has been chemically bonded to the surface, or fine particles that have stuck into the surface by mechanical force during processing Can be cleaned.
Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）は、下記一般式（１）で表されるものである。
Ｒ１−ＮＨ（ＣＨ２）３ＮＨ２・２Ｒ２−ＣＯＯＨ ・・・（１）
（式（１）において、Ｒ１およびＲ２は、炭素数７〜２２のアルキル基である）
The N-alkylpropylenediamine fatty acid salt (B-1) is represented by the following general formula (1).
R 1 —NH (CH 2 ) 3 NH 2 .2R 2 —COOH (1)
(In formula (1), R 1 and R 2 are alkyl groups having 7 to 22 carbon atoms)
Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）のアミンとしては、アルキル基（Ｒ１）の炭素数が７〜２２、好ましくは１０〜２０、より好ましくは１４〜１８のものである。中でも、オクタデシルプロピレンジアミン、ヘキサデシルプロピレンジアミン、テトラデシルプロピレンジアミンが入手の容易さから特に好適に使用できる。 The amine of the N-alkylpropylenediamine fatty acid salt (B-1) has 7 to 22, preferably 10 to 20, more preferably 14 to 18 carbon atoms in the alkyl group (R 1 ). Among these, octadecyl propylene diamine, hexadecyl propylene diamine, and tetradecyl propylene diamine can be particularly preferably used because of their availability.
Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）の脂肪酸としては、アルキル基（Ｒ２）の炭素数が７〜２２、好ましくは８〜２０のものが使用できる。具体的には、オクタン酸、デカン酸、ドデカン酸（ラウリン酸）、テトラデカン酸（ミリスチン酸）、ヘキサデカン酸（パルミチン酸）、オクタデカン酸（ステアリン酸）等の飽和脂肪酸や、オレイン酸等の不飽和脂肪酸を挙げることができる。これらの中でも、オレイン酸等の不飽和脂肪酸は、融点が低い点で好適に使用できる。 As the fatty acid of the N-alkylpropylenediamine fatty acid salt (B-1), those having 7 to 22, preferably 8 to 20 carbon atoms in the alkyl group (R 2 ) can be used. Specifically, saturated fatty acids such as octanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), and unsaturateds such as oleic acid Mention may be made of fatty acids. Among these, unsaturated fatty acids such as oleic acid can be suitably used because of their low melting point.
Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）は、種々の方法で合成できる。例えば、相当するＮ−アルキル一級アミンとアクリロニトリルを窒素雰囲気下、１００〜２００℃で触媒を用いて反応させ、さらに水素化し、得られたＮ−アルキルプロピレンジアミンに窒素雰囲気下で脂肪酸を加える方法等を採用することができる。Ｎ−アルキルプロピレンジアミンや脂肪酸は、単一のものである必要はなく、２種以上の混合物や、天然由来のものを用いることは何等問題がない。特に、牛脂や植物油を原料として用いる場合は、原料が安価であるため、製品を安価に製造する上で好ましい。 The N-alkylpropylenediamine fatty acid salt (B-1) can be synthesized by various methods. For example, a method in which a corresponding N-alkyl primary amine and acrylonitrile are reacted in a nitrogen atmosphere at 100 to 200 ° C. using a catalyst, hydrogenated, and a fatty acid is added to the obtained N-alkylpropylenediamine in a nitrogen atmosphere. Can be adopted. N-alkyl propylene diamine and fatty acid do not need to be a single one, and there is no problem in using a mixture of two or more kinds or a natural one. In particular, when beef tallow or vegetable oil is used as a raw material, the raw material is inexpensive, which is preferable in producing a product at low cost.
サルコシン類（Ｂ−２）は、下記一般式（２）で表される分子内にアミノ基およびカルボキシル基をそれぞれ１つ以上有する化合物である。
下記一般式（２）で表されるサルコシン類（Ｂ−２）、
Ｒ３−Ｃ（Ｏ）−Ｎ（ＣＨ３）−ＣＨ２−ＣＯＯＨ ・・・（２）
（式（２）において、Ｒ３は、炭素数７〜２１のアルキル基、アルケニル基またはフェニル基である）
Sarcosines (B-2) are compounds each having one or more amino groups and carboxyl groups in the molecule represented by the following general formula (2).
