JP5763129B2 - Degreasing agent for photo solder resist pretreatment and degreasing method using the same - Google Patents
Degreasing agent for photo solder resist pretreatment and degreasing method using the same Download PDFInfo
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- JP5763129B2 JP5763129B2 JP2013137450A JP2013137450A JP5763129B2 JP 5763129 B2 JP5763129 B2 JP 5763129B2 JP 2013137450 A JP2013137450 A JP 2013137450A JP 2013137450 A JP2013137450 A JP 2013137450A JP 5763129 B2 JP5763129 B2 JP 5763129B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
- C23G5/036—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds having also nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P50/00—Etching of wafers, substrates or parts of devices
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Description
本発明は、フォトソルダーレジスト前処理用脱脂剤及びこれを用いた脱脂方法に関する。 The present invention relates to a degreasing agent for photo solder resist pretreatment and a degreasing method using the same.
プリント基板、特に、ＢＯＣ（Ｂｏａｒｄ Ｏｎ Ｃｈｉｐ）パッケージを製造するときに、フォトソルダーレジスト（Ｐｈｏｔｏ Ｓｏｌｄｅｒ Ｒｅｓｉｓｔ：ＰＳＲ）が多用されている。 A photo solder resist (PSR) is frequently used when manufacturing a printed circuit board, in particular, a BOC (Board On Chip) package.
以下、本明細書において、用語「ソルダーレジスト（Ｓｏｌｄｅｒ Ｒｅｓｉｓｔ：ＳＲ）」は、ＰＳＲと実質的に同一の意味で特別な区分なく使用される。 Hereinafter, in the present specification, the term “Solder Resist (SR)” is used without any special meaning in the same meaning as PSR.
ＰＳＲの使用目的は、回路パターン間のショート（ｓｈｏｒｔ）を防止し且つソルダーボール（ｓｏｌｄｅｒ ｂａｌｌ）を支持することにある。 The purpose of using PSR is to prevent shorts between circuit patterns and to support a solder ball.
リードフレーム（ｌｅａｄ ｆｒａｍｅ）タイプのＰＳＲは、ソルダーペースト（ｓｏｌｄｅｒ ｐａｓｔｅ）でリードフレームを基板に付着させる場合に回路パターン間のショートを防止するための絶縁の役割を果たし、ＢＧＡ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）タイプのＰＳＲは、ソルダーボールを基板上の位置に付着させることを可能とする役割と、リフロー（ｒｅｆｌｏｗ）の際に隣接のボールとソルダーペーストによるショートを防止する役割を果たす。 Lead frame type PSR plays a role of insulation to prevent short circuit between circuit patterns when a lead frame is attached to a substrate with a solder paste, and is a BGA (Ball Grid Array) type. The PSR serves to allow the solder ball to adhere to a position on the substrate and to prevent a short circuit caused by the adjacent ball and the solder paste during reflow.
ところが、プリント基板にＰＳＲを形成するとき、テープの糊やドライフィルム（Ｄｒｙ ｆｉｌｍ、Ｄ／Ｆ）などのアクリレート系異物によるＳＲ異物不良（すなわち、異物によりソルダーレジストがプリント基板上によく付着又は形成されていない現象）が持続的に発生した。さらに、ＳＲ外観不良の中でも、ＳＲ異物による不良が最も高い頻度を示した。ＳＲ異物不良試料を手に入れて成分分析を行った結果、糊性異物による外観不良として分析された。 However, when PSR is formed on a printed circuit board, SR foreign material failure due to acrylate-based foreign material such as tape glue or dry film (D / F) (that is, the solder resist adheres or forms well on the printed circuit board). The phenomenon that was not done) occurred continuously. Furthermore, among the SR appearance defects, the defect due to the SR foreign matter showed the highest frequency. As a result of obtaining a SR foreign material defective sample and analyzing the components, it was analyzed as an appearance defect due to adhesive foreign material.
異物発生は、主に、ＰＳＲ工程の前に、回路現像エッチング剥離（ＤＥＳ）工程及び／又は回路形成（ＡＯＩ）検査工程の際に無塵テープ、クリーンパッド（Ｃｌｅａｎ Ｐａｄ）、接着テープ（Ａｄｈｅｓｉｖｅ Ｔａｐｅ）などから転移された異物によることである。異物成分分析の結果、アクリレート成分が５０％以上占有する。 The generation of foreign matter is mainly caused by a dust-free tape, a clean pad (Clean Pad), and an adhesive tape (Adhesive Tape) during a circuit development etching peeling (DES) process and / or a circuit formation (AOI) inspection process before the PSR process. ) And the like. As a result of the foreign component analysis, 50% or more of the acrylate component is occupied.
