JP3980162B2 - Cleaning agent for resin stains of electronic parts - Google Patents

Description

【００７８】
〔実施例５〕
ベアシリコンウェハ（直径４インチ）を、ポリスチレンラテックス（日本合成ゴム株式会社製；商品名 ＳＴＡＤＥＸ、粒径０．３０９μｍ）を分散させた希フッ酸液に浸漬し、ポリスチレンラテックスを上記ベアシリコンウェハ表面に付着させた。ベアシリコンウェハ表面に付着したポリスチレンラテックスの粒子数を表面検査装置（Surfscan 4500)を用いて測定した。
【００７９】
その後、このベアシリコンウェハを、実施例（１）で得られた洗浄液（１）を用いて１０分間洗浄し、ポリスチレンラテックスの除去を行った。洗浄後のベアシリコンウェハを超純水で５分間水洗し、スピンドライによって所定時間乾燥した後、上記の表面検査装置を用いて、ベアシリコンウェハ表面に残留する、粒子径０．２４μｍ以上のポリスチレンラテックスの粒子数を測定した。この結果を、洗浄前のベアシリコンウェハ表面に付着していたポリスチレンラテックスの粒子数と併せて表２に示す。
〔実施例６〕
実施例５において、洗浄液（１）に代えて、実施例（２）で得られた洗浄液（２）を用いた以外は、実施例５と同様の方法により、洗浄前後のベアシリコンウェハ表面のポリスチレンラテックスの粒子数を測定した。この結果を表２に示す。
〔実施例７〕
実施例５において、洗浄液（１）に代えて、実施例（３）で得られた洗浄液（３）を用いた以外は、実施例５と同様の方法により、洗浄前後のベアシリコンウェハ表面のポリスチレンラテックスの粒子数を測定した。この結果を表２に示す。
〔実施例８〕
実施例５において、洗浄液（１）に代えて、実施例（４）で得られた洗浄液（４）を用いた以外は、実施例５と同様の方法により、洗浄前後のベアシリコンウェハ表面のポリスチレンラテックスの粒子数を測定した。この結果を表２に示す。
〔比較例２〕
実施例５において、洗浄液（１）に代えて、比較例１で得られた比較用の洗浄液（５）を用いた以外は、実施例５と同様の方法により、洗浄前後のベアシリコンウェハ表面のポリスチレンラテックスの粒子数を測定した。この結果を表２に示す。
【００８０】
【表２】

【００８１】
〔参考例１〕
水と、実施例１で得られた水溶性グラフト重合体（１）のナトリウム塩と、アルカリ金属水酸化物とを、８０重量％：５重量％：１５重量％の割合で混合し、本参考例にかかる洗浄剤（６）を調製した。
【００８２】
続いて、上記洗浄液（６）５００ｍｌを、５００ｍｌガラスビーカーに採取し、該ガラスビーカーを恒温槽（温水槽）に設置した。次いで、上記洗浄液（６）の温度を６０℃に昇温させて該温度で保持し、該洗浄液（６）にテストピースを２０分間浸漬した。その後、このテストピースを、水道水の流水下で１分間すすぎ、さらに、１分間エアーブローを行った。
【００８３】
上記テストピースには、８ｃｍ×４ｃｍ×０．５ｍｍの鋼板を用いて得られたアクリルメラミン静電塗装品（プライマー：エポキシメラミン樹脂、塗装厚：合計４０μｍ）を用いた。
【００８４】
上記テストピース表面に塗装された樹脂の剥離・洗浄の程度を目視で評価することにより、上記洗浄剤（６）の洗浄性を評価した。評価基準は下記の通りである。樹脂が１００％完全に剥離・洗浄されているものを「◎」とし、樹脂の少なくとも７０％程度が剥離・洗浄されているものを「○」とし、剥離・洗浄されている樹脂の割合が７０％未満（一部分）であるものを「△」とし、樹脂が全く剥離・洗浄されていないものを「×」とした。この結果を、主な洗浄条件と併せて表３に示す。
〔参考例２〕
水と、実施例（２）で得られた水溶性グラフト重合体（２）のナトリウム塩と、アルカリ金属水酸化物とを、８０重量％：５重量％：１５重量％の割合で混合し、本参考例にかかる洗浄剤（７）を調製した。
【００８５】
続いて、参考例１において、洗浄液（６）に代えて上記洗浄液（７）を用いた以外は、参考例１と同様の操作を行って、テストピース表面に塗装された樹脂の剥離・洗浄の程度を目視で評価することにより、上記洗浄剤（７）の洗浄性を参考例１と同様にして評価した。上記テストピースには、参考例１と同様のアクリルメラミン静電塗装品を用いた。上記評価の結果を、主な洗浄条件と併せて表３に示す。
〔比較例３〕
水とアルカリ金属水酸化物とを、８５重量％：１５重量％の割合で混合することにより、比較用の洗浄剤（８）を調製した。
【００８６】
続いて、参考例１において、洗浄液（６）に代えて上記洗浄液（８）を用いた以外は、参考例１と同様の操作を行って、テストピース表面に塗装された樹脂の剥離・洗浄の程度を目視で評価することにより、上記洗浄剤（８）の洗浄性を参考例１と同様にして評価した。上記テストピースには、参考例１と同様のアクリルメラミン静電塗装品を用いた。上記評価の結果を、主な洗浄条件と併せて表３に示す。
〔参考例３〕
水と、実施例（３）で得られた水溶性グラフト重合体（３）のナトリウム塩と、アルカリ金属水酸化物とを、８０重量％：５重量％：１５重量％の割合で混合し、本参考例にかかる洗浄剤（９）を調製した。
【００８７】
続いて、上記洗浄液（９）を、５００ｍｌガラスビーカーに採取し、該ガラスビーカーを恒温槽（温水槽）に設置した。次いで、上記洗浄液（９）の温度を６０℃に昇温させて該温度で保持し、該洗浄液（９）にテストピースを８時間浸漬した。その後、このテストピースを、参考例１と同様の条件にて、水道水の流水下で１分間すすぎ、さらに、１分間エアーブローを行った。
【００８８】
本参考例では、上記テストピースとして、８ｃｍ×４ｃｍ×０．５ｍｍの鋼板を用いて得られたポリエステル粉体静電塗装品（塗装厚：最大４４００μｍ）を用いた。
【００８９】
上記テストピース表面に塗装された樹脂の剥離・洗浄の程度を目視で評価することにより、上記洗浄剤（９）の洗浄性を、参考例１と同様にして評価した。この結果を、主な洗浄条件と併せて表３に示す。
〔参考例４〕
水と、実施例（４）で得られた水溶性グラフト重合体（４）のナトリウム塩と、アルカリ金属水酸化物とを、８０重量％：５重量％：１５重量％の割合で混合し、本参考例にかかる洗浄剤（１０）を調製した。
【００９０】
続いて、実施例１１において、洗浄液（９）に代えて上記洗浄液（１０）を用いた以外は、参考例３と同様の操作を行って、テストピース表面に塗装された樹脂の剥離・洗浄の程度を目視で評価することにより、上記洗浄剤（１０）の洗浄性を実施例９と同様にして評価した。上記テストピースには、参考例３と同様のポリエステル粉体静電塗装品を用いた。上記評価の結果を、主な洗浄条件と併せて表３に示す。
〔比較例４〕
参考例３において、洗浄液（９）に代えて、比較例３と同様の操作により得られた洗浄剤（８）を用いた以外は、参考例３と同様の操作を行って、テストピース表面に塗装された樹脂の剥離・洗浄の程度を目視で評価することにより、上記洗浄剤（８）の洗浄性を参考例１と同様にして評価した。上記テストピースには、参考例３と同様のポリエステル粉体静電塗装品を用いた。上記評価の結果を、主な洗浄条件と併せて表３に示す。
【００９１】
【表３】

【００９２】
表１〜３に記載の結果から、本発明にかかる水溶性グラフト重合体を洗浄剤の成分として用いれば、上記水溶性グラフト重合体を用いない場合と比較して、洗浄剤を調製してから３０分経過後の泡立ちが少なく、しかも、洗浄性に優れていることが判る。
【００９３】
【発明の効果】
本発明に係る電子部品の樹脂汚れ用洗浄剤は、以上のように、モノエチレン性不飽和カルボン酸系単量体を含むモノエチレン性不飽和単量体成分をポリエーテル化合物にグラフト重合してなる水溶性グラフト重合体、アンモニア、過酸化水素、水、フッ素系界面活性剤およびホスホン酸化合物を含む構成である。上記電子部品の樹脂汚れ用洗浄剤において、上記水溶性グラフト重合体の配合割合は０．５重量％〜６０重量％の範囲内であり、上記アンモニアの配合割合は２重量％〜９０重量％の範囲内であり、上記過酸化水素の配合割合は０．５重量％〜７０重量％の範囲内であり、上記フッ素系界面活性剤の配合割合は０．１重量％〜４０重量％の範囲内であり、上記ホスホン酸化合物の配合割合は０．０１重量％〜２０重量％の範囲内であることが好ましい。さらに、水は、各成分の合計量を１００重量部としたときの残部であり、水の配合割合は５重量％〜９８重量％の範囲内であることが好ましい。
【００９４】
上記の構成によれば、低発泡性、消泡性に優れると共に、洗浄性に優れた電子部品の樹脂汚れ用洗浄剤を提供することができるという効果を奏する。
【００９５】
また、上記の水溶性グラフト重合体は、製造にかかる費用が安価であり、かつ、上記水溶性グラフト重合体を含む電子部品の樹脂汚れ用洗浄剤が、低泡性、消泡性、洗浄性に優れることから、作業性にも優れ、洗浄時間や洗浄回数、すすぎ水の量等を削減することができ、洗浄にかかる費用を低減させることができる。また、上記の水溶性グラフト重合体は、残存する単量体量が少なく、ほとんど毒性がない。しかも、上記の水溶性グラフト重合体は、洗浄性を向上させることができるため、より穏和な条件で洗浄を行うことができる。従って、上記電子部品の樹脂汚れ用洗浄剤は、経済性並びに安全性が非常に高いものである。
【００９６】
上記の電子部品の樹脂汚れ用洗浄剤は、例えば、シリコンウェハ等に付着した樹脂汚れの洗浄・除去に特に好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
  The present invention is an electronic component suitably used for cleaning electronic components such as semiconductor substrates and lead frames.Resin stainsIt relates to a cleaning agent.
[0002]
[Prior art]
  In recent years, along with the complexity of electronic devices such as high integration of semiconductor devices, pattern miniaturization and complexity in electronic components such as semiconductor substrates and lead frames used in these electronic devices, and thin films Is progressing.
[0003]
  The surface of these electronic components such as semiconductor substrates and lead frames is very sensitive. If these electronic component surfaces are contaminated, the surface conduction and other parameters of these electronic components may be affected, or the pn junction breakdown voltage may be reduced. Lowering and film peeling are caused. For this reason, contamination of the surface of these electronic components leads to a shortened life of these electronic components and a decrease in reliability. Accordingly, in the manufacturing process of these electronic components, a cleaning process for removing the contaminants attached to these electronic components is indispensable. By removing the contaminants on the surface of these electronic components, the characteristics of these electronic components are reduced. Stability and reproducibility can be remarkably improved.
