TW201425568A - A degreasing agent for pretreatment process of photo solder resist and degreasing method using the same - Google Patents
A degreasing agent for pretreatment process of photo solder resist and degreasing method using the same Download PDFInfo
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- TW201425568A TW201425568A TW102128721A TW102128721A TW201425568A TW 201425568 A TW201425568 A TW 201425568A TW 102128721 A TW102128721 A TW 102128721A TW 102128721 A TW102128721 A TW 102128721A TW 201425568 A TW201425568 A TW 201425568A
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- solder resist
- amine
- degreasing
- degreaser
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 64
- 239000013527 degreasing agent Substances 0.000 title claims abstract description 61
- 238000005237 degreasing agent Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000005238 degreasing Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 alcohol amine Chemical class 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000005422 blasting Methods 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 29
- 230000007547 defect Effects 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 206010010957 Copper deficiency Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Detergent Compositions (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本發明係關於感光防焊劑(Photo Solder Resist， PSR)前處理用脫脂劑及應用其之脫脂方法。在本說明書中，用語「防焊劑(Solder Resist，SR)」與感光防焊劑實質上為相同的意思，而在以下不特別加以區分使用。 The invention relates to a photosensitive solder resist (Photo Solder Resist, PSR) Degreaser for pretreatment and degreasing method using it. In the present specification, the term "Solder Resist (SR)" is substantially the same as the photosensitive solder resist, and is not particularly distinguished from the following.
印刷基板，特別是製造晶片貼板(Board On Chip，BOC)封裝時經常使用感光防焊劑。使用感光防焊劑的目的係防止電路圖案之間的短路(short)，並支持銲珠(solder ball)。在銲料膠(solder paste)使導線架附著在基板之情形下，導線架(lead frame)型感光防焊劑係扮演用以防止電路圖案間的短路之絕緣角色，而球閘陣列封裝(Ball Grid Array，BGA)型感光防焊劑則扮演能將銲珠附著在基板上的位置之角色，以及在回焊(reflow)時擔任防止相鄰的銲珠與銲料膠所引起的短路之角色。 Printed substrates, especially for the manufacture of wafer boards (Board On Chip, BOC) Photosensitive solder resists are often used in packaging. The purpose of using a photosensitive solder resist is to prevent short circuits between circuit patterns and to support solder balls. In the case where a solder paste adheres a lead frame to a substrate, a lead frame type photosensitive solder resist plays an insulating role for preventing a short circuit between circuit patterns, and a ball grid array package (Ball Grid Array) , BGA) type photosensitive solder resist plays the role of attaching the solder beads to the substrate, and acts as a short circuit caused by the adjacent solder balls and solder paste during reflow.
然而，在印刷基板上形成感光防焊劑時，會持續 地發生由膠帶的糊或乾膜(Dry film，D/F)等的丙烯酸酯系雜質 所造成之防焊劑雜質缺陷(亦即，因雜質致使防焊劑未良好地附著或被形成於印刷基板之現象)。此外，在防焊劑外觀缺陷之中，也顯示出因防焊劑雜質所造成的缺陷最常發生。採集防焊劑雜質缺陷的試料來進行成分分析的結果，分析認為是由於糊性雜質所引起的外觀缺陷。雜質之產生主要是在感光防焊劑步驟前，於電路顯影蝕刻剝離(DES)步驟及/或電路形成(AOI)檢查步驟之時，自無塵膠帶、清潔墊(Clean Pad)、膠帶(Adhesive Tape)等轉移而來之雜質所引起的。雜質成分分析的結果，丙烯酸酯成分之佔有率達50%以上。 However, when a photosensitive solder resist is formed on a printed substrate, it continues Acrylate-based impurities such as paste or dry film (Dry film, D/F) The solder resist impurity defect (that is, the phenomenon that the solder resist is not well adhered or formed on the printed substrate due to impurities). In addition, among the defects in the appearance of the solder resist, it is also shown that defects due to the impurities of the solder resist most frequently occur. The results of the component analysis were carried out by taking samples of the flux-preventing impurity defects, and the analysis was considered to be an appearance defect caused by the paste impurities. The impurities are mainly generated before the photosensitive solder resist step, during the circuit development etch stripping (DES) step and/or the circuit forming (AOI) inspection step, from the dust-free tape, the cleaning pad (Clean Pad), the tape (Adhesive Tape). ) caused by impurities transferred from the transfer. As a result of impurity component analysis, the occupation ratio of the acrylate component was 50% or more.