Sarcosines (B-2) represented by the following general formula (2),
R 3 —C (O) —N (CH 3 ) —CH 2 —COOH (2)
(In the formula (2), R 3 is an alkyl group, alkenyl group or phenyl group having 7 to 21 carbon atoms)
サルコシン類（Ｂ−２）としては、Ｒ３の炭素数が７〜２１、好ましくは１０〜２０、より好ましくは１４〜１８のものである。また、Ｒ３は置換基を有していてもよい。中でも、ラウロイルサルコシン、オレオイルサルコシン、ココイルサルコシン等が好適に使用できる。 As the sarcosines (B-2), R 3 has 7 to 21, preferably 10 to 20, more preferably 14 to 18 carbon atoms. R 3 may have a substituent. Of these, lauroyl sarcosine, oleoyl sarcosine, cocoyl sarcosine, and the like can be preferably used.
炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとの混合物（Ｂ−３）とは、炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとを実際に混合したものに加え、炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとを単独で配合、すなわち、炭化水素系溶剤（Ａ）に加える際、炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとを個別に配合したものを含む。 The mixture (B-3) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms is added to the actual mixture of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms. When a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms are blended alone, that is, when added to the hydrocarbon solvent (A), the fatty acid having 7 to 22 carbon atoms and the amine having 7 to 22 carbon atoms And those individually blended.
脂肪酸としては、炭素数が７〜２２、好ましくは８〜２０のものが使用できる。具体的には、オクタン酸、デカン酸、ドデカン酸（ラウリン酸）、テトラデカン酸（ミリスチン酸）、ヘキサデカン酸（パルミチン酸）、オクタデカン酸（ステアリン酸）等の飽和脂肪酸や、オレイン酸等の不飽和脂肪酸を挙げることができる。 As the fatty acid, those having 7 to 22, preferably 8 to 20 carbon atoms can be used. Specifically, saturated fatty acids such as octanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), and unsaturateds such as oleic acid Mention may be made of fatty acids.
アミンとしては、炭素数が７〜２２、好ましくは８〜２０のものが使用できる。具体的には、オクチルアミン、デシルアミン、ドデシルアミン、テトラデシルアミン、ヘキサデシルアミン、オクタデシルアミン、２−エチルヘキシルアミン、ジ（２−エチルヘキシル）アミン、オレオイルアミン等を挙げることができる。アミンや脂肪酸は、単一のものである必要はなく、２種以上の混合物や、天然由来のものを用いることは何等問題がない。 As the amine, those having 7 to 22, preferably 8 to 20 carbon atoms can be used. Specific examples include octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 2-ethylhexylamine, di (2-ethylhexyl) amine, oleoylamine and the like. The amine and fatty acid need not be a single one, and there is no problem in using a mixture of two or more kinds or a naturally derived one.
本発明にかかる銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物は、炭化水素系溶剤（Ａ）を６０．０〜９９．７質量％、化合物または混合物（Ｂ）を０．３〜３０．０質量％含有する。化合物または混合物（Ｂ）の割合が０．３質量％を下回ると、エッチング速度が低下し、洗浄性能が不十分となるおそれがある。化合物または混合物（Ｂ）の割合が３０．０質量％を超えると、洗浄剤組成物の粘度が著しく高くなり、エッチング性能が低下するおそれがある。炭化水素系溶剤（Ａ）を８８．０〜９９．７質量％、化合物または混合物（Ｂ）の配合割合は、０．５〜５．０質量％が好ましい。 The cleaning composition for alloys containing copper, zinc, or these metals according to the present invention comprises 60.0 to 99.7% by mass of the hydrocarbon solvent (A) and 0.3% of the compound or mixture (B). It contains ~ 30.0 mass%. When the ratio of the compound or the mixture (B) is less than 0.3% by mass, the etching rate is decreased and the cleaning performance may be insufficient. When the ratio of the compound or the mixture (B) exceeds 30.0% by mass, the viscosity of the cleaning composition is remarkably increased and the etching performance may be deteriorated. The hydrocarbon solvent (A) is preferably 88.0 to 99.7% by mass, and the compounding ratio of the compound or mixture (B) is preferably 0.5 to 5.0% by mass.