このようなアクリレート成分は、ＰＳＲ前処理前の外観検査の際に確認され、ＰＳＲ前処理進行の際に除去されないため、ＳＲ塗布の際にインクと混合されて銅見え（すなわち、銅回路パターン上に異物により金メッキが形成されないため、銅が露出して銅が視覚的に見える現象）やＳＲ異物などの不良が発生する。 Such an acrylate component is confirmed during the appearance inspection before the PSR pretreatment and is not removed during the progress of the PSR pretreatment. In this case, the gold plating is not formed by the foreign matter, so that the copper is exposed and the copper is visually visible) or the SR foreign matter is generated.
このようなアクリレート成分を除去するために、既存のＰＳＲ前処理の際に使用された薬品はいずれも硫酸及び硫酸過水などの表面酸化除去タイプであるが、アクリレート成分などの高接着性異物は硫酸系薬品で除去することができない。 In order to remove such an acrylate component, the chemicals used in the existing PSR pretreatment are all surface oxidation removal types such as sulfuric acid and sulfuric acid / hydrogen peroxide. It cannot be removed with sulfuric acid chemicals.
一方、特許文献１では、Ｎ−メチルピロリドン及びジメチルホルムアミドを主成分とする組成物がアクリル成分を除去することができると開示しているが、これは、ＰＳＲ前処理用でないだけでなく、洗浄力にも劣る傾向がある。 On the other hand, Patent Document 1 discloses that a composition containing N-methylpyrrolidone and dimethylformamide as main components can remove an acrylic component, but this is not only for PSR pretreatment but also for cleaning. There is a tendency to be inferior in power.
ＰＳＲ前処理薬品でＰＳＲを前処理する薬品処理装置の長さが約１ｍ以内であって、薬品処理時間が約２０秒の水準に過ぎないから、高反応性洗浄薬品の開発が求められる。また、ＰＳＲ前処理に適用可能なアルカリ洗浄薬品は、アルカリ成分によりプリント基板とＰＳＲインクとの接合性が低下してはならない。ところが、ＰＳＲ前処理専用に開発されたアルカリ薬品は、未だない状況である。 Since the length of the chemical treatment apparatus for pretreating PSR with the PSR pretreatment chemical is about 1 m and the chemical treatment time is only about 20 seconds, development of a highly reactive cleaning chemical is required. In addition, the alkali cleaning chemicals applicable to the PSR pretreatment should not lower the bondability between the printed circuit board and the PSR ink due to the alkaline component. However, there is still no alkaline chemical developed for PSR pretreatment.
そこで、本発明者は、上述した問題点を解決することができる、アミン−エーテル（ａｍｉｎｅ−ｅｔｈｅｒ）化合物を含む新規なアルカリ系脱脂剤組成物の開発に成功し、これに基づいて本発明を完成した。 Therefore, the present inventors have succeeded in developing a novel alkaline degreasing agent composition containing an amine-ether compound that can solve the above-mentioned problems, and based on this, the present invention has been developed. completed.
よって、本発明の目的は、プリント基板とＰＳＲインクとの接合性が低下しないうえ、洗浄力にも優れ、銅見え不良及びＳＲ異物不良を著しく減少させることができるフォトソルダーレジスト前処理用脱脂剤を提供することにある。 Therefore, an object of the present invention is to provide a photo solder resist pretreatment degreasing agent that does not deteriorate the bondability between the printed circuit board and the PSR ink, has excellent cleaning power, and can significantly reduce copper appearance defects and SR foreign matter defects. Is to provide.
本発明の他の目的は、前記フォトソルダーレジスト前処理用脱脂剤を用いて既存の硫酸の使用を著しく減少させることにより、環境にやさしくプリント基板を脱脂させる方法を提供することにある。 Another object of the present invention is to provide a method for degreasing a printed circuit board in an environmentally friendly manner by significantly reducing the use of existing sulfuric acid using the photo solder resist pretreatment degreasing agent.
本発明のある観点によれば、１０〜７０重量％のグリコールエーテル、１〜２５重量％のアルコールアミン、１０〜７０重量％のアミン系界面活性剤及び残部として水を含むフォトソルダーレジスト前処理用脱脂剤（以下「第１発明」という）を提供する。 According to an aspect of the present invention, 10 to 70 wt% of glycol ethers, 1 to 25 wt% alcohol amine, photo solder resists pretreatment containing 10-70 wt% of an amine-based surfactant and water as the balance A degreasing agent (hereinafter referred to as “first invention”) is provided.
第１発明において、前記グリコールエーテルは、エチレングリコール（Ｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ）、ポリエチレングリコールモノブチルエーテル（ｐｏｌｙｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ ｍｏｎｏｂｕｔｙｌ ｅｔｈｅｒ）、又はポリエチレングリコールモノメチルエーテル（ｐｏｌｙｅｔｈｙｌｅｎｅ ｇｌｙｃｏｌ ｍｏｎｏｍｅｔｈｙｌ ｅｔｈｅｒ）であることを特徴とする。 In the first invention, the glycol ether is characterized by being ethylene glycol, polyethylene glycol monobutyl ether, or polyethylene glycol monomethyl ether.