[0004]
  Examples of contamination on the surface of these electronic components include, for example, resin such as wax, resin, and photoresist, so-called resin stains due to unreacted monomers, and metal (fine) particles such as copper and nickel used for wiring and plating, and metal Examples include adhesion of ions and metal impurities.
[0005]
  Conventionally, as a cleaning agent used for decomposing and removing (fine) particles and metal impurities on a silicon wafer, an aqueous solution obtained by adding other chemicals to ammonia water is often used. A so-called SC-1 cleaning liquid in which hydrogen and water are mixed is generally used.
[0006]
  However, in the recent cleaning situation of electronic parts where the pattern is becoming finer, more complicated, and thinner, the SC-1 cleaning liquid has the ability to remove contaminants such as (fine) particles adhering to the surface of the electronic part. In addition, there is a problem that metal impurities are easily adsorbed on the surface of the silicon wafer and have an etching action on the silicon substrate.
[0007]
  Accordingly, in order to solve the above problems, a cleaning composition comprising a specific fluorine-based surfactant, a compound having two or more phosphonic acid groups, and ammonia as a composition for cleaning a silicon wafer. (JP 9-286999 A) and a cleaning composition obtained by adding a specific oxidizing agent to an alkaline aqueous solution or an acidic aqueous solution (JP 9-279189 A).
[0008]
  On the other hand, as cleaning agents used for resin stains such as semiconductor substrates and lead frames, alkaline cleaning agents mainly composed of sodium hydroxide or potassium hydroxide, methylene chloride, and the like are frequently used. Furthermore, in recent years, with regard to the cleaning of such resin soil, the resin soil is disintegrated and dissolved with a cleaning composition (I) containing a specific aromatic monocyclic compound, glycol ether compound, and ethylene glycol-based compound. Proposed is a method (Japanese Patent Laid-Open No. 9-263792) for removing resin stains with a detergent composition (II) containing an aromatic compound, a metal sealant, an alkali metal hydroxide, and water.
[0009]
[Problems to be solved by the invention]
  However, the alkali cleaning agents mainly composed of sodium hydroxide and potassium hydroxide, which have been used as a cleaning agent for resin stains, have insufficient cleaning power, and it takes time and effort to completely remove the resin stains. And has the problem that it is necessary. Furthermore, methylene chloride is questioned for its carcinogenicity and is strictly regulated against leakage into drainage and the atmosphere, and its use is required to be reduced or prohibited.
[0010]
  In addition, the cleaning compositions (I) and (II) described in JP-A No. 9-263793 are not sufficient in cleaning properties by themselves and are used by being mixed with each other, or the cleaning compositions (I ), And further washing with the detergent composition (II). For this reason, since preparation of a cleaning composition becomes complicated or time is required for cleaning, the cost for cleaning increases, which is not economical.
[0011]
  Furthermore, the cleaning composition described in JP-A-9-279189 used for cleaning a semiconductor substrate such as a silicon wafer is prepared by preparing ammonia aqueous solution or acidic aqueous solution with ammonia, hydrogen fluoride, (concentrated) hydrochloric acid, or Uses (concentrated) sulfuric acid and is toxic and irritating.
[0012]
  Further, as a result of the study by the inventors of the present application, the cleaning composition described in JP-A-9-286999 is still insufficient in the defoaming property of bubbles generated by the action of the added surfactant, and silicon It has been found that the ability to remove particles adhering to the wafer surface is not satisfactory.
[0013]
  The present invention has been made in view of the above-described conventional problems, and its object is to provide an inexpensive and safe electronic component that is excellent in defoaming and cleaning properties.Resin stainsIt is to provide a cleaning agent.
[0014]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above-described conventional problems, the inventors of the present application grafted a monoethylenically unsaturated monomer component containing a monoethylenically unsaturated carboxylic acid monomer to a polyether compound. The present invention has been completed by finding that a detergent containing a water-soluble graft polymer is excellent in antifoaming properties, detergency and safety, is inexpensive, and suitable for washing electronic components. .