此種丙烯酸酯成分，可在感光防焊劑前處理前的 外觀檢查時被確認，由於它在進行感光防焊劑前處理時沒有被去除，因而在防焊劑塗布時與油墨混合而產生露銅(亦即，銅電路圖案上，因雜質而金屬鍍敷未形成金屬鍍敷，以致銅露出而可以目視看見銅的現象)、或者產生防焊劑雜質等之缺陷。 This acrylate component can be used before the pre-treatment of the photosensitive solder resist It was confirmed during the visual inspection that it was not removed during the pre-treatment of the photosensitive solder resist, so that it was mixed with the ink during the application of the solder resist to produce copper (i.e., on the copper circuit pattern, metal plating was not formed due to impurities. The metal is plated so that the copper is exposed to visually see the phenomenon of copper, or defects such as solder resist impurities are generated.
為了去除此種丙烯酸酯成分，因而在現有的感光 防焊劑前處理時所使用之藥品皆使用硫酸及硫酸-過氧化氫等表面氧化去除型的，但是以硫酸系藥品無法去除丙烯酸酯成分等高黏著性雜質。另一方面，在專利文獻1中，雖然揭示了可以N-甲基吡咯啶酮及二甲基甲醯胺為主成分之組成物來去除丙烯酸類成分，但它不僅不是感光防焊劑前處理用的，而且也有使洗淨力變差的傾向。 In order to remove such acrylate components, the existing sensitization The chemicals used in the pretreatment of the solder resist are surface-oxidized and removed such as sulfuric acid and sulfuric acid-hydrogen peroxide. However, high-adhesive impurities such as acrylate components cannot be removed by the sulfuric acid-based drug. On the other hand, in Patent Document 1, although a composition containing N-methylpyrrolidone and dimethylformamide as a main component is disclosed to remove an acrylic component, it is not only used for pretreatment of photosensitive solder resist. There is also a tendency to deteriorate the detergency.
因為以感光防焊劑前處理藥品進行感光防焊劑 前處理之藥品處理裝置，其長度為在約1公尺以內，且藥品處 理時間為不超過約20秒的水準，故要求開發出一種高反應性洗淨藥品。又，可適用於感光防焊劑前處理之鹼性洗淨藥品，由於是鹼性成分，因而不會降低印刷基板與感光防焊劑油墨的接合性。然而，現況為尚未開發出感光防焊劑前處理專用的鹼性藥品。 Because the photosensitive solder resist pretreatment drug is used for photosensitive solder resist Pretreatment drug treatment device, the length of which is within about 1 meter, and the drug department The rational time is no more than about 20 seconds, so it is required to develop a highly reactive cleaning drug. Moreover, the alkaline cleaning drug which can be applied to the pretreatment of the photosensitive solder resist does not lower the bondability between the printed substrate and the photosensitive solder resist ink because it is an alkaline component. However, the current situation is that alkaline chemicals for the pretreatment of photosensitive solder resist have not yet been developed.
〔專利文獻1〕韓國公開專利第2006-0098100號說明書 [Patent Document 1] Korean Patent Publication No. 2006-0098100
因此，本案發明人成功開發出可解決上述問題之包按胺-醚(amine-ether)化合物之新穎的鹼系脫脂劑組成物，並基於它而完成本發明。 Therefore, the inventors of the present invention have succeeded in developing a novel alkali-based degreaser composition containing an amine-ether compound which can solve the above problems, and have completed the present invention based thereon.