第１発明において、前記アルコールアミンは、メチルジエタノールアミン（Ｍｅｔｈｙｌｄｉｅｔｈａｎｏｌａｍｉｎｅ）又はモノエタノールアミン（ｍｏｎｏｅｔｈａｎｏｌａｍｉｎｅ）であることを特徴とする。 1st invention WHEREIN: The said alcohol amine is methyldiethanolamine (Methyldiethanolamine) or monoethanolamine (Monoethanolamine), It is characterized by the above-mentioned.
第１発明において、前記アミン系界面活性剤は、化学式Ｒ−ＮＨ２で表わされる（式中、Ｒが炭素数１１〜１８のアルキル基である）非イオン性界面活性剤であることを特徴とする。 In the first invention, the amine-based surfactant is a nonionic surfactant represented by the chemical formula R—NH 2 (wherein R is an alkyl group having 11 to 18 carbon atoms). To do.
第１発明において、前記脱脂剤は、酸化防止剤、消泡剤またはこれらの混合物を０．１〜５重量％の範囲でさらに含むことを特徴とする。 In the first invention, the degreasing agent further includes an antioxidant, an antifoaming agent or a mixture thereof in the range of 0.1 to 5% by weight.
本発明の別の観点によれば、フォトソルダーレジストの形成前に、異物が残存するプリント基板の表面に、１０〜７０重量％のグリコールエーテル、１〜２５重量％のアルコールアミン、１０〜７０重量％のアミン系界面活性剤及び残部として水を含む脱脂剤を塗布する段階と、前記脱脂剤で処理されたプリント基板の表面をＡｌ２Ｏ３粒でジェット研磨する段階と、前記ジェット研磨されたプリント基板の表面を硫酸で処理する段階とを含んでなるフォトソルダーレジスト前処理用脱脂剤を用いた脱脂方法（以下「第２発明」という）を提供する。 According to another aspect of the present invention, before the formation of the photo solder resist, 10 to 70% by weight of glycol ether, 1 to 25% by weight of alcohol amine, 10 to 70 % by weight on the surface of the printed board on which foreign matters remain. % Of a surface active agent and a degreasing agent containing water as a balance, a step of jet polishing a surface of a printed circuit board treated with the degreasing agent with Al 2 O 3 grains, and the jet polishing A degreasing method (hereinafter referred to as “second invention”) using a degreasing agent for photo solder resist pretreatment comprising the step of treating the surface of a printed board with sulfuric acid is provided.
第２発明において、前記グリコールエーテルは、エチレングリコール、ポリエチレングリコールモノブチルエーテル又はポリエチレングリコールモノメチルエーテルであることを特徴とする。 In the second invention, the glycol ether is ethylene glycol, polyethylene glycol monobutyl ether or polyethylene glycol monomethyl ether.
第２発明において、前記アルコールアミンは、メチルジエタノールアミン又はモノエタノールアミンであることを特徴とする。 In the second invention, the alcohol amine is methyldiethanolamine or monoethanolamine.
第２発明において、前記アミン系界面活性剤は、化学式Ｒ−ＮＨ２で表示される（式中、Ｒが炭素数１１〜１８のアルキル基である）非イオン性界面活性剤であることを特徴とする。 In the second invention, the amine-based surfactant is a nonionic surfactant represented by the chemical formula R—NH 2 (wherein R is an alkyl group having 11 to 18 carbon atoms). And
第２発明において、前記脱脂剤は、酸化防止剤、消泡剤又はこれらの混合物を０．１〜５重量％の範囲でさらに含むことを特徴とする。 In the second invention, the degreasing agent further includes an antioxidant, an antifoaming agent or a mixture thereof in a range of 0.1 to 5% by weight.
第２発明において、前記脱脂剤の塗布段階では、１〜２ｋｇｆの圧力で１０〜４０秒間スプレー噴射されることを特徴とする。 2nd invention WHEREIN: In the application | coating stage of the said degreasing agent, it sprays for 10 to 40 second by the pressure of 1-2 kgf, It is characterized by the above-mentioned.
本発明に係るフォトソルダーレジスト前処理用脱脂剤は、プリント基板とＰＳＲインクとの接合性が低下しないうえ、優れた洗浄力を有するので、銅見え不良、ＳＲ異物不良及び既存の硫酸使用を著しく減少させて環境調和的にプリント基板を脱脂させることができる。 The degreasing agent for photo solder resist pretreatment according to the present invention does not deteriorate the bondability between the printed circuit board and the PSR ink, and has excellent cleaning power. The printed circuit board can be degreased in an environmentally friendly manner by reducing the amount.