また、化合物または混合物（Ｂ）の選択肢の１つであるＮ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）は、炭化水素系溶剤（Ａ）への溶解性が低いため、Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）の配合量を３０．０質量％程度とすることが困難であるが、脂肪酸アルカノールアミド（Ｃ）を配合することにより、Ｎ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）の溶解性を向上することができる。 Moreover, since N-alkyl propylene diamine fatty acid salt (B-1) which is one of the choices of a compound or a mixture (B) has low solubility to a hydrocarbon solvent (A), it is N-alkyl propylene diamine fatty acid. Although it is difficult to make the compounding quantity of a salt (B-1) about 30.0 mass%, by mix | blending fatty acid alkanolamide (C), N-alkyl propylene diamine fatty acid salt (B-1) Solubility can be improved.
脂肪酸アルカノールアミド（Ｃ）の配合量は、化合物または混合物（Ｂ）と合わせて０．３〜４０．０質量％とすることが好ましく、０．５〜１０．０％がさらに好ましく、０．５〜５．０質量％が特に好ましい。また、化合物または混合物（Ｂ）と脂肪酸アルカノールアミド（Ｃ）との配合割合は、脂肪酸アルカノールアミド（Ｃ）が化合物または混合物（Ｂ）に対し、０．０１〜２．０倍、好ましくは０．１〜１．５倍、より好ましくは０．３〜１．０倍の範囲とするのが望ましい。 The blending amount of the fatty acid alkanolamide (C) is preferably 0.3 to 40.0% by mass, more preferably 0.5 to 10.0%, together with the compound or the mixture (B), 0.5 -5.0 mass% is especially preferable. Moreover, the compounding ratio of the compound or mixture (B) and the fatty acid alkanolamide (C) is 0.01 to 2.0 times, preferably 0. 0, to the compound or mixture (B) of the fatty acid alkanolamide (C). It is desirable to set it in the range of 1 to 1.5 times, more preferably 0.3 to 1.0 times.
本発明の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物には、本発明の目的を損なわない範囲、望ましくは１０質量％以下で、エステル類、アルコール類、ケトン類等の配合成分や、他の界面活性剤、酸化防止剤、紫外線吸収剤、防錆剤等の慣用の添加剤を含めることができる。 In the cleaning composition for copper, zinc, or an alloy containing these metals of the present invention, blending of esters, alcohols, ketones, etc. within a range that does not impair the purpose of the present invention, desirably 10% by mass or less. Ingredients and other conventional additives such as surfactants, antioxidants, ultraviolet absorbers, rust inhibitors can be included.
他の界面活性剤としては非イオン性界面活性剤が好ましく、例えば高級アルコールエチレンオキサイド付加物、アルキルフェノールエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、高級アルキルアミンエチレンオキサイド付加物、ソルビトール及びソルビタンの脂肪酸エステル、ショ糖脂肪酸エステル、シリコン系、フッ素系等いずれのものも使用できる。 Other surfactants are preferably nonionic surfactants, such as higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, sorbitol and sorbitan fatty acid esters. Any of sucrose fatty acid ester, silicon type, fluorine type and the like can be used.
また、紫外線吸収剤及び酸化防止剤としては、本発明の洗浄剤組成物に溶解するものであれば公知のものが使用でき、洗浄剤組成物の長期保存等における安定性の向上に役立つ。紫外線吸収剤としては例えばベンゾトリアゾール系、ベンゾフェノン系、ヒンダードアミン系等の紫外線吸収剤が挙げられる。
さらに、酸化防止剤としては例えばフェノール系、アミン系、硫黄系、リン系等の酸化防止剤が挙げられ、フェノール系酸化防止剤を１００〜１０００ｐｐｍ添加することが特に好ましい。
Moreover, as a ultraviolet absorber and antioxidant, a well-known thing can be used if it melt | dissolves in the cleaning composition of this invention, and it is useful for the stability improvement in the long-term preservation | save etc. of cleaning composition. Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, and hindered amine-based ultraviolet absorbers.