[0015]
  That is,BookinventionPertaining toElectronic componentsResin stainsIn order to solve the above-described problems, the cleaning agent for water-soluble graft weight obtained by graft polymerization of a monoethylenically unsaturated monomer component containing a monoethylenically unsaturated carboxylic acid monomer to a polyether compound is used. Coalescence, Ammonia, hydrogen peroxide, water, fluorosurfactants and phosphonic acid compoundsIt is characterized by including.In the cleaning agent for resin stains of the electronic component, the blending ratio of the water-soluble graft polymer is in the range of 0.5 wt% to 60 wt%, and the blending ratio of the ammonia is 2 wt% to 90 wt%. The blending ratio of the hydrogen peroxide is in the range of 0.5 to 70% by weight, and the blending ratio of the fluorosurfactant is in the range of 0.1 to 40% by weight. The blending ratio of the phosphonic acid compound is preferably in the range of 0.01 wt% to 20 wt%. Furthermore, water is the balance when the total amount of each component is 100 parts by weight, and the blending ratio of water is preferably in the range of 5% by weight to 98% by weight.
[0016]
  The above water-soluble graft polymer is excellent in chelating ability and dispersibility of polyvalent metal ions, and is used for electronic parts when cleaning a cleaning liquid, that is, an object to be cleaned.Resin stainsChelates polyvalent metal ions in the cleaning agent to suppress (re) adhesion of polyvalent metal ions to the object to be cleaned, as well as contaminants such as resin and (fine) particles that have peeled off the object to be cleaned Reattachment to the object to be cleaned can be suppressed. The water-soluble graft polymer has less foaming and is excellent in antifoaming properties.
[0017]
  Further, the above water-soluble graft polymer is inexpensive to manufacture, and an electronic component comprising the water-soluble graft polymerResin stainsThe cleaning agent is excellent in low-foaming property, defoaming property, and detergency, so it is excellent in workability and can reduce the washing time, the number of washings, the amount of rinse water, etc. Cost can be reduced. Further, the above water-soluble graft polymer has a small amount of remaining monomer and is hardly toxic. And since said water-soluble graft polymer can improve washability, it can wash | clean on milder conditions. Therefore, according to the above configuration, an inexpensive and safe electronic component having excellent defoaming properties and cleanability.Resin stainsA cleaning agent can be provided.
[0018]
  The present invention is described in detail below.
[0019]
  The water-soluble graft polymer according to the present invention grafts a monoethylenically unsaturated monomer component (B) containing a monoethylenically unsaturated carboxylic acid monomer as an essential component to a polyether compound (A). Polymerized.
[0020]
  In the present invention, the polyether compound (A) used as a raw material for the water-soluble graft polymer is not particularly limited, but preferably has a number average molecular weight of 100 containing ethylene oxide as a main constituent unit. These compounds are more preferable, and compounds containing 80 mol% or more of ethylene oxide as a structural unit are more preferable.
[0021]
  For example, the polyether compound (A) is obtained by polymerizing ethylene oxide and an alkylene oxide copolymerizable with the ethylene oxide (hereinafter referred to as other alkylene oxide) by a known method using water or alcohol as a starting point. Thus, it can be easily obtained.
[0022]
  Although it does not specifically limit as said other alkylene oxide, A propylene oxide or a butylene oxide is preferable.
[0023]
  The proportion of the structural unit composed of ethylene oxide and the structural unit composed of other alkylene oxide in the polyether compound (A), that is, the ethylene oxide in producing the polyether compound (A) and the other alkylene oxide The usage ratio is preferably such that ethylene oxide is 80 mol% or more of the whole and the amount of the other alkylene oxide is less than 20 mol% as a whole. If the amount of the other alkylene oxide is 20 mol% or more, the graft ratio of the water-soluble graft polymer obtained using the polyether compound (A) may be lowered.
[0024]
  Moreover, as alcohol for obtaining the said polyether compound (A), specifically, C1-C22 primary or secondary alcohol, such as methanol, ethanol, n-propanol, n-butanol, etc .; Secondary alcohols having 3 to 18 carbon atoms such as isopropanol and 2-butanol; tertiary alcohols such as t-butanol; diols such as ethylene glycol, diethylene glycol, propanediol, butanediol, and propylene glycol; glycerin, trimethylolpropane, and the like Triols; polyols such as sorbitol; aromatic alcohols such as phenol and naphthol;
[0025]
  The polyether compound (A) thus obtained preferably has a number average molecular weight of 100 or more, more preferably 500 or more. Further, the upper limit of the number average molecular weight of the polyether compound (A) is not particularly limited, but is preferably 20,000 or less, and the polyether compound (A) has two or more hydroxyl groups. Is preferably 6,000 or less. When the number average molecular weight of the said polyether compound (A) is less than 100, the polyether compound (A) which does not participate in graft polymerization increases. Moreover, when a number average molecular weight exceeds 20,000, there exists a possibility that a gelatinization-proof performance may fall and a polyvalent metal ion chelating ability may fall.
[0026]
  In addition, as said polyether compound (A), dicarboxylic acid, such as a C2-C22 fatty acid, a succinic acid, a succinic anhydride, a maleic acid, a maleic anhydride, an adipic acid, is used for all the terminal or a part of terminal hydroxyl groups. Those esterified with an acid are also included.
[0027]
  Of the raw materials for the water-soluble graft polymer, the monoethylenically unsaturated monomer component (B) contains a monoethylenically unsaturated carboxylic acid monomer as an essential component.
[0028]
  In the present invention, the monoethylenically unsaturated carboxylic acid monomer is particularly preferably (meth) acrylic acid, and the monoethylenically unsaturated monomer component (B) contains (meth) acrylic acid. Is preferably contained within a range of 40 mol% to 100 mol%.
[0029]
  In the present invention, the graft ratio of the monoethylenically unsaturated monomer component (B) to the polyether compound (A) is as follows: The monomer component (B) is preferably graft-polymerized by 25% by weight or more, and among the monoethylenically unsaturated monomer component (B), as the monoethylenically unsaturated carboxylic acid monomer, ( More preferably, the (meth) acrylic acid is 20% by weight or more graft-polymerized with respect to 100% by weight of the polyether compound (A). If the ratio of the monoethylenically unsaturated monomer component (B) to the polyether compound (A) is less than 25% by weight, the resulting water-soluble graft polymer has a reduced carboxylic acid density, and various performances such as The polyvalent metal ion chelating ability, dispersibility and the like are not satisfactory. Moreover, when the usage-amount of a monoethylenically unsaturated monomer component (B) is 100 weight% or more, the carboxylic acid amount (carboxylic acid density) of the water-soluble graft polymer obtained becomes too high, and polyvalent The resulting water-soluble graft polymer is easily gelled by the metal ions.
[0030]
  Monoethylenically unsaturated monomers copolymerizable with the (meth) acrylic acid, that is, monoethylenically unsaturated carboxylic monomers other than the (meth) acrylic acid, and these monoethylenically unsaturated carboxylic acids Monoethylenically unsaturated monomers other than the monomer based monomers (hereinafter, these are collectively referred to as other monoethylenically unsaturated monomers) are not particularly limited, but the above (meth) Specific examples of the monoethylenically unsaturated carboxylic acid monomer other than acrylic acid include (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride and the like. Specific examples of monoethylenically unsaturated monomers other than these monoethylenically unsaturated carboxylic acid monomers include maleic acid alkyl esters such as dimethyl maleate and diethyl maleate; Alkyl esters of fumaric acid such as dimethyl fumarate and diethyl fumarate; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (mea) acrylate; hydroxyethyl ( Hydroxyalkyl (meth) acrylates such as meth) acrylate and hydroxypropyl (meth) acrylate; Acetic acid alkenyl esters such as vinyl acetate; Aromatic vinyls such as styrene; (Meth) acrylonitrile, (meth) acrolein, (meth) acrylamide Dialkyl aminoethyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 2-acrylamido-2-methylpropane sulfonic acid and the like. These other monoethylenically unsaturated monomers may be used alone or in a suitable mixture of two or more. Among these other monoethylenically unsaturated monomers, maleic acid, fumaric acid and maleic anhydride are selected from the above (meth) acrylic acid in order to increase the carboxylic acid density and dispersibility of the resulting water-soluble graft polymer. It is preferable to share with.