因此，本發明之目的係提供一種感光防焊劑前處理用脫脂劑，其除了不會降低印刷基板與感光防焊劑油墨之接合性以外，而且洗淨力優良，並可以顯著地減少露銅缺陷及防焊劑雜質缺陷。 Accordingly, it is an object of the present invention to provide a degreaser for pretreatment of a photosensitive solder resist which, in addition to not lowering the bondability between a printed substrate and a photosensitive solder resist ink, has excellent cleaning power and can significantly reduce copper defects and Solder flux impurity defects.
本發明之其他的目的係提供一種印刷基板脫脂之方法，其為藉由使用前述感光防焊劑前處理用脫脂劑，藉以顯著減少現有的硫酸之使用量，並可對環境友善。 Another object of the present invention is to provide a method for degreasing a printed substrate by using the aforementioned degreaser for pretreatment of the photosensitive solder resist, whereby the amount of the existing sulfuric acid used is remarkably reduced, and the environment is friendly.
依據本發明之某一觀點，可提供一種包括二醇醚、醇胺、胺系界面活性劑、及水之感光防焊劑前處理用脫脂劑(以下稱為「第1發明」)。 According to one aspect of the present invention, a degreaser for pretreatment of a photosensitive solder resist comprising a glycol ether, an alcohol amine, an amine surfactant, and water (hereinafter referred to as "first invention") can be provided.
第1發明之特徵為：前述脫脂劑係包括10~70重量%的二醇醚、1~25重量%的醇胺、10~70重量%的胺系界面活性劑，而剩餘部分為水。 According to a first aspect of the invention, the degreasing agent comprises 10 to 70% by weight of a glycol ether, 1 to 25% by weight of an alcohol amine, and 10 to 70% by weight of an amine-based surfactant, and the remainder is water.
第1發明之特徵為：前述二醇醚係乙二醇 (Ethylene glycol)、聚乙二醇單丁基醚(polyethylene glycol monobutyl ether)、或聚乙二醇單甲基醚(polyethylene glycol monomethyl ether)。 The first invention is characterized in that the glycol ether-based ethylene glycol (Ethylene glycol), polyethylene glycol monobutyl ether, or polyethylene glycol monomethyl ether.
第1發明之特徵為：前述醇胺係甲基二乙醇胺 (Methyldiethanolamine)、或單乙醇胺(monoethanolamine)。 The first invention is characterized in that the aforementioned alcohol amine methyl diethanolamine (Methyldiethanolamine), or monoethanolamine.
第1發明之特徵為：前述胺系界面活性劑係以化 學式R-NH2表示(式中，R係碳數11~18的烷基)之非離子性界面活性劑。 According to a first aspect of the 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).
第1發明之特徵為：前述脫脂劑係更進一步包括 在0.1~5重量%之範圍的抗氧化劑、消泡劑或它們的混合物。 The first invention is characterized in that the aforementioned degreasing agent further comprises An antioxidant, an antifoaming agent or a mixture thereof in the range of 0.1 to 5% by weight.
依據本發明之另一觀點，提供一種使用感光防焊 劑前處理用脫脂劑之脫脂方法，其係包括：在形成感光防焊劑前，將包含有二醇醚、醇胺、胺系界面活性劑及水之脫脂劑塗布在殘留有雜質之印刷基板的表面之步驟；以Al2O3粒對以前述脫脂劑處理過的印刷基板之表面進行噴砂研磨之步驟；及以硫酸來處理經前述噴砂研磨處理過之印刷基板的表面之步驟(以下稱為「第2發明」)。。 According to another aspect of the present invention, there is provided a degreasing method using a degreaser for pretreatment of a photosensitive solder resist, comprising: comprising a glycol ether, an alcohol amine, an amine surfactant, and a surfactant before forming the photosensitive solder resist a step of applying a water degreaser to the surface of the printed substrate on which the impurities remain; a step of sandblasting the surface of the printed substrate treated with the degreaser with Al 2 O 3 particles; and treating the surface by the blasting with sulfuric acid The step of treating the surface of the printed substrate (hereinafter referred to as "the second invention"). .