Furthermore, examples of the antioxidant include phenol-based, amine-based, sulfur-based, and phosphorus-based antioxidants, and it is particularly preferable to add 100 to 1000 ppm of the phenol-based antioxidant.
本発明の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物は、上記した各成分を所定量計量し、混合、撹拌して製造することができる。配合の順番、撹拌方法には何ら制限がなく、所定の割合の各成分を混合、撹拌することで、本発明にかかる洗浄剤組成物を製造することができる。 The cleaning composition for an alloy containing copper, zinc, or these metals of the present invention can be produced by weighing a predetermined amount of each of the above components, mixing and stirring them. There is no restriction | limiting in the order of mixing | blending and the stirring method, The cleaning composition concerning this invention can be manufactured by mixing and stirring each component of a predetermined ratio.
また、本発明の洗浄剤組成物を使用する洗浄方法としては、本発明にかかる洗浄剤組成物に銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物を浸漬し洗浄した後、被洗浄物を上記した炭化水素系溶剤（Ａ）に浸漬して、被洗浄物に付着する洗浄剤組成物をすすぐことにより行えばよい。本発明にかかる洗浄剤組成物中に被洗浄物を浸漬することで、被洗浄物の銅、亜鉛、またはこれらの金属を含む合金の表面をわずかにエッチングでき、これにより被洗浄物と汚れの間の付着、例えば、機械的付着、電気的付着、分子間力による付着、化学結合による付着を解消でき、洗浄可能となる。また、本発明にかかる洗浄剤組成物は、汚れが付着する銅、亜鉛、またはこれらの金属を含む合金の表面をエッチングすることにより汚れを洗浄するため、汚れの種類にかかわらず洗浄することができる。 Further, as a cleaning method using the cleaning composition of the present invention, an object to be cleaned made of copper, zinc, or an alloy containing these metals is immersed in the cleaning composition according to the present invention and then cleaned. What is necessary is just to carry out by immersing a washing | cleaning thing in the above-mentioned hydrocarbon-type solvent (A), and rinsing the cleaning composition which adheres to a to-be-washed object. By immersing the object to be cleaned in the cleaning composition according to the present invention, the surface of the object to be cleaned can be slightly etched, such as copper, zinc, or an alloy containing these metals. Adhesion between layers, for example, mechanical adhesion, electrical adhesion, adhesion due to intermolecular force, adhesion due to chemical bonding can be eliminated, and cleaning becomes possible. In addition, the cleaning composition according to the present invention cleans dirt by etching the surface of copper, zinc, or an alloy containing these metals to which dirt adheres. it can.
本発明にかかる洗浄剤組成物中への被洗浄物の浸漬の際、洗浄効果を高めるために、攪拌、揺動、超音波照射、噴流又はエアバブリング等を組み合わせることが好ましい。超音波の場合、この照射条件は、例えば発振周波数２０〜１００ｋＨｚ、発振出力０．１〜２００Ｗ／Ｌが好ましい。超音波照射により被洗浄物表面のエッチング速度が向上するとともに、洗浄液組成物に不溶性の汚れを分離して気泡と共に上昇させ、除去することもできる。 In order to enhance the cleaning effect when the object to be cleaned is immersed in the cleaning composition according to the present invention, it is preferable to combine stirring, shaking, ultrasonic irradiation, jet flow, air bubbling, or the like. In the case of ultrasonic waves, the irradiation conditions are preferably an oscillation frequency of 20 to 100 kHz and an oscillation output of 0.1 to 200 W / L, for example. The etching rate of the surface of the object to be cleaned is improved by the ultrasonic irradiation, and the insoluble dirt in the cleaning liquid composition can be separated and raised together with bubbles to be removed.