本発明の特徴及び利点は、添付図面に基づいて次の詳細な説明からさらに明白になるであろう。 The features and advantages of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
本発明をさらに具体的に説明する前に、本明細書及び特許請求の範囲に使用された用語又は単語は、通常的且つ辞典的な意味に限定されてはならず、発明を最善の方法で説明するために用語の概念を適切に定義することができるという原則に立脚して、本発明の技術的思想に符合する意味と概念で解釈されなければならない。よって、本明細書に記載された実施例の構成は、本発明の好適な一例に過ぎず、本発明の技術的思想をすべて代弁するものではない。このため、本出願時点においてこれらを代替することが可能な様々な均等物及び変形例があり得ることを理解すべきである。 Before describing the present invention more specifically, the terms or words used in the specification and claims should not be limited to the ordinary and lexical meaning, and the invention is best practiced. Based on the principle that the terminology can be appropriately defined for the purpose of explanation, it should be interpreted with the meaning and concept consistent with the technical idea of the present invention. Therefore, the structure of the Example described in this specification is only a suitable example of this invention, and does not represent all the technical thoughts of this invention. Thus, it should be understood that there are various equivalents and variations that can be substituted at the time of this application.
以下、本発明の属する技術分野における通常の知識を有する者が本発明を容易に実施し得るように、本発明の好適な実施例を詳細に説明する。尚、本発明を説明するにあたり、本発明の要旨を不明瞭にする可能性がある係る公知技術についての詳細な説明は省略する。 Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily carry out the present invention. In describing the present invention, detailed descriptions of known techniques that may obscure the subject matter of the present invention are omitted.
前述したように、従来、プリント基板の表面の酸化膜及び油膜を取り除くために硫酸を使用したが、アクリレート及びドライフィルム（Ｄ／Ｆ）などの接着力がある異物の場合、硫酸では除去することができない。アクリレート及び／またはＤ／Ｆなどの糊性異物は、硫酸とは全く反応しない。糊性異物を除去するためには、イオン化物質による中和反応及び界面活性剤の物理的膨潤（ｓｗｅｌｌｉｎｇ）反応が必要である。 As described above, sulfuric acid has been used to remove the oxide film and oil film on the surface of the printed circuit board. However, foreign substances with adhesive strength such as acrylate and dry film (D / F) should be removed with sulfuric acid. I can't. Paste-like foreign substances such as acrylate and / or D / F do not react with sulfuric acid at all. In order to remove adhesive foreign substances, a neutralization reaction with an ionized substance and a physical swelling reaction of a surfactant are required.
下記反応式１及び反応式２は、一般の洗浄用ディッピングライン（Ｄｉｐｐｉｎｇ Ｌｉｎｅ）で使用している脱脂剤の糊除去反応メカニズムである。 The following reaction formula 1 and reaction formula 2 are degreasing paste removal reaction mechanisms used in general dipping lines for cleaning (Dipping Line).
脱脂剤の洗浄原理には、下記反応式１のような接着剤成分のＯＨ環を切断するキレート反応と同じような化学反応や、下記反応式２のような膨潤による物理的脱着反応がある。また、このような洗浄力は、温度と時間によって比例する（運動エネルギーと温度との法則、アレニウスの法則）。 The cleaning principle of the degreasing agent includes a chemical reaction similar to the chelate reaction that cleaves the OH ring of the adhesive component as shown in the following reaction formula 1, and a physical desorption reaction due to swelling as shown in the following reaction formula 2. Such detergency is proportional to temperature and time (the law of kinetic energy and temperature, the law of Arrhenius).
上記反応式１のようなイオン化反応性が高いＮａ＋を用いた化学的反応の場合、接着剤成分と直接反応するので、除去効果には優れる。ところが、中和反応による固体結晶（水ガラス現象）が発生するので、試験結果、ＰＣＢの前処理ラインの適用が不可能であった。前記反応式２のような一般な界面活性剤タイプの脱脂剤の場合、スプレー噴射の際に過度な泡が発生するため、スプレータイプの湿式ライン（ｗｅｔ−ｌｉｎｅ）では適さない。 In the case of a chemical reaction using Na + having high ionization reactivity as shown in the above reaction formula 1, since it reacts directly with the adhesive component, the removal effect is excellent. However, since solid crystals (water glass phenomenon) are generated by the neutralization reaction, it was impossible to apply the pretreatment line for PCB as a result of the test. In the case of a general surfactant type degreasing agent such as the reaction formula 2, excessive foam is generated during spray injection, and therefore, it is not suitable for a spray type wet-line.