第2發明之特徵為：前述脫脂劑係包括10~70重量 %的二醇醚、1~25重量%的醇胺、10~70重量%的胺系界面活性劑，而剩餘部分為水。 According to a second aspect of the invention, the degreasing agent comprises 10 to 70 weights. % glycol ether, 1 to 25% by weight of an alcohol amine, 10 to 70% by weight of an amine-based surfactant, and the balance being water.
第2發明之特徵為：前述二醇醚係乙二醇、聚乙 二醇單丁基醚、或聚乙二醇單甲基醚。 The second invention is characterized in that the glycol ether is ethylene glycol or polyethylene glycol. Glycol monobutyl ether, or polyethylene glycol monomethyl ether.
第2發明之特徵為：前述醇胺係甲基二乙醇胺、 或單乙醇胺。 According to a second aspect of the invention, the alcohol amine is methyldiethanolamine, Or monoethanolamine.
第2發明之特徵為：前述胺系界面活性劑係以化 學式R-NH2表示(式中，R係碳數11~18的烷基)之非離子性界面活性劑。 According to a second aspect of the 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).
第2發明之特徵為：前述脫脂劑係更進一步包括 在0.1~5重量%之範圍的抗氧化劑、消泡劑或它們的混合物。 The second invention is characterized in that the aforementioned degreasing agent further comprises An antioxidant, an antifoaming agent or a mixture thereof in the range of 0.1 to 5% by weight.
第2發明之特徵為：於前述脫脂劑的塗布步驟為 以1~2kgf之壓力進行噴霧噴射歷10~40秒鐘。 According to a second aspect of the invention, the coating step of the degreasing agent is The spray is sprayed at a pressure of 1 to 2 kgf for 10 to 40 seconds.
本發明之感光防焊劑前處理用脫脂劑，除了不會降低印刷基板與感光防焊劑油墨之接合性以外，由於具有優良的洗淨力，因而具有可以顯著地減少露銅缺陷、防焊劑雜質缺陷及現有的硫酸之使用量，並且可以對環境友善地使印刷基板脫脂之效果。 The degreaser for pretreatment of the photosensitive solder resist of the present invention has a remarkable detergency, and has excellent detergency, thereby significantly reducing copper defects and solder paste impurity defects. And the amount of sulfuric acid used in the prior art, and the effect of degreasing the printed substrate to the environment is friendly.
為了對本發明之上述及其他方面有更佳的瞭解，下文特舉實施例，並配合所附圖式，作詳細說明如下： In order to provide a better understanding of the above and other aspects of the present invention, the following detailed description of the embodiments and the accompanying drawings
10‧‧‧印刷基板 10‧‧‧Printing substrate
20‧‧‧電路圖案 20‧‧‧ circuit pattern
第1圖為顯示使用本發明的脫脂劑來去除雜質(膠帶的糊等)之原理的示意圖。 Fig. 1 is a schematic view showing the principle of removing impurities (paste of tape, etc.) using the degreasing agent of the present invention.
第2圖為顯示使用本發明的脫脂劑之脫脂方法的示意圖。 Fig. 2 is a schematic view showing a degreasing method using the degreasing agent of the present invention.
第3圖為比較本發明的較佳實施例之脫脂劑與現有的脫脂劑之洗淨效果的相片。 Fig. 3 is a photograph comparing the cleaning effect of the degreaser of the preferred embodiment of the present invention with a conventional degreaser.