[0031]
  The ratio of the monoethylenically unsaturated monomer component (B) to the other monoethylenically unsaturated monomer copolymerizable with (meth) acrylic acid is the introduction of carboxylic acid into the water-soluble graft polymer. From the rate and the amount of residual monomers, in the range of 0 mol% to 60 mol% of other monoethylenically unsaturated monomers with respect to (meth) acrylic acid 40 mol% to 100 mol% (however, the total of both Is preferably 100 mol%), more preferably maleic acid is used in the range of 20 mol% to 50 mol%, most preferably in the range of 30 mol% to 45 mol%. preferable.
[0032]
  The monoethylenically unsaturated monomer component (B) is a monoethylenically unsaturated monomer other than the monoethylenically unsaturated carboxylic acid monomer, among other monoethylenically unsaturated monomers. When a monomer is included, the content of a monoethylenically unsaturated monomer other than the unsaturated carboxylic acid monomer (that is, a monoethylenically unsaturated monomer having no carboxyl group) is 20 It is preferable that it is below mol%. When the content of the monoethylenically unsaturated monomer other than the unsaturated carboxylic acid monomer exceeds 20 mol%, the introduction rate of the carboxylic acid into the resulting water-soluble graft polymer is lowered and remains. This is not preferable because the amount of monomers increases, the carboxylic acid density decreases, and the polyvalent metal ion chelating ability and dispersibility are not satisfied.
[0033]
  When a monoethylenically unsaturated carboxylic acid monomer other than (meth) acrylic acid is used as the other monoethylenically unsaturated monomer, the content of (meth) acrylic acid is 40 mol%. Even if it is less than this, the carboxylic acid density of the water-soluble graft polymer obtained does not fall. However, in this case, if the content of (meth) acrylic acid is less than 40 mol%, the rate of introduction into the water-soluble graft polymer such as maleic acid, fumaric acid, and maleic anhydride is reduced, and the residual There is a tendency for the amount of monomer to increase.
[0034]
  In the present invention, the graft polymerization of the polyether compound (A) and the monoethylenically unsaturated monomer component (B) is carried out in the presence of a polymerization initiator, substantially without using a catalyst and a solvent.
[0035]
  When the polyether compound (A) and the monoethylenically unsaturated monomer component (B) are graft-polymerized in the presence of water or an organic solvent such as alcohol or toluene, the polyether compound (A) Since the grafting efficiency of the monoethylenically unsaturated monomer (B) onto the resin is lowered, it is not preferable. Therefore, when a solvent is used for the addition of the polymerization initiator or the monoethylenically unsaturated monomer component (B), it is preferable to reduce the amount as much as possible. Specifically, the amount is preferably 5% by weight or less with respect to the total amount of the polymerization reaction system, or it is preferably distilled immediately from the polymerization reaction system after the addition of the solvent.
[0036]
  As the polymerization initiator, known radical polymerization initiators can be used, and among these, organic peroxides are particularly preferable. Specific examples of the organic peroxide that can be used as a radical polymerization initiator in the present invention include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; t-butyl hydroperoxide, cumene. Hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Peroxides; di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxy) p-diisopropylbenzene, α, α′-bis (t -Butylpa Oxy) dialkyl peroxides such as p-diisopropylhexyne; t-butyl peroxyacetate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5- Peroxyesters such as dimethyl-2,5-di (benzoylperoxy) hexane and t-butylperoxyisopropyl carbonate; n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2- Peroxyketals such as bis (t-butylperoxy) butane; diacyl peroxides such as dibenzoyl peroxide; and the like.
[0037]
  The amount of these polymerization initiators used is not particularly limited, but it is preferably used in a proportion of 0.1% by weight to 15% by weight with respect to the monoethylenically unsaturated monomer component (B). More preferably, it is used at a ratio of 0.5 wt% to 10 wt%. When the usage-amount of a polymerization initiator deviates from said range, the graft polymerization efficiency of the monoethylenically unsaturated monomer component (B) with respect to a polyether compound (A) falls. The polymerization initiator may be added to the polyether compound (A) in advance, or may be added simultaneously with the monoethylenically unsaturated monomer component (B).
[0038]
  Moreover, polymerization temperature is 100 degreeC or more, Preferably it exists in the range of 110 to 160 degreeC, More preferably, it exists in the range of 110 to 140 degreeC. If the polymerization temperature is lower than 100 ° C., the grafting efficiency of the monoethylenically unsaturated monomer component (B) onto the polyether compound (A) is lowered. On the other hand, when the polymerization temperature exceeds 160 ° C., the polyether compound (A) and the resulting water-soluble graft polymer may be thermally decomposed.
[0039]
  In the present invention, when the graft polymerization is performed, it is preferable that a part or all of the polyether compound (A) is initially charged. In addition, in the monoethylenically unsaturated monomer component (B), monoethylenically unsaturated carboxylic acid monomers such as maleic acid, fumaric acid, maleic anhydride and the like as the other monoethylenically unsaturated monomers In the case of using the above, after mixing at least half of these other monoethylenically unsaturated monomers in advance with the polyether compound (A) in advance, and heating the resulting mixture to 100 ° C. or higher The method of graft polymerization by adding the remaining monoethylenically unsaturated monomer component (B) and the polymerization initiator separately to the mixture is particularly preferred. As a method for adding the monoethylenically unsaturated monomer component (B) and the polymerization initiator separately, for example, using a dropping device, the monoethylenically unsaturated monomer component (B) and Although the method etc. of dripping a polymerization initiator at the same time to the said mixture from a separate dripping apparatus are mentioned, It does not specifically limit.
[0040]
  By adopting the above method, it is possible to significantly improve the rate of introduction of monoethylenically unsaturated carboxylic acid monomers such as maleic acid, fumaric acid and maleic anhydride into the water-soluble graft polymer. When a part of the polyether compound (A) is initially charged, the remaining polyether compound (A) is mixed with a polymerization initiator or a monoethylenically unsaturated monomer component (B) and added. May be.
[0041]
  The water-soluble graft polymer thus obtained has a polyanion structure having a large number of carboxyl groups by a monoethylenic carboxylic acid monomer grafted on a polyethylene glycol chain, is difficult to foam, and has a defoaming property. Also excellent.
[0042]
  The water-soluble graft polymer is a polymer having a solubility in water of 1% or more. The water-soluble graft polymer may be used as it is, and after completion of the graft polymerization reaction, by adding a basic compound and neutralizing, for example, a monovalent metal salt such as sodium salt or potassium salt; calcium salt Divalent metal salts such as aluminum salts; Trivalent metal salts such as aluminum salts; Ammonium salts; Organic amine salts such as monoethanolamine salts and triethanolamine salts; Alternatively, it may be used after complete neutralization. The solvent used when adding the basic compound is preferably water, but is not particularly limited.
[0043]
  The weight average molecular weight of the water-soluble graft polymer is not particularly limited, but is preferably in the range of 500 to 50,000. If said weight average molecular weight is less than 500, there exists a tendency for detergency to fall as a result of a chelate power falling. On the other hand, when the weight average molecular weight exceeds 50,000, the water-soluble graft polymer is easily gelled by polyvalent metal ions, and the detergency tends to decrease.