このような２つの問題により、一般のディッピングラインで使用される脱脂剤は、脱脂効果には優れるが、量産ラインへの適用は不可能である。かかる問題点を克服するために先決されるべき課題は、次のとおりである。 Due to these two problems, a degreasing agent used in a general dipping line is excellent in the degreasing effect, but cannot be applied to a mass production line. The issues to be determined in order to overcome such problems are as follows.
１）結晶異物の未発生−金属成分が必要なイオン化物質は適用不可。
２）高い反応性要求−短い湿式ラインの限界を克服することが可能な高反応性薬品。
３）泡発生不可−界面活性剤の適用不可、同じ役割の代替物質が必要。
４）ＳＲ接合性に対する阻害（リスク）なし。
1) No occurrence of crystalline foreign matter-Ionized substances that require metal components are not applicable.
2) High reactivity requirement-highly reactive chemicals that can overcome the limitations of short wet lines.
3) No foam generation-Surfactant not applicable, need alternative material with same role.
4) No inhibition (risk) on SR zygosity.
本発明では、このような要求条件を満足させることが可能なＰＳＲ前処理専用アミン−エーテル（ａｍｉｎｅ−ｅｔｈｅｒ）成分に基づいた脱脂剤を開発した。 In the present invention, a degreasing agent based on an amine-ether component dedicated to PSR pretreatment capable of satisfying such requirements has been developed.
既存のアミン−エーテル成分を有する脱脂及び洗浄剤は、ＰＳＲ前処理用としては使用できない。前述したように、既存の洗浄剤はＰＳＲインクとの接合信頼性に阻害があるので、完璧な水溶性が求められる。さらに、短時間で高い異物除去効果だけでなく、長時間使用の際に薬品のバランスが崩れず持続的に維持できる耐久性も求められる。 Degreasing and cleaning agents with existing amine-ether components cannot be used for PSR pretreatment. As described above, since the existing cleaning agent impedes the bonding reliability with the PSR ink, perfect water solubility is required. Furthermore, not only a high foreign matter removal effect in a short time, but also a durability that can be maintained continuously without breaking the balance of chemicals when used for a long time.
本発明に係るアミン−エーテル化合物は、界面活性剤と同じような膨潤及び剥離効果を有するが、泡が発生しない特性を持つ。 The amine-ether compound according to the present invention has a swelling and peeling effect similar to that of a surfactant, but has a characteristic that bubbles are not generated.
図１を参照すると、本発明のアミン−エーテル化合物は、アミン−エーテル化合物のＮＨが接着剤成分に直接浸透して溶解すること、及びエーテルによる膨潤効果により、試片の境界表面（ＰＳＲ試片と糊）での糊性を低下させる効果を有する。 Referring to FIG. 1, the amine-ether compound according to the present invention has a boundary surface of a specimen (PSR specimen) due to the fact that NH of the amine-ether compound directly penetrates and dissolves in the adhesive component and the swelling effect by ether. And paste) have the effect of lowering the paste property.
本発明に係るフォトソルダーレジスト前処理用脱脂剤は、グリコールエーテル、アルコールアミン、アミン系界面活性剤、及び水を含む。好ましくは、前記脱脂剤は、１０〜７０重量％のグリコールエーテル、１〜２５重量％のアルコールアミン、１０〜７０重量％のアミン系界面活性剤、及び残部として水を含む。 The degreasing agent for photo solder resist pretreatment according to the present invention contains glycol ether, alcohol amine, amine surfactant, and water. Preferably, the degreasing agent comprises 10-70% by weight glycol ether, 1-25% by weight alcohol amine, 10-70% by weight amine surfactant, and the balance water.
本発明において、前記グリコールエーテルは、組成物の膨潤及び浸透力の向上のために添加されるもので、例えば、エチレングリコール、ポリエチレングリコールモノブチルエーテル、またはポリエチレングリコールモノメチルエーテルなどが挙げられるが、これに限定されない。また、前記グリコールエーテルの混合量は、１０〜７０重量％が好ましく、１０重量％未満の場合、洗浄力が低下する傾向があり、７０重量％超過の場合、前記グリコールエーテルが引火性物質であるため腐食、信頼性などに問題がある。 In the present invention, the glycol ether is added to improve the swelling and penetrating power of the composition, and examples thereof include ethylene glycol, polyethylene glycol monobutyl ether, and polyethylene glycol monomethyl ether. It is not limited. Further, the mixing amount of the glycol ether is preferably 10 to 70% by weight, and if it is less than 10% by weight, the detergency tends to decrease, and if it exceeds 70% by weight, the glycol ether is a flammable substance. Therefore, there are problems with corrosion and reliability.