洗浄時間は、好ましくは１５秒間〜１０分、特に好ましくは３０秒間〜５分間である。上記範囲未満では洗浄が不十分で、付着した汚れを十分に除去し得ず、一方、上記範囲を超えるとエッチング量が大きくなるおそれがある。洗浄温度は、好ましくは２０〜１２０℃である。洗浄温度が上記範囲未満では、洗浄が不十分となり易いため、より高温で処理することにより洗浄効果を著しく上昇させることができるが、引火等の危険性を考慮し上記範囲内で洗浄することが好ましい。 The washing time is preferably 15 seconds to 10 minutes, particularly preferably 30 seconds to 5 minutes. If the amount is less than the above range, cleaning is insufficient, and attached dirt cannot be sufficiently removed. On the other hand, if the range is exceeded, the etching amount may increase. The washing temperature is preferably 20 to 120 ° C. If the cleaning temperature is less than the above range, the cleaning is likely to be insufficient, so that the cleaning effect can be remarkably increased by processing at a higher temperature. preferable.
本発明の洗浄剤組成物による被洗浄物の洗浄後、化合物または混合物（Ｂ）等の除去を目的として、炭化水素系溶剤（Ａ）によりすすぎ工程を行うが、すすぎ工程で使用する炭化水素系溶剤（Ａ）は、本発明の洗浄剤組成物で使用する炭化水素系溶剤（Ａ）より低沸点であれば同一である必要はない。また、すすぎ工程は、１回でもよく、または２回以上行なってもよい。 After washing the object to be washed with the cleaning composition of the present invention, the rinsing step is performed with the hydrocarbon solvent (A) for the purpose of removing the compound or the mixture (B), etc., but the hydrocarbon type used in the rinsing step The solvent (A) need not be the same as long as it has a lower boiling point than the hydrocarbon solvent (A) used in the cleaning composition of the present invention. The rinsing step may be performed once or may be performed twice or more.
また、本発明の洗浄剤組成物は、汚れとして銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去に使用することができる。例えば、本発明にかかる洗浄剤組成物に、銅、亜鉛、またはこれらの金属を含む合金からなる微粒子が付着した被洗浄物を浸漬し微粒子を除去した後、被洗浄物を炭化水素系溶剤（Ａ）に浸漬してすすぎを行う。本発明にかかる洗浄剤組成物中に銅等からなる微粒子が付着した被洗浄物を浸漬することで、銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の表面がわずかにエッチングされ、これにより被洗浄物と微粒子との間の付着、例えば、機械的付着、電気的付着、分子間力による付着、化学結合による付着を解消、すなわち洗浄することができる。 Moreover, the cleaning composition of the present invention can be used for removing fine particles composed of copper, zinc, or an alloy containing these metals as dirt. For example, the cleaning object according to the present invention is immersed in an object to be cleaned to which fine particles made of copper, zinc, or an alloy containing these metals are attached to remove the fine particles, and then the object to be cleaned is removed with a hydrocarbon solvent ( Rinse by immersing in A). The surface of the fine particles made of copper, zinc, or an alloy containing these metals is slightly etched by immersing the object to be cleaned to which the fine particles made of copper or the like are attached in the cleaning composition according to the present invention. Thus, adhesion between the object to be cleaned and the fine particles, for example, mechanical adhesion, electrical adhesion, adhesion due to intermolecular force, adhesion due to chemical bonding, can be eliminated, that is, washing can be performed.
汚れとして銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去の際の、洗浄条件、例えば、攪拌、揺動、超音波照射、噴流又はエアバブリング等との組み合わせ、洗浄時間、洗浄温度、すすぎに使用する炭化水素系溶剤（Ａ）は、銅等からなる被洗浄物を洗浄する場合と同様の条件で行えばよい。 Cleaning conditions such as stirring, rocking, ultrasonic irradiation, jet or air bubbling, cleaning time, cleaning temperature when removing fine particles of copper, zinc, or alloys containing these metals as dirt The hydrocarbon solvent (A) used for rinsing may be performed under the same conditions as in the case of cleaning an object to be cleaned made of copper or the like.