[0044]
  Electronic component according to the present inventionResin stainsCleaning agent (hereinafter simply referred to as cleaning agent) contains the above water-soluble graft polymer. The object to be cleaned to which the cleaning with the cleaning agent can be applied is not particularly limited. For example, a semiconductor substrate such as a silicon wafer, a lead frame, a liquid crystal color filter, a ceramic electronic component such as a magnetic head, A printed wiring board etc. are mentioned. Examples of contaminants removed by the cleaning agent include, for example, resins such as wax, resin, and photoresist, and unreacted monomers, metal (fine) particles such as copper and nickel used for wiring and plating, and the like. Examples include metal ions and metal impurities.
[0045]
  In the present invention, components other than the water-soluble graft polymer contained in the cleaning agent are not particularly limited, and examples thereof include surfactants, phosphonic acid compounds, ammonia, hydrogen peroxide, and alkali metals. What is necessary is just to mix | blend suitably according to the kind etc. of the to-be-cleaned object or the contaminant which should be removed from hydroxide, a metal sealing agent, etc.
[0046]
  When the cleaning agent according to the present invention is used as a cleaning agent for silicon wafers, the cleaning agent preferably contains the water-soluble graft polymer, and further contains ammonia, hydrogen peroxide, and water. In addition to these ammonia, hydrogen peroxide, and water, it is more preferable to further contain a fluorine-based surfactant and a phosphonic acid-based compound.
[0047]
  The blending ratio of the water-soluble graft polymer in the cleaning agent is preferably in the range of 0.5 wt% to 60 wt%, more preferably in the range of 0.8 wt% to 40 wt%, from the viewpoint of detergency. The range of 1% to 30% by weight is most preferable.
[0048]
  Further, the mixing ratio of the ammonia is preferably in the range of 2% by weight to 90% by weight, more preferably in the range of 10% by weight to 60% by weight, and in the range of 20% by weight to 50% by weight from the viewpoint of detergency. Within the range is most preferred. As the ammonia, commercially available aqueous ammonia can be used by appropriately adjusting so that the blending amount of ammonia is within the above range.
[0049]
  The blending ratio of the hydrogen peroxide is preferably in the range of 0.5% by weight to 70% by weight, more preferably in the range of 1% by weight to 50% by weight from the viewpoint of detergency, and 2% by weight to 30% by weight. % Is most preferred. As the hydrogen peroxide, a commercially available hydrogen peroxide solution can be appropriately adjusted so that the blending amount of hydrogen peroxide is within the above range.
[0050]
  Moreover, as said fluorine-type surfactant, the well-known compound marketed as a fluorine-type surfactant can be used. Examples of the fluorosurfactant include:FluoroA fluoroalkylsulfonamide type fluorosurfactant such as butylsulfonamide is preferred. Only one kind of these fluorine-based surfactants may be used, or two or more kinds may be appropriately mixed and used. These fluorosurfactants are used by dissolving in ammonia water.
[0051]
  The blending ratio of the fluorosurfactant in the cleaning agent is not particularly limited, but is preferably in the range of 0.1% by weight to 40% by weight, and in the range of 0.2% by weight to 30% by weight. Is more preferable, and the range of 0.3% by weight to 20% by weight is most preferable. By using the fluorine-based surfactant at the above ratio, the cleaning property of the cleaning agent is further improved, and the so-called compactness of the detergent agent can be achieved. If the amount of the fluorosurfactant used is less than 0.1% by weight, the performance as a surfactant tends to decrease. On the other hand, even if the amount of the fluorosurfactant used is more than 40% by weight, further improvement in cleaning performance, etc. in proportion to the increase in the fluorosurfactant amount cannot be expected. Part of the agent is wasted, which is not preferable because it is economically disadvantageous.
[0052]
  Specific examples of the phosphonic acid compounds include N, N, N ′, N′-ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotris ( Methylenephosphonic acid), glycine-N, N-bismethylenephosphonic acid, phytic acid, methyldiphosphonic acid, ethylidenediphosphonic acid, ethylenediaminebis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa ( Methylenephosphonic acid), propylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), glycol etherdiaminetetra (methylenephosphonic acid), hexenediaminetetrakis (methylenephosphonic acid), trans 1,2-cyclohexanediaminetetra (methylenephosphonic acid), triaminotriethylamine hexa (methylenephosphonic acid), tetraethylenepentamine hexa (methylenephosphonic acid), tetraethylenepentaminehepta (methylenephosphonic acid), ethylaminobis (methylene Phosphonic acid), dodecylaminobis (methylenephosphonic acid), 1-hydroxypropylidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid and the like. Particularly preferably, N, N, N ′, N′-ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), glycine-N, N-bismethylenephosphone Examples of the acid include, but are not particularly limited to. Only one kind of these phosphonic acid compounds may be used, or two or more kinds may be appropriately mixed and used. These phosphonic acid compounds are also used by dissolving in ammonia water.
[0053]
  The blending ratio of the phosphonic acid compound in the cleaning agent is not particularly limited, but is preferably in the range of 0.01% by weight to 20% by weight, and in the range of 0.05% by weight to 10% by weight. More preferably, it is most preferably in the range of 0.1 wt% to 5 wt%. By using the phosphonic acid-based compound at the above ratio, it is possible to further suppress the decomposition of hydrogen peroxide in the cleaning liquid and further improve the cleaning properties of the cleaning agent.
[0054]
  In addition, the above electronicResin dirt on partsIf necessary, the cleaning agent may contain other additives usually contained in the cleaning agent for silicon wafers as long as the effects of the present invention are not impaired.
[0055]
  In the cleaning agent, the remainder other than the water-soluble graft polymer, ammonia, hydrogen peroxide, fluorine-based surfactant, phosphonic acid compound, and other additives is water. Moreover, these components used for the said cleaning agent are used so that the total amount may be 100 weight part. The water contained in the cleaning agent is not particularly limited as long as it does not impair the effects of the cleaning agent, such as ultrapure water, pure water, ion exchange water, distilled water, and tap water. The mixing ratio of water in the cleaning agent is preferably in the range of 5% to 98% by weight, more preferably in the range of 10% to 90% by weight, and most preferably in the range of 20% to 80% by weight. .
[0056]
  In addition, when the cleaning agent according to the present invention is used as a cleaning agent for resin stains in electronic components such as semiconductor substrates and lead frames, the cleaning agent includes the water-soluble graft polymer as an essential component, and an alkali metal. Preferably it contains hydroxide and water. Moreover, the said washing | cleaning agent may contain the metal sealing agent and other additives as needed.
[0057]
  The blending ratio of the water-soluble graft polymer in the cleaning agent is preferably in the range of 0.2% by weight to 60% by weight and more preferably in the range of 0.5% by weight to 50% by weight from the viewpoint of cleaning properties. Preferably, it is in the range of 0.8 wt% to 40 wt%.
[0058]
  Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, and sodium hydroxide and potassium hydroxide are particularly preferably used. Only one kind of these alkali metal hydroxides may be used, or two or more kinds may be appropriately mixed and used.
[0059]
  The blending ratio of the alkali metal hydroxide in the cleaning agent is preferably in the range of 0.1% by weight to 60% by weight and more preferably in the range of 0.5% by weight to 40% by weight from the viewpoint of cleaning properties. Most preferred is in the range of 3% to 30% by weight. If the amount of the alkali metal hydroxide used is less than 0.1% by weight, the detergency tends to decrease. On the other hand, if the amount of the alkali metal hydroxide used exceeds 60% by weight, the uniformity of the resulting cleaning agent may be hindered or the danger due to alkali may increase.