前記アルコールアミンは、例えば、メチルジエタノールアミン又はモノエタノールアミンなどが挙げられるが、これに限定されない。前記アルコールアミンの混合量は、１〜２５重量％が好ましく、１重量％未満の場合、洗浄力が低下し、２５重量％超過の場合、信頼性などに問題がある。 Examples of the alcohol amine include, but are not limited to, methyldiethanolamine and monoethanolamine. The mixing amount of the alcohol amine is preferably 1 to 25% by weight, and if it is less than 1% by weight, the detergency is reduced, and if it exceeds 25% by weight, there is a problem in reliability.
前記アミン系界面活性剤は、例えば、化学式Ｒ−ＮＨ２で表わされる非イオン性界面活性剤であって、上記式中、Ｒは炭素数１１〜１８のアルキル基である。前記アミン系界面活性剤の混合量は、１０〜７０重量％が好ましく、１０重量％未満の場合、組成物自体の混和性が低下し、７０重量％超過の場合、洗浄力が低下する傾向がある。 The amine-based surfactant is, for example, a nonionic surfactant represented by the chemical formula R—NH 2 , wherein R is an alkyl group having 11 to 18 carbon atoms. The mixing amount of the amine-based surfactant is preferably 10 to 70% by weight, and if it is less than 10% by weight, the miscibility of the composition itself is lowered, and if it exceeds 70% by weight, the detergency tends to be lowered. is there.
前記アミン系界面活性剤でエポキシ硬化物を除去する洗浄メカニズムは、下記反応式３のとおりである。 The cleaning mechanism for removing the epoxy cured product with the amine-based surfactant is as shown in the following reaction formula 3.
反応式３を参照すると、前記アミン系界面活性剤のアミン基は、エポキシ硬化物のエポキシ基を切断することによりエポキシ硬化物の接着力を弱化させて除去する。 Referring to Reaction Formula 3, the amine group of the amine surfactant is removed by weakening the adhesive force of the epoxy cured product by cleaving the epoxy group of the epoxy cured product.
一方、本発明の脱脂剤組成物は、本発明の効果を損傷しない範囲で、必要に応じて酸化防止剤、消泡剤またはこれらの混合物を０．１〜５重量％の範囲でさらに含んで、好ましい物性や機能を発現させることができる。 On the other hand, the degreasing agent composition of the present invention further contains an antioxidant, an antifoaming agent, or a mixture thereof in the range of 0.1 to 5% by weight as necessary, as long as the effects of the present invention are not damaged. Therefore, preferable physical properties and functions can be expressed.
本発明によれば、前記樹脂組成物を水溶液状態で混合して本発明の脱脂剤を得る。 According to the present invention, the resin composition is mixed in an aqueous solution state to obtain the degreasing agent of the present invention.
前記脱脂剤を用いたプリント基板のＰＳＲ前処理工程について、図２を参照して考察する。 A PSR pretreatment process for a printed circuit board using the degreasing agent will be discussed with reference to FIG.
まず、１）銅回路パターン２０が形成されたプリント基板１０の酸化膜及びその他の異物除去のために本発明の脱脂剤を約１〜２ｋｇｆの圧力で１０〜４０秒間スプレー噴射して処理した後、水洗し、乾燥させる。 First, after removing the degreasing agent of the present invention by spraying for 10 to 40 seconds at a pressure of about 1 to 2 kgf to remove oxide film and other foreign matters on the printed circuit board 10 on which the copper circuit pattern 20 is formed. Wash with water and dry.
そして、２）前記基板表面の異物を取り除くためにジェット研磨を行う。前記ジェット研磨では、サイズ５０〜１００μｍのＡｌ２Ｏ３粒を約１〜３ｋｇｆの圧力で２０〜５０秒間物理的で打撃した後、水洗し、乾燥させる。 2) Jet polishing is performed to remove foreign substances on the substrate surface. In the jet polishing, Al 2 O 3 grains having a size of 50 to 100 μm are physically hit at a pressure of about 1 to 3 kgf for 20 to 50 seconds, then washed with water and dried.
更に、３）ＰＳＲの密着力を向上させるために最終約１０％の硫酸を約１〜２ｋｇｆの圧力で１０〜３０秒間スプレー噴射して処理した後、水洗し、乾燥させる。 3) In order to improve the adhesion of PSR, about 10% of sulfuric acid is sprayed at a pressure of about 1 to 2 kgf for 10 to 30 seconds, and then washed and dried.
このように本発明に係るフォトソルダーレジスト前処理用脱脂剤で脱脂処理されたプリント基板は、ＰＳＲインクとの接合性に優れるうえ、銅見え不良及びＳＲ異物不良が著しく減少する。 Thus, the printed circuit board degreased with the photo solder resist pretreatment degreasing agent according to the present invention is excellent in bondability with the PSR ink, and the copper appearance defect and SR foreign matter defect are remarkably reduced.
以下、実施例及び比較例によって本発明をさらに具体的に説明する。本発明の範疇はこれらの実施例に限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The scope of the present invention is not limited to these examples.