本発明の洗浄剤組成物は、銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物の表面をわずかにエッチングすることにより洗浄を行うので、付着する汚れの種類にかかわらず洗浄を行うことができる。また、本発明の洗浄剤組成物は、銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物のさびを抑制できる。 Since the cleaning composition of the present invention performs cleaning by slightly etching the surface of an object to be cleaned made of copper, zinc, or an alloy containing these metals, cleaning is performed regardless of the type of dirt attached. be able to. Moreover, the cleaning composition of this invention can suppress the rust of the to-be-cleaned object which consists of copper, zinc, or the alloy containing these metals.
以下、実施例および比較例により、本発明を具体的に説明するが、本発明は、下記の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to the following Example.
実施例１〜２９、比較例１〜１４として調製した洗浄剤組成物の組成を表１〜表３に示す。実施例１〜２９、比較例１〜１４において使用した成分は以下のとおりである。
＜成分＞
炭化水素系溶剤（Ａ）
イソパラフィン系溶剤 イソドデカン
混合ナフテン系溶剤 炭素数１１〜１３のナフテンの混合物
芳香族系溶剤 炭素数１１〜１３の芳香族炭化水素の混合物
ノルマルパラフィン系溶剤 ドデカン
The compositions of the cleaning compositions prepared as Examples 1 to 29 and Comparative Examples 1 to 14 are shown in Tables 1 to 3. The components used in Examples 1 to 29 and Comparative Examples 1 to 14 are as follows.
<Ingredients>
Hydrocarbon solvent (A)
Isoparaffinic solvent Isododecane Mixed naphthenic solvent Mixture of naphthene having 11 to 13 carbon atoms Aromatic solvent Mixture of aromatic hydrocarbons having 11 to 13 carbon atoms Normal paraffinic solvent Dodecane
（被洗浄物のエッチング性）
表１〜表３にその組成を示す実施例または比較例の洗浄液組成物を用い、表面を研磨した銅、亜鉛、黄銅の各テストピース（７５×１２．５×３ｍｍ）を、それぞれ３０ｍＬの洗浄剤組成物中に１００℃で３時間浸漬した後、洗浄液組成物中に溶出した金属量をＩＣＰ発光分析法にて定量した。金属量が１０質量ｐｐｍ以上であれば○（エッチング性良好）、１０質量ｐｐｍより小さければ×（エッチング性不良）とした。結果を表１〜表３に示す。
(Etching property of the object to be cleaned)
Using the cleaning liquid compositions of Examples or Comparative Examples whose compositions are shown in Tables 1 to 3, each of the test pieces (75 × 12.5 × 3 mm) of polished copper, zinc, and brass was cleaned with 30 mL each. After immersing in the agent composition at 100 ° C. for 3 hours, the amount of metal eluted in the cleaning liquid composition was quantified by ICP emission spectrometry. When the amount of metal was 10 mass ppm or more, it was evaluated as “Good” (good etching property), and when it was less than 10 mass ppm, “No” (poor etching property). The results are shown in Tables 1 to 3.
（洗浄性評価）
不水溶性切削油（サンワケミカル株式会社製スーパーカット）にて加工した銅製ワーク（被洗浄物）を、表１〜表３に示す実施例１〜２９および比較例１〜１４の洗浄剤組成物中に浸漬し、超音波洗浄器（商品名：Ｗ−１１３（本多電子（株）製））を用いて、２８ＫＨｚ、室温で１０分間洗浄した。洗浄後の被洗浄物をノルマルパラフィン系溶剤に浸漬し、室温で１分間すすぎを行った後、７０℃で４０分間乾燥した。被洗浄物を乾燥後、被洗浄物表面を目視観察した。洗浄残渣なしが○、洗浄残渣ありを×とした。結果を表１〜表３に示す。
(Cleanability evaluation)
Cleaning compositions of Examples 1 to 29 and Comparative Examples 1 to 14 shown in Tables 1 to 3 for copper workpieces (objects to be cleaned) processed with a water-insoluble cutting oil (Super Cut manufactured by Sanwa Chemical Co., Ltd.) It was immersed in and washed for 10 minutes at 28 KHz and room temperature using an ultrasonic cleaner (trade name: W-113 (manufactured by Honda Electronics Co., Ltd.)). The object to be cleaned after washing was immersed in a normal paraffin solvent, rinsed at room temperature for 1 minute, and then dried at 70 ° C. for 40 minutes. After drying the object to be cleaned, the surface of the object to be cleaned was visually observed. “No” indicates that there is no cleaning residue, and “X” indicates that there is a cleaning residue. The results are shown in Tables 1 to 3.