[0060]
  Moreover, as said metal sealing agent, specifically, for example, gluconic acid, tannic acid, 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, Carboxylic acids such as poly-α-hydroxyacrylic acid and glucuronic acid, and heptonic acid, 2,3-dihydroxyphenol, 2-hydroxyphenol, D-sorbit, D-mannit, dulcit, D-arabit, xylit, gluco Examples include norlactone, D-mannose, D-galactose, threitol, aminonaphthol, aminonaphtholsulfonic acid, salts of these exemplified compounds with alkali metals, triethanolamine, and the like.
[0061]
  Only one kind of the metal sealant may be used, or two or more kinds may be appropriately mixed and used. Among the above metal sealants, carboxylic acids such as gluconic acid, tannic acid, 3,4-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,3-dihydroxyphenol, and D-sorbit , D-mannitol, gluconolactone, D-galactose, aminonaphthol, aminonaphtholsulfonic acid, salts of these exemplified compounds with alkali metals, and triethanolamine are preferable from the viewpoints of detergency and rinsing properties. .
[0062]
  The blending ratio of the metal sealant in the cleaning agent is preferably in the range of 0.01 wt% to 20 wt%, more preferably in the range of 0.1 wt% to 10 wt%, and 0.2 wt%. Most preferred is in the range of ˜5% by weight. If the usage-amount of the said metal sealing agent is less than 0.01 weight%, it exists in the tendency for a washability to fall. On the other hand, if the amount of the metal sealant used exceeds 20% by weight, undissolved material may remain or the viscosity may increase and workability may decrease.
[0063]
  Moreover, the said cleaning agent may contain the other additive normally contained in the cleaning agent for resin stains in the range which does not impair the effect concerning this invention as needed. The other additives are not particularly limited, and specific examples include chelating agents, antiseptics, rust inhibitors, antifoaming agents such as silicone, antioxidants, amine compounds, palms, and the like. Examples include esters such as fatty acid methyl and benzyl acetate, hydrocarbon solvents, alcohols and the like. Examples of the chelating agent include aminocarboxylates such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid and ethylenediaminetetraacetic acid, which are usually used as components of cleaning agents, but are not particularly limited. .
[0064]
  In the above-mentioned cleaning agent, the remainder excluding each component such as the water-soluble graft polymer, alkali metal hydroxide, metal sealant and other additives is water. Moreover, these components used for the said cleaning agent are used so that the total amount may be 100 weight part. The water contained in the cleaning agent is not particularly limited as long as it does not impair the effects of the cleaning agent, such as ultrapure water, pure water, ion exchange water, distilled water, and tap water. The mixing ratio of water in the cleaning agent is preferably in the range of 5% to 98% by weight, more preferably in the range of 10% to 90% by weight, and most preferably in the range of 20% to 80% by weight. .
[0065]
  In the present invention, the method of cleaning and removing contaminants attached to the surface of electronic components using these cleaning agents is not particularly limited, but specifically, for example, immersion method, ultrasonic cleaning method And a method of rinsing with a solvent or (warm) water after washing by a method selected from various conventionally known methods such as an immersion rocking method and a spray method. The rinse water is not particularly limited as long as it can remove contaminants on the surface of the electronic component. For example, ultrapure water, pure water, ion exchange water, distilled water, tap water, and the like are preferable from the viewpoint of rinsing properties. .
[0066]
  As described above, the electronic component according to the present inventionResin stainsThe cleaning agent for water has a structure containing the water-soluble graft polymer having the above structure. The water-soluble graft polymer is particularly excellent in gelation resistance, dispersibility, and chelating ability of polyvalent metal ions. For this reason, the water-soluble graft polymer is used in combination with, for example, aqueous ammonia and hydrogen peroxide as described above in order to decompose and remove (fine) particles, metal impurities, and the like attached to the surface of a semiconductor substrate such as a silicon wafer. In this case, wasteful decomposition of hydrogen peroxide derived from polyvalent metal ions contained in or eluted from the cleaning liquid using the above-described cleaning agent is suppressed, and is derived from oxygen generated by this wasteful decomposition of hydrogen peroxide. Foaming can be suppressed. Moreover, the water-soluble graft polymer is also excellent in antifoaming properties, and for example, foaming can be reduced even when used in combination with a surfactant.
[0067]
  Furthermore, since the water-soluble graft polymer is excellent in the chelating ability of polyvalent metal ions, the polyvalent metal ions in the cleaning liquid are chelated to suppress (re) attachment of the polyvalent metal ions to the object to be cleaned. be able to. In addition, the water-soluble graft polymer is excellent in dispersibility, and it is possible to suppress the reattachment of contaminants once separated from the object to be cleaned to the object to be cleaned. Therefore, according to said structure, the cleaning agent suitable for the washing | cleaning of the electronic component excellent in a defoaming property and a washability can be provided.
[0068]
  In addition, since the above water-soluble graft polymer can be synthesized from the polyether compound (A) and the monoethylenically unsaturated monomer component (B) by graft polymerization, it can be produced at low cost and has low foaming properties. The water-soluble graft polymer can reduce the cleaning time, the number of times of washing, the amount of rinse water, etc. Can be reduced. Therefore, the electronic componentResin stainsThe cleaning agent for cleaning is a highly economical cleaning agent.
[0069]
  Further, the above water-soluble graft polymer has a small amount of remaining monomer and is hardly toxic. And since said water-soluble graft polymer can improve washability, it can wash | clean on milder conditions. Therefore, the above electronic componentsResin stainsThe cleaning agent is very safe.
[0070]
【Example】
  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. In the examples and comparative examples, “part” indicates “part by weight”, and “%” indicates “% by weight”.
[Example 1]
  A glass reactor equipped with a thermometer, a stirrer, a nitrogen gas inlet tube, two dripping devices, and a reflux condenser, 100 parts of polyethylene glycol having a number average molecular weight of 200 as a polyether compound (A), and monoethylenic As the unsaturated monomer component (B), 51.8 parts of maleic acid and 4.5 parts of p-toluenesulfonic acid monohydrate were charged. Also, 48.2 parts of acrylic acid, which is a monoethylenically unsaturated carboxylic acid monomer, was charged into one dropping device, and perbutyl I (trade name; Nippon Oil & Fats Co., Ltd.) as a polymerization initiator was charged into the other dropping device. 8 parts of 95% t-butyl peroxyisopropyl monocarbonate (manufactured by company).
[0071]
  Next, the contents in the reactor were heated and dissolved while stirring under a nitrogen gas stream, and the temperature was raised to 128 ° C. Subsequently, the acrylic acid and perbutyl I were continuously dropped over 1 hour while maintaining the temperature of the contents in the reactor in a temperature range of 126 ° C. to 131 ° C., and then stirred for another hour. Graft polymerization was performed.
[0072]
  As a result, a water-soluble graft polymer (1) having a weight average molecular weight of 5,000, a graft ratio of 80%, and a purity of 85% was obtained as the graft polymer according to the present invention. Subsequently, a predetermined amount of water is added to the water-soluble graft polymer (1), neutralized with an aqueous sodium hydroxide solution to adjust the pH of the aqueous solution of the water-soluble graft polymer (1) to 8, and the water-soluble graft polymer (1). The sodium salt of the graft polymer (1) was obtained.