（比較例１）
水に１０重量％のアルコールアミン（Ｃａｓ Ｎｏ．１１１−４２−２）及び７重量％のアミン系界面活性剤（Ｃａｓ Ｎｏ．６１７９０−８５−０）を添加してよく混合することにより、脱脂剤を製造した。
(Comparative Example 1)
A degreasing agent is obtained by adding 10% by weight alcohol amine (Cas No. 111-42-2) and 7% by weight amine surfactant (Cas No. 61790-85-0) to water and mixing well. Manufactured.
（実施例１）
水に１５重量％のグリコールエーテル（Ｃａｓ Ｎｏ．１１１−４６−６）、１０重量％のアルコールアミン（Ｃａｓ Ｎｏ．１１１−４２−２）、及び２５重量％のアミン系界面活性剤（Ｃａｓ Ｎｏ．６１７９０−８５−０）を添加してよく混合し、本発明の脱脂剤を製造した。
Example 1
15 wt% glycol ether (Cas No. 111-46-6), 10 wt% alcohol amine (Cas No. 111-42-2), and 25 wt% amine surfactant (Cas No. 11) in water. 61790-85-0) was added and mixed well to produce the degreasing agent of the present invention.
銅板の表面に糊を任意に付着させて硫酸、水酸化ナトリウム及び本発明の脱脂剤を用いて２０秒及び３０秒間浸漬試験を行い、さらに工程能力Ｂ／Ｄを用いて無電解金メッキまで行った。その試験結果を図３及び下記表１に示す。図３において、Ａは１０％硫酸、Ｂは１０％水酸化ナトリウム溶液、Ｃは比較例１の脱脂剤、Ｄは実施例１の脱脂剤をそれぞれ示す。 Adhesive was arbitrarily attached to the surface of the copper plate, and the immersion test was performed for 20 seconds and 30 seconds using sulfuric acid, sodium hydroxide and the degreasing agent of the present invention, and further electroless gold plating was performed using the process capability B / D. . The test results are shown in FIG. In FIG. 3, A is 10% sulfuric acid, B is a 10% sodium hydroxide solution, C is a degreasing agent of Comparative Example 1, and D is a degreasing agent of Example 1.
図３及び表１から分かるように、浸漬試験の際に、１０％硫酸溶液では、テープの糊が殆ど除去されない部分が確認された。脱脂剤の場合は、３０秒以前から洗浄効果を示し、完全に除去される部分を確認することができた。しかも、本発明の脱脂剤のみが約２０秒程度に１００％糊除去力を示した。 As can be seen from FIG. 3 and Table 1, in the immersion test, a portion in which the adhesive on the tape was hardly removed was confirmed with the 10% sulfuric acid solution. In the case of a degreasing agent, the cleaning effect was exhibited from 30 seconds before, and the part to be completely removed could be confirmed. Moreover, only the degreasing agent of the present invention showed 100% adhesive removal power in about 20 seconds.
一方、工程能力Ｂ／Ｄを用いて前処理設備に投入してスプレー試験を行った結果、本発明の脱脂剤は、硫酸に比べて５０％以上の糊除去性能を示し、量産適用の前に先検証のための試験の際に、メッキの粗さ及びＳＲの浮き上りが発生しなかった（泡発生なし）。本発明の脱脂剤の場合は、前処理進行の前に発見された糊性異物が前処理通過の後に除去される部分を確認することができた。 On the other hand, as a result of throwing into the pretreatment equipment using the process capability B / D and performing a spray test, the degreasing agent of the present invention exhibits a paste removal performance of 50% or more compared with sulfuric acid, and before mass production application. In the test for the previous verification, the plating roughness and SR did not rise (no bubbles were generated). In the case of the degreasing agent of the present invention, it was possible to confirm a portion where the adhesive foreign matter discovered before the pretreatment progressed was removed after passing through the pretreatment.
（実施例２）
プリント基板の表面に糊を任意に付着させてＰＳＲ前処理薬品処理装置に位置させた。次に、実施例１に係る脱脂剤を約２ｋｇｆの圧力で約２０秒間スプレー噴射して処理し、水洗し、乾燥させた。その後、前記基板をサイズ約５０〜１００μｍのＡｌ２Ｏ３粒を約２ｋｇｆの圧力で約４０秒間物理的に打撃した後、水洗し、乾燥させた。その後、約１０％の硫酸を約２ｋｇｆの圧力で約１５秒間スプレー噴射して処理した後、水洗し、乾燥させた。
(Example 2)
Adhesive was arbitrarily attached to the surface of the printed circuit board and placed in the PSR pretreatment chemical treatment apparatus. Next, the degreasing agent according to Example 1 was treated by spraying for about 20 seconds at a pressure of about 2 kgf, washed with water, and dried. Thereafter, the substrate was physically struck with Al 2 O 3 grains having a size of about 50 to 100 μm at a pressure of about 2 kgf for about 40 seconds, then washed with water and dried. Thereafter, about 10% sulfuric acid was sprayed for about 15 seconds at a pressure of about 2 kgf, and then washed with water and dried.