在進一步具體說明本發明之前，首先確立以下之 原則，即使用於本說明書及申請專利範圍之用語或單詞並未 限定於通常上的與辭典上的意思，可以是為了以最佳方法來說明發明而適切地定義用語的概念之原則，而解釋上則需符合本發明之技術思想的意思與概念。因此，記載於本說明書的實施例之構成，不過是本發明的較佳例之一，並非用以表達本發明之全部的技術思想。因此，應理解到本案申請當時之時點，存在有能夠代替它們之各種的等價物及變形例。 Before further elaboration of the present invention, first establish the following Principle, even if the terms or words used in this specification and the scope of the patent application are not The meanings that are limited to the general term and the dictionary may be the principles for appropriately defining the concept of the term in order to explain the invention in an optimal manner, and the explanation is in accordance with the meaning and concept of the technical idea of the present invention. Therefore, the configuration of the embodiment described in the present specification is merely one of the preferred embodiments of the present invention, and is not intended to express all of the technical idea of the present invention. Therefore, it should be understood that at the time of the application of the present application, there are various equivalents and modifications that can be substituted for them.
以下，以讓本發明所屬技術領域中具有通常知識者能容易地實施本發明之方式，而詳細地說明本發明之較佳實施例。另外，在說明本發明時，對於有可能讓本發明之要旨不清楚之公知技術，則省略其詳細說明。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail by way of the embodiments of the present invention. In addition, in the description of the present invention, a detailed description of known techniques that may obscure the gist of the present invention will be omitted.
如前述般，在過去，為了去除印刷基板表面的氧化膜及油膜而使用硫酸，但是在丙烯酸酯及乾膜(D/F)等有黏著力的雜質之情形下，無法以硫酸去除之。丙烯酸酯及/或D/F等糊性雜質，完全不會與硫酸起反應。為了去除糊性雜質，則需要由離子化物質產生的中和反應、及界面活性劑的物理膨潤(swelling)反應。 As described above, in the past, sulfuric acid was used to remove the oxide film and the oil film on the surface of the printed substrate. However, in the case of adhesive impurities such as acrylate and dry film (D/F), it cannot be removed by sulfuric acid. Paste impurities such as acrylate and/or D/F do not react with sulfuric acid at all. In order to remove the paste impurities, a neutralization reaction by the ionized substance and a physical swelling reaction of the surfactant are required.
下述反應式1及2為使用於一般的洗淨用浸漬線(Dipping Line)之脫脂劑的糊去除反應機構。脫脂劑的洗淨原理，其為如下述反應式1般之與切斷黏著劑成分的OH環之螯合反應相同的化學反應，或者是如下述反應式2般之由膨潤產生的物理脫附反應。又，此種洗淨力係與溫度及時間成比例(動能與溫度之定律、阿瑞尼斯定律)。 The following Reaction Formulas 1 and 2 are paste removal reaction mechanisms for a degreasing agent used in a general Dipping Line for washing. The principle of washing the degreaser is the same chemical reaction as the chelation reaction of the OH ring for cutting the adhesive component as in the following Reaction Formula 1, or physical desorption by swelling as in the following Reaction Formula 2 reaction. Moreover, such a cleaning power is proportional to temperature and time (the law of kinetic energy and temperature, Arrhenius's law).
在使用如上述反應式1般的離子化反應性高之鈉離子(Na+)的化學反應之情形，因為是與黏著劑成分直接反應，所以去除效果優良。然而，由於因中和反應而產生固體結晶(水玻璃現象)，所以試驗結果為它不能適用於PCB的前處理線。在如前述反應式2般的一般界面活性劑型的脫脂劑之情形，由於在噴霧噴射時會產生過多的泡沫，因而不適合噴霧型的濕式線(wet-line)。 In the case of using a chemical reaction of sodium ion (Na + ) having high ionization reactivity as in the above Reaction Formula 1, since it is directly reacted with the binder component, the removal effect is excellent. However, since solid crystallization (water glass phenomenon) occurs due to the neutralization reaction, the test result is that it cannot be applied to the pretreatment line of the PCB. In the case of the degreaser of the general surfactant type as in the above Reaction Formula 2, since it is excessively foamed at the time of spray spraying, it is not suitable for a spray type wet-line.
由於像這樣的2個問題，雖然於一般的浸漬線所使用的脫脂劑之脫脂效果是優良的，但卻不能夠適用於量產線。為了解決這些問題，首先應該要解決的課題為如下所述。 Due to such two problems, the degreasing effect of the degreasing agent used in the general dipping line is excellent, but it cannot be applied to the mass production line. In order to solve these problems, the first problem to be solved is as follows.