（被洗浄物への影響）
洗浄性評価後の銅製ワーク（被洗浄物）のうち、洗浄残渣がない被洗浄物について、目視によりさびの有無を確認した。さびがないものを○、さびがあるものを×とした。結果を表１〜表３に示す。
(Influence on the object to be cleaned)
Of the copper workpieces (objects to be cleaned) after the evaluation of the cleaning performance, the presence or absence of rust was visually confirmed for the objects to be cleaned that had no cleaning residue. The one without rust was marked with ○, and the one with rust was marked with ×. The results are shown in Tables 1 to 3.
表１〜表３に示すように、炭化水素系溶剤（Ａ）６０．０〜９９．７質量％、被洗浄物の表面をわずかにエッチングする化合物または混合物（Ｂ）を０．３〜３０．０質量％、あるいは、化合物または混合物（Ｂ）と脂肪酸アルカノールアミン（Ｃ）を合わせて０．３〜４０．０質量％含む実施例１〜２９の洗浄剤組成物は、銅、亜鉛、および黄銅の表面をエッチングする。また、銅製の被洗浄物の表面をエッチングすることにより、銅製の被洗浄物の表面に固着した不水溶性切削油成分が洗浄できることが確認された。また、本発明にかかる洗浄剤組成物により被洗浄物がさびないことも確認できた。 As shown in Tables 1 to 3, the hydrocarbon solvent (A) is 60.0 to 99.7% by mass, and the compound or mixture (B) that slightly etches the surface of the object to be cleaned is 0.3 to 30. The cleaning composition of Examples 1 to 29 containing 0 to 4% by mass, or 0.3 to 40.0% by mass of the compound or mixture (B) and the fatty acid alkanolamine (C) is copper, zinc, and brass. Etch the surface. Moreover, it was confirmed that the water-insoluble cutting oil component fixed to the surface of the copper object to be cleaned can be cleaned by etching the surface of the copper object to be cleaned. Moreover, it was also confirmed that the cleaning object was not rusted by the cleaning composition according to the present invention.
本発明の洗浄剤組成物は、自動車、機械、精密機器、電気、電子、光学等の各種工業分野において扱われる部品であって、銅、亜鉛、またはこれらの金属を含む合金からなる部品の洗浄に好適に使用可能である。 The cleaning composition of the present invention is a part handled in various industrial fields such as automobiles, machines, precision instruments, electricity, electronics, optics, etc., and is a part that is made of copper, zinc, or an alloy containing these metals. Can be suitably used.
Claims (6)
下記一般式（１）で表されるＮ−アルキルプロピレンジアミン脂肪酸塩（Ｂ−１）、
Ｒ１−ＮＨ（ＣＨ２）３ＮＨ２・２Ｒ２−ＣＯＯＨ ・・・（１）
（式（１）において、Ｒ１およびＲ２は、炭素数７〜２２のアルキル基である）
下記一般式（２）で表されるサルコシン類（Ｂ−２）、
Ｒ３−Ｃ（Ｏ）−Ｎ（ＣＨ３）−ＣＨ２−ＣＯＯＨ ・・・（２）
（式（２）において、Ｒ３は、炭素数７〜２１のアルキル基である）
および炭素数７〜２２の脂肪酸と炭素数７〜２２のアミンとの混合物（Ｂ−３）からなる群から選ばれる少なくとも１種の化合物または混合物（Ｂ）と、を含み、
前記炭化水素系溶剤（Ａ）を６０．０〜９９．７質量％、前記化合物または混合物（Ｂ）を０．３〜３０．０質量％含有することを特徴とする、銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物。 A hydrocarbon solvent (A);
N-alkylpropylenediamine fatty acid salt (B-1) represented by the following general formula (1),
R 1 —NH (CH 2 ) 3 NH 2 .2R 2 —COOH (1)
(In formula (1), R 1 and R 2 are alkyl groups having 7 to 22 carbon atoms)
Sarcosines (B-2) represented by the following general formula (2),
R 3 —C (O) —N (CH 3 ) —CH 2 —COOH (2)
(In Formula (2), R 3 is an alkyl group having 7 to 21 carbon atoms)
And at least one compound or mixture (B) selected from the group consisting of a mixture (B-3) of a fatty acid having 7 to 22 carbon atoms and an amine having 7 to 22 carbon atoms,
Copper, zinc, or these, characterized by containing 60.0-99.7% by mass of the hydrocarbon solvent (A) and 0.3-30.0% by mass of the compound or mixture (B) A cleaning composition for alloys containing any metal.