その結果、糊性異物の主原因であるアクリレート、ポリジメチルスルフィド（ＰＤＭＳ）成分が除去される部分を確認することができる。脱脂剤適用前後の銅見え不良率を比較した結果、脱脂剤の適用後は、適用前に比べて約４０％（３，０８０ｐｐｍから１，８２０ｐｐｍに）改善されたうえ、糊性異物によるＳＲ異物が減少することにより、信頼性を確保することができた。しかも、既存の硫酸処理を、本発明の脱脂剤処理に変更することにより、硫酸廃水処理費用を節減する追加効果も確認された。 As a result, it is possible to confirm a portion where the acrylate and polydimethyl sulfide (PDMS) components, which are the main causes of pasty foreign substances, are removed. As a result of comparing the copper defect rate before and after the application of the degreasing agent, it was improved by about 40% (from 3,080 ppm to 1,820 ppm) after applying the degreasing agent, and the SR foreign matter due to adhesive foreign matter. As a result, the reliability was ensured. Moreover, an additional effect of reducing the sulfuric acid wastewater treatment cost was confirmed by changing the existing sulfuric acid treatment to the degreasing treatment of the present invention.
以上、本発明を具体的な実施例に基づいて詳細に説明したが、これは本発明を具体的に説明するためのものであり、本発明はこれに限定されず、当該分野における通常の知識を有する者であれば、本発明の技術的思想内にての変形や改良が可能であることは明白であろう。 The present invention has been described in detail on the basis of specific embodiments. However, the present invention is intended to specifically describe the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and improvements within the technical idea of the present invention are possible.
本発明の単純な変形乃至変更はいずれも本発明の領域に属するものであり、本発明の具体的な保護範囲は添付の特許請求の範囲より明確になるであろう。 All simple variations and modifications of the present invention belong to the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.
本発明は、フォトソルダーレジスト前処理用脱脂剤及びこれを用いた脱脂方法に適用可能である。 The present invention is applicable to a degreasing agent for pretreatment of a photo solder resist and a degreasing method using the same.
１０ プリント基板
２０ 回路パターン
10 Printed circuit board 20 Circuit pattern
Claims (11)
前記脱脂剤で処理されたプリント基板の表面をＡｌ２Ｏ３粒でジェット研磨する段階と、
前記ジェット研磨されたプリント基板の表面を硫酸で処理する段階と、
を含んでなるフォトソルダーレジスト前処理用脱脂剤を用いた脱脂方法。 Before the formation of the photo solder resist, 10% to 70% by weight of glycol ether, 1% to 25% by weight of alcohol amine, 10% to 70% by weight of amine surfactant, and the balance a step of applying a degreasing agent containing water as,
Jet polishing the surface of the printed circuit board treated with the degreasing agent with Al 2 O 3 grains;
Treating the jet-polished printed circuit board surface with sulfuric acid;
A degreasing method using a degreasing agent for photo solder resist pretreatment comprising:
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| KR1020120149773A KR101432389B1 (en) | 2012-12-20 | 2012-12-20 | A degreasing agent for pretreatment process of photo solder resist and degreasing method using the same |
| KR10-2012-0149773 | 2012-12-20 |
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| CN111770642A (en) * | 2020-06-11 | 2020-10-13 | 珠海斗门超毅实业有限公司 | Application method of bonding agent in surface treatment of circuit board and circuit board |
| JP2024546237A (en) * | 2021-12-14 | 2024-12-19 | ダウ グローバル テクノロジーズ エルエルシー | Cleaning formulations |
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| JPH08917B2 (en) * | 1990-06-27 | 1996-01-10 | 花王株式会社 | Detergent composition |
| JPH0551599A (en) * | 1991-08-27 | 1993-03-02 | Toho Chem Ind Co Ltd | Cleaning composition |
| JPH05125395A (en) * | 1991-11-05 | 1993-05-21 | Metsuku Kk | Cleaner composition |
| JPH05295365A (en) * | 1992-04-24 | 1993-11-09 | Mitsubishi Gas Chem Co Inc | Copper-clad laminated board surface treatment agent |
| JPH0754178A (en) * | 1993-08-16 | 1995-02-28 | Showa Shell Sekiyu Kk | Degreasing method |
| JPH08309662A (en) * | 1995-05-16 | 1996-11-26 | Sumitomo Metal Mining Co Ltd | Lead frame plating pretreatment equipment |
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| JP2007335856A (en) * | 2006-05-19 | 2007-12-27 | Sanyo Chem Ind Ltd | Detergent for electronics material |
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