1)不產生結晶雜質-不適用需要金屬成分的離子 化物質。 1) No crystal impurities are produced - ions that require metal components are not suitable Chemical substances.
2)高反應性要求-能克服短濕式線之限制的高反應性藥品。 2) High reactivity requirements - highly reactive drugs that overcome the limitations of short wet lines.
3)不能產生泡沫-不適用界面活性劑，需要擔任同樣角色的替代物質。 3) Can't produce foam - no surfactants are needed and need to be an alternative substance in the same role.
4)須對防焊劑接合性沒有阻礙(風險)。 4) There must be no obstruction (risk) of solder resist bonding.
本發明中開發出了一種能夠滿足此種要求條件之感光防焊劑前處理專用胺-醚(amine-ether)成分之脫脂劑。 現有的具有胺-醚成分之脫脂及洗淨劑，不能夠使用來當做感光防焊劑前處理用。如前述般，現有的洗淨劑，因它會阻礙與感光防焊劑油墨間的接合可靠度，故要求具有完美的水溶性。此外，還要求不僅是在短時間內具有高雜質去除效果，而且要求在長時間使用時之藥品平衡不會崩壞，並且能維持持續之耐久性。 In the present invention, a degreaser for an amine-ether component which is suitable for the pretreatment of a photosensitive solder resist which satisfies such a requirement is developed. The existing degreasing and detergent having an amine-ether component cannot be used as a pretreatment for photosensitive solder resist. As described above, the conventional detergent is required to have perfect water solubility because it hinders the bonding reliability with the photosensitive solder resist ink. In addition, it is required not only to have a high impurity removal effect in a short period of time, but also to ensure that the drug balance does not collapse during long-term use, and to maintain sustained durability.
本發明之胺-醚化合物具有與界面活性劑相同之膨潤及剝離效果，並具有不產生泡沫的特性。參照第1圖，本發明之胺-醚化合物，胺-醚化合物的NH直接滲透並溶解於黏著劑成分，並藉由醚的膨潤效果，具有降低試片的邊界表面(感光防焊劑試片與糊)之糊性的效果。 The amine-ether compound of the present invention has the same swelling and peeling effect as the surfactant, and has a property of not generating foam. Referring to Fig. 1, the amine-ether compound of the present invention, the NH of the amine-ether compound directly permeates and dissolves in the adhesive component, and has a lowering of the boundary surface of the test piece by the swelling effect of the ether (photosensitive solder resist test piece and Paste effect of paste).
本發明之感光防焊劑前處理用脫脂劑係包括二醇醚、醇胺、胺系界面活性劑、及水。較佳者為前述脫脂劑係包括10~70重量%的二醇醚、1~25重量%的醇胺、10~70重量%的胺系界面活性劑，而剩餘部分為水。 The degreaser for pretreatment of the photosensitive solder resist of the present invention includes a glycol ether, an alcohol amine, an amine surfactant, and water. Preferably, the degreasing agent comprises 10 to 70% by weight of glycol ether, 1 to 25% by weight of an alkanolamine, and 10 to 70% by weight of an amine-based surfactant, and the remainder is water.
本發明中，前述二醇醚係為了膨潤組成物及提升 滲透力而添加之物，舉例而言，例如，乙二醇、聚乙二醇單丁基醚、或聚乙二醇單甲基醚等，但非限定於此。而前述二醇醚的混合量，較佳為10~70重量%，在小於10重量%之情形下，洗淨力會有降低的傾向，而在大於70重量%之情形，則因前述二醇醚為易燃物質而會有腐蝕、可靠度等方面之問題。 In the present invention, the glycol ether is used for swelling compositions and lifting The substance to be added by the osmotic force is, for example, ethylene glycol, polyethylene glycol monobutyl ether, or polyethylene glycol monomethyl ether, but is not limited thereto. The amount of the glycol ether blended is preferably from 10 to 70% by weight. In the case of less than 10% by weight, the detergency tends to decrease, and in the case of more than 70% by weight, the diol is Ether is a flammable substance and has problems such as corrosion and reliability.