[0073]
  Subsequently, 0.05 g of the sodium salt of the water-soluble graft polymer (1) with respect to 5 g of 29% aqueous ammonia,FluoroAlkylsulfonamide type fluorosurfactantFluoroAqueous ammonia solution (a) was prepared by dissolving 0.5 g of butylsulfonamide and 0.5 g of phosphonobutanetricarboxylic acid, which is a phosphonic acid compound. Next, this aqueous ammonia solution (a), 30% hydrogen peroxide solution and water were mixed at a volume ratio of 1: 1: 6 to prepare the cleaning agent (1) according to the present invention. 800 ml of this cleaning agent (1) was put into a 1 liter beaker and kept at 50 ° C. After 30 minutes, the height of the generated foam was measured. The results are shown in Table 1.
[Example 2]
  In Example 1, the same reaction and operation as in Example 1 except that 100 parts of naphthoxypolyethylene glycol having a number average molecular weight of 600 as the polyether compound (A) was used instead of polyethylene glycol having a number average molecular weight of 200. To obtain a water-soluble graft polymer (2). The average number of moles of ethylene oxide added to naphthol in the naphthoxypolyethylene glycol is 10 moles. The obtained water-soluble graft polymer (2) had a weight average molecular weight of 5,500, a graft ratio of 82%, and a purity of 86%. Subsequently, a predetermined amount of water is added to the water-soluble graft polymer (2), neutralized with an aqueous sodium hydroxide solution to adjust the pH of the aqueous solution of the water-soluble graft polymer (2) to 8, and the water-soluble graft polymer (2). The sodium salt of the graft polymer (2) was obtained.
[0074]
  Subsequently, in Example 1, the same operation as in Example 1 was performed except that the sodium salt of the water-soluble graft polymer (2) was used instead of the sodium salt of the water-soluble graft polymer (1). A cleaning agent (2) according to the present invention was prepared. Using this cleaning agent (2), the same experiment as in Example 1 was performed, and the height of the generated foam was measured. The results are shown in Table 1.
Example 3
  In Example 1, the same reaction as in Example 1 except that 200 parts of naphthoxypolyethylene glycol having a number average molecular weight of 1,000 as the polyether compound (A) was used instead of polyethylene glycol having a number average molecular weight of 200. -Operation was performed to obtain a water-soluble graft polymer (3). The average number of moles of ethylene oxide added to naphthol in the naphthoxypolyethylene glycol is 20 moles. The obtained water-soluble graft polymer (3) had a weight average molecular weight of 4,300, a graft ratio of 80%, and a purity of 83%. Subsequently, a predetermined amount of water is added to the water-soluble graft polymer (3), neutralized with an aqueous sodium hydroxide solution to adjust the pH of the aqueous solution of the water-soluble graft polymer (3) to 8, Sodium salt of the graft polymer (3) was obtained.
[0075]
  Subsequently, in Example 1, the same operation as in Example 1 was performed except that the sodium salt of the water-soluble graft polymer (3) was used instead of the sodium salt of the water-soluble graft polymer (1). A cleaning agent (3) according to the present invention was prepared. Using this cleaning agent (3), the same experiment as in Example 1 was performed, and the height of the generated foam was measured. The results are shown in Table 1.
Example 4
  In Example 1, instead of polyethylene glycol having a number average molecular weight of 200, the polyether compound (A) was used except that 200 parts of an adduct having an average of 7 moles of ethylene oxide in an alkyl having 12 to 15 carbon atoms was used. The same reaction and operation as in Example 1 were carried out to obtain a water-soluble graft polymer (4). The obtained water-soluble graft polymer (4) had a weight average molecular weight of 6,800, a graft ratio of 78%, and a purity of 82%. Subsequently, a predetermined amount of water is added to the water-soluble graft polymer (4), neutralized with an aqueous sodium hydroxide solution to adjust the pH of the aqueous solution of the water-soluble graft polymer (4) to 8, The sodium salt of the graft polymer (4) was obtained.
[0076]
  Subsequently, in Example 1, the same operation as in Example 1 was performed except that the sodium salt of the water-soluble graft polymer (4) was used instead of the sodium salt of the water-soluble graft polymer (1). A cleaning agent (4) according to the present invention was prepared. Using this cleaning agent (4), the same experiment as in Example 1 was performed, and the height of the generated foam was measured. The results are shown in Table 1.
[Comparative Example 1]
  In Example 1, except that the water-soluble graft polymer (1) was not used, the same operation as in Example 1 was performed to prepare a comparative cleaning agent (5). Using this cleaning agent (5), the same experiment as in Example 1 was performed, and the height of the generated foam was measured. The results are shown in Table 1.
[0077]
[Table 1]

[0078]
Example 5
  A bare silicon wafer (4 inches in diameter) is immersed in a dilute hydrofluoric acid solution in which polystyrene latex (manufactured by Nippon Synthetic Rubber Co., Ltd .; trade name STADEX, particle size 0.309 μm) is dispersed, and the polystyrene latex is surfaced on the bare silicon wafer. Adhered to. The number of polystyrene latex particles adhering to the bare silicon wafer surface was measured using a surface inspection device (Surfscan 4500).
[0079]
  Then, this bare silicon wafer was washed for 10 minutes using the cleaning liquid (1) obtained in Example (1) to remove the polystyrene latex. The cleaned bare silicon wafer is washed with ultrapure water for 5 minutes, dried for a predetermined time by spin drying, and then remains on the bare silicon wafer surface using the above-described surface inspection apparatus. The polystyrene having a particle diameter of 0.24 μm or more. The number of latex particles was measured. This result is shown in Table 2 together with the number of polystyrene latex particles adhering to the bare silicon wafer surface before cleaning.
Example 6
  In Example 5, in place of the cleaning liquid (1), the polystyrene on the bare silicon wafer surface before and after cleaning was obtained in the same manner as in Example 5 except that the cleaning liquid (2) obtained in Example (2) was used. The number of latex particles was measured. The results are shown in Table 2.
Example 7
  In Example 5, in place of the cleaning liquid (1), the polystyrene on the bare silicon wafer surface before and after cleaning was obtained in the same manner as in Example 5 except that the cleaning liquid (3) obtained in Example (3) was used. The number of latex particles was measured. The results are shown in Table 2.
Example 8
  In Example 5, instead of the cleaning liquid (1), the polystyrene on the bare silicon wafer surface before and after cleaning was obtained in the same manner as in Example 5 except that the cleaning liquid (4) obtained in Example (4) was used. The number of latex particles was measured. The results are shown in Table 2.
[Comparative Example 2]
  In Example 5, instead of the cleaning liquid (1), the comparative cleaning liquid (5) obtained in Comparative Example 1 was used, and the bare silicon wafer surface before and after cleaning was subjected to the same method as in Example 5. The number of particles of polystyrene latex was measured. The results are shown in Table 2.
[0080]
[Table 2]

[0081]
[Reference example 1]
  Water, a sodium salt of the water-soluble graft polymer (1) obtained in Example 1 and an alkali metal hydroxide were mixed at a ratio of 80% by weight: 5% by weight: 15% by weight,Reference exampleA cleaning agent (6) was prepared.
[0082]
  Subsequently, 500 ml of the cleaning liquid (6) was collected in a 500 ml glass beaker, and the glass beaker was placed in a constant temperature bath (warm water bath). Next, the temperature of the cleaning liquid (6) was raised to 60 ° C. and held at that temperature, and the test piece was immersed in the cleaning liquid (6) for 20 minutes. Thereafter, the test piece was rinsed for 1 minute under running tap water and further air blown for 1 minute.
[0083]
  As the test piece, an acrylic melamine electrostatic coating product (primer: epoxy melamine resin, coating thickness: 40 μm in total) obtained using an 8 cm × 4 cm × 0.5 mm steel plate was used.