前記炭化水素系溶剤（Ａ）を６０．０〜９９．７質量％、前記化合物または混合物（Ｂ）と前記脂肪酸アルカノールアミド（Ｃ）とを合わせて０．３〜４０．０量％の割合で含有することを特徴とする、請求項１に記載の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物。 A fatty acid alkanolamide (C) which is a salt of a fatty acid having 7 to 22 carbon atoms and an alkanolamine having 7 to 22 carbon atoms;
The hydrocarbon solvent (A) is 60.0 to 99.7% by mass, and the compound or mixture (B) and the fatty acid alkanolamide (C) are combined at a ratio of 0.3 to 40.0% by mass. The cleaning composition for an alloy containing copper, zinc, or a metal thereof according to claim 1, wherein the composition is contained.
請求項１〜４のいずれか一つに記載の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物に前記被洗浄物を浸漬し洗浄する洗浄工程と、
前記洗浄工程後、前記被洗浄物を前記炭化水素系溶剤（Ａ）に浸漬するすすぎ工程と、を有し、
前記洗浄工程において、銅、亜鉛、またはこれらの金属を含む合金からなる前記被洗浄物の銅、亜鉛、またはこれらの金属を含む合金の表面をエッチングすることにより被洗浄物の表面に付着する汚れを洗浄することを特徴とする銅、亜鉛、またはこれらの金属を含む合金からなる被洗浄物の洗浄方法。 A method for cleaning an object to be cleaned comprising copper, zinc, or an alloy containing these metals,
A cleaning step of immersing and cleaning the object to be cleaned in a cleaning composition for an alloy containing copper, zinc, or a metal thereof according to any one of claims 1 to 4,
A rinsing step of immersing the object to be cleaned in the hydrocarbon solvent (A) after the cleaning step;
In the cleaning step, dirt that adheres to the surface of the object to be cleaned by etching the surface of copper, zinc, or an alloy including these metals of the object to be cleaned made of copper, zinc, or an alloy including these metals. A method for cleaning an object to be cleaned made of copper, zinc, or an alloy containing these metals.
請求項１〜４のいずれか一つに記載の銅、亜鉛、またはこれらの金属を含む合金用洗浄剤組成物に前記微粒子が付着した被洗浄物を浸漬し前記微粒子を除去する除去工程と、
前記除去工程後、前記被洗浄物を前記炭化水素系溶剤（Ａ）に浸漬するすすぎ工程と、を有し、
前記除去工程において、銅、亜鉛、またはこれらの金属を含む合金からなる前記微粒子の表面をエッチングすることにより被洗浄物の表面から前記微粒子を除去することを特徴とする銅、亜鉛、またはこれらの金属を含む合金からなる微粒子の除去方法。 A method for removing fine particles comprising copper, zinc, or an alloy containing these metals,
A removing step of removing the fine particles by immersing the object to be cleaned, in which the fine particles are attached to the cleaning composition for copper, zinc, or an alloy containing these metals according to any one of claims 1 to 4,
A rinsing step of immersing the object to be cleaned in the hydrocarbon solvent (A) after the removing step;
In the removing step, the fine particles are removed from the surface of the object to be cleaned by etching the surface of the fine particles made of copper, zinc, or an alloy containing these metals. A method for removing fine particles made of an alloy containing a metal.
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