前述醇胺，舉例而言，例如，甲基二乙醇胺或單乙醇胺等，但非限定於此。前述醇胺的混合量，較佳者為1~25重量%，在小於1重量%之情形下，洗淨力會降低，而在大於25重量%之情形下，則會有可靠度等方面之問題。 The alcoholamine is, for example, methyldiethanolamine or monoethanolamine, but is not limited thereto. The amount of the aforementioned alcohol amine is preferably from 1 to 25% by weight. In the case of less than 1% by weight, the detergency is lowered, and in the case of more than 25% by weight, there is reliability and the like. problem.
前述胺系界面活性劑，例如，可以是以化學式R-NH2所表示之非離子性界面活性劑，在上述式中，R係碳數11~18之烷基。前述胺系界面活性劑的混合量，較佳者為10~70重量%，在小於10重量%之情形下，組成物本身的混合性會降低，而在大於70重量%之情形，則會有洗淨力降低之傾向。 The amine-based surfactant may be, for example, a nonionic surfactant represented by the chemical formula R-NH 2 , and in the above formula, R is an alkyl group having 11 to 18 carbon atoms. The amount of the amine-based surfactant to be mixed is preferably from 10 to 70% by weight. In the case of less than 10% by weight, the mixing property of the composition itself may be lowered, and in the case of more than 70% by weight, there may be The tendency to reduce the detergency.
以前述胺系界面活性劑來去除環氧硬化物之洗淨機構係如下述反應式3般。參照反應式3，可知前述胺系界面活性劑的胺基，係經由切斷環氧硬化物的環氧基，藉以弱化環氧硬化物的黏著力並予以去除。 The cleaning mechanism for removing the epoxy cured product by the above-described amine-based surfactant is as in the following Reaction Formula 3. Referring to Reaction Formula 3, it is understood that the amine group of the amine-based surfactant is obtained by cutting the epoxy group of the epoxy-cured material, thereby weakening the adhesion of the epoxy-cured material and removing it.
另一方面，本發明之脫脂劑組成物，在不損害本 發明之效果的範圍內，可以視需要而更進一步包括在0.1~5重量%之範圍內的抗氧化劑、消泡劑或彼等之混合物，因而可以發揮較佳的物性與機能。 On the other hand, the degreasing agent composition of the present invention does not damage the present Within the scope of the effects of the invention, an antioxidant, an antifoaming agent or a mixture thereof in an amount of 0.1 to 5% by weight may be further included as needed, so that preferable physical properties and functions can be exhibited.
依據本發明，可以水溶液狀態混合前述樹脂組成物來得到本發明之脫脂劑。參照第2圖來考察使用前述脫脂劑之印刷基板的感光防焊劑前處理步驟。首先，1)為了去除形成有銅電路圖案20之印刷基板10的氧化膜及其它的雜質，則以約1~2kgf之壓力，噴霧噴射本發明之脫脂劑來進行處理歷10~40秒鐘後，進行水洗並加以乾燥。2)為了去除前述基板表面的雜質，則進行噴砂研磨。前述噴砂研磨係以大小50~100μm之Al2O3粒，以約1~3kgf的壓力，進行物理性打撃20~50秒鐘後，進行水洗並加以乾燥。3)為了提升感光防焊劑的密合力，最後以約1~2kgf之壓力，噴霧噴射約10%的硫酸處理10~30秒鐘後，進行水洗並加以乾燥。 According to the invention, the above resin composition can be mixed in an aqueous solution state to obtain the degreasing agent of the present invention. The photosensitive flux pretreatment step of the printed substrate using the aforementioned degreaser is examined with reference to Fig. 2. First, in order to remove the oxide film and other impurities of the printed circuit board 10 on which the copper circuit pattern 20 is formed, the degreaser of the present invention is spray-sprayed at a pressure of about 1 to 2 kgf for 10 to 40 seconds. , washed with water and dried. 2) Sandblasting is performed in order to remove impurities on the surface of the substrate. The blasting polishing is performed by physically rubbing for 20 to 50 seconds with an Al 2 O 3 particle having a size of 50 to 100 μm at a pressure of about 1 to 3 kgf, followed by washing with water and drying. 3) In order to improve the adhesion of the photosensitive solder resist, the spray is sprayed with about 10% sulfuric acid for about 10 to 30 seconds at a pressure of about 1 to 2 kgf, then washed with water and dried.