[0084]
  The cleaning property of the cleaning agent (6) was evaluated by visually evaluating the degree of peeling and cleaning of the resin coated on the test piece surface. The evaluation criteria are as follows. “◎” indicates that the resin is completely peeled and washed, and “◯” indicates that at least about 70% of the resin is peeled and washed, and the ratio of the resin that is peeled and washed is 70. % (Part) was defined as “Δ”, and “x” was defined as the resin having not been peeled off or washed at all. The results are shown in Table 3 together with main cleaning conditions.
[Reference example 2]
  Water, a sodium salt of the water-soluble graft polymer (2) obtained in Example (2), and an alkali metal hydroxide were mixed in a ratio of 80% by weight: 5% by weight: 15% by weight; BookReference exampleA cleaning agent (7) was prepared.
[0085]
  continue,Reference example 1Except that the cleaning liquid (7) was used instead of the cleaning liquid (6).Reference example 1By performing the same operation as above and visually evaluating the degree of peeling and cleaning of the resin coated on the surface of the test piece, the cleaning property of the cleaning agent (7) is improved.Reference example 1And evaluated in the same manner. In the above test piece,Reference example 1The same acrylic melamine electrostatic coating product was used. The results of the evaluation are shown in Table 3 together with main cleaning conditions.
[Comparative Example 3]
  A comparative cleaning agent (8) was prepared by mixing water and alkali metal hydroxide in a ratio of 85% by weight to 15% by weight.
[0086]
  continue,Reference example 1Except that the cleaning liquid (8) was used instead of the cleaning liquid (6).Reference example 1By performing the same operation as above and visually evaluating the degree of peeling and cleaning of the resin coated on the test piece surface, the cleaning property of the cleaning agent (8) is improved.Reference example 1And evaluated in the same manner. In the above test piece,Reference example 1The same acrylic melamine electrostatic coating product was used. The results of the evaluation are shown in Table 3 together with main cleaning conditions.
[Reference example 3]
  Water, a sodium salt of the water-soluble graft polymer (3) obtained in Example (3), and an alkali metal hydroxide were mixed at a ratio of 80% by weight: 5% by weight: 15% by weight; BookReference exampleA cleaning agent (9) was prepared.
[0087]
  Then, the said washing | cleaning liquid (9) was extract | collected to the 500 ml glass beaker, and this glass beaker was installed in the thermostat (warm water tank). Next, the temperature of the cleaning liquid (9) was raised to 60 ° C. and held at that temperature, and the test piece was immersed in the cleaning liquid (9) for 8 hours. After that, this test pieceReference example 1Under the same conditions as above, the sample was rinsed for 1 minute under running tap water and further air blown for 1 minute.
[0088]
  BookReference exampleThen, as the test piece, a polyester powder electrostatic coating product (coating thickness: maximum 4400 μm) obtained using a steel plate of 8 cm × 4 cm × 0.5 mm was used.
[0089]
  By visually evaluating the degree of peeling and cleaning of the resin coated on the test piece surface, the cleaning property of the cleaning agent (9)Reference example 1And evaluated in the same manner. The results are shown in Table 3 together with main cleaning conditions.
[Reference example 4]
  Water, a sodium salt of the water-soluble graft polymer (4) obtained in Example (4), and an alkali metal hydroxide were mixed in a ratio of 80% by weight: 5% by weight: 15% by weight; BookReference exampleA cleaning agent (10) was prepared.
[0090]
  Subsequently, in Example 11, except that the cleaning liquid (10) was used instead of the cleaning liquid (9),Reference example 3The cleaning performance of the cleaning agent (10) was evaluated in the same manner as in Example 9 by performing the same operation as above and visually evaluating the degree of peeling and cleaning of the resin coated on the surface of the test piece. In the above test piece,Reference example 3The same polyester powder electrostatic coating product was used. The results of the evaluation are shown in Table 3 together with main cleaning conditions.
[Comparative Example 4]
  Reference example 3However, instead of the cleaning liquid (9), except that the cleaning agent (8) obtained by the same operation as Comparative Example 3 was used,Reference example 3By performing the same operation as above and visually evaluating the degree of peeling and cleaning of the resin coated on the test piece surface, the cleaning property of the cleaning agent (8) is improved.Reference example 1And evaluated in the same manner. In the above test piece,Reference example 3The same polyester powder electrostatic coating product was used. The results of the evaluation are shown in Table 3 together with main cleaning conditions.
[0091]
[Table 3]

[0092]
  From the results described in Tables 1 to 3, if the water-soluble graft polymer according to the present invention is used as a component of the cleaning agent, compared with the case where the water-soluble graft polymer is not used, the cleaning agent is prepared. It can be seen that there is little foaming after 30 minutes and the cleaning property is excellent.
[0093]
【The invention's effect】
  BookinventionPertaining toElectronic componentsResin stainsAs described above, the detergent is a water-soluble graft polymer obtained by graft-polymerizing a monoethylenically unsaturated monomer component containing a monoethylenically unsaturated carboxylic acid monomer to a polyether compound., Ammonia, hydrogen peroxide, water, fluorosurfactants and phosphonic acid compoundsIt is the structure containing.In the cleaning agent for resin stains of the electronic component, the blending ratio of the water-soluble graft polymer is in the range of 0.5 wt% to 60 wt%, and the blending ratio of the ammonia is 2 wt% to 90 wt%. The blending ratio of the hydrogen peroxide is in the range of 0.5 to 70% by weight, and the blending ratio of the fluorosurfactant is in the range of 0.1 to 40% by weight. The blending ratio of the phosphonic acid compound is preferably in the range of 0.01 wt% to 20 wt%. Furthermore, water is the balance when the total amount of each component is 100 parts by weight, and the blending ratio of water is preferably in the range of 5% by weight to 98% by weight.
[0094]
  According to the above configuration,Electronic components with excellent low-foaming and defoaming properties as well as excellent cleaning propertiesResin stainsThere is an effect that a cleaning agent can be provided.
[0095]
  In addition, the water-soluble graft polymer is inexpensive in production, and an electronic component comprising the water-soluble graft polymerResin stainsThe cleaning agent has excellent low-foaming properties, defoaming properties, and detergency, so it has excellent workability and can reduce the washing time, the number of washings, the amount of rinse water, etc., and reduce the cost of washing. Can be made. Further, the above water-soluble graft polymer has a small amount of remaining monomer and is hardly toxic. And since said water-soluble graft polymer can improve washability, it can wash | clean on milder conditions. Therefore, the electronic componentResin stainsThe cleaning agent is very economical and safe.
[0096]
  The above electronic componentsResin stainsThe cleaning agent is, for example, a silicon waferAttached toIt can be particularly suitably used for washing and removing resin stains.

Claims (3)

Water-soluble graft polymer obtained by graft polymerization of a monoethylenically unsaturated monomer component containing a monoethylenically unsaturated carboxylic acid monomer to a polyether compound , ammonia, hydrogen peroxide, water, fluorine-based surface activity A cleaning agent for resin stains of electronic parts , comprising an agent and a phosphonic acid compound . The blending ratio of the water-soluble graft polymer is in the range of 0.5 wt% to 60 wt%, the blending ratio of the ammonia is in the range of 2 wt% to 90 wt%, and the blending ratio of the hydrogen peroxide The ratio is in the range of 0.5 wt% to 70 wt%, the blending ratio of the fluorosurfactant is in the range of 0.1 wt% to 40 wt%, and the blending ratio of the phosphonic acid compound is The cleaning agent for resin stains of electronic components according to claim 1, wherein the cleaning agent is in the range of 0.01 wt% to 20 wt%. The electronic component according to claim 2, wherein water is a balance when the total amount of each component is 100 parts by weight, and a mixing ratio of water is in a range of 5% by weight to 98% by weight. Cleaning agent for resin stains.