像這樣，以本發明之感光防焊劑前處理用脫脂劑進行脫脂處理過的印刷基板，除了與感光防焊劑油墨的接合性優良以外，還顯著地減少露銅缺陷及防焊劑雜質缺陷。 As described above, the printed substrate subjected to the degreasing treatment with the degreaser for photo-sensitive solder resist pretreatment of the present invention is excellent in adhesion to the photosensitive solder resist ink, and also significantly reduces copper defects and solder paste impurity defects.
以下，藉由實施例及比較例而更進一步具體地說明本發明。但，本發明之範疇並非受限於這些實施例。 Hereinafter, the present invention will be further specifically described by way of examples and comparative examples. However, the scope of the invention is not limited to these embodiments.
於水中，添加10重量%的醇胺(Cas No.111-42-2)、及7重量%的胺系界面活性劑(Cas No.61790-85-0)並均勻混合，而製造成脫脂劑。 10% by weight of an alcohol amine (Cas No. 111-42-2) and 7% by weight of an amine surfactant (Cas No. 61790-85-0) were added to the water and uniformly mixed to prepare a degreaser. .
於水中，添加15重量%的二醇醚(Cas No.111-46-6)、10重量%的醇胺(Cas No.111-42-2)、及25重量%的胺系界面活性劑(Cas No.61790-85-0)並均勻混合，而製造成本發明之脫脂劑。 In water, 15% by weight of glycol ether (Cas No. 111-46-6), 10% by weight of alcohol amine (Cas No. 111-42-2), and 25% by weight of an amine-based surfactant ( Cas No. 61790-85-0) was uniformly mixed to produce a degreasing agent of the invention.
讓糊任意地附著在銅板表面上，再使用硫酸、氫氧化鈉及本發明之脫脂劑，進行20秒及30秒間之浸漬試驗，再進一步地使用製程能力B/D進行無電解金屬鍍敷。其試驗結果示於第3圖及下述表1。第3圖中，A表示10%硫酸、B表示10%氫氧化鈉溶液、C表示比較例1之脫脂劑、D表示實施例1之脫脂劑。 The paste was arbitrarily attached to the surface of the copper plate, and then immersion test was performed for 20 seconds and 30 seconds using sulfuric acid, sodium hydroxide, and the degreaser of the present invention, and electroless metal plating was further performed using the process capability B/D. The test results are shown in Figure 3 and Table 1 below. In Fig. 3, A represents 10% sulfuric acid, B represents a 10% sodium hydroxide solution, C represents a degreasing agent of Comparative Example 1, and D represents a degreasing agent of Example 1.
由第3圖及表1可明白：於浸漬試驗時，確認有未能以10%硫酸溶液完全除去膠帶的糊之部分。在脫脂劑之情形下，顯示出30秒以前的洗淨效果，並可確認到完全去除之部分。而且，只有本發明之脫脂劑顯示出約20秒左右之100%糊去除力。 It can be understood from Fig. 3 and Table 1: In the immersion test, it was confirmed that there was a portion of the paste which could not completely remove the tape with a 10% sulfuric acid solution. In the case of the degreasing agent, the washing effect before 30 seconds was exhibited, and the completely removed portion was confirmed. Moreover, only the degreaser of the present invention exhibits a 100% paste removal force of about 20 seconds.
另一方面，使用製程能力B/D，投入前處理設備來進行噴霧試驗之結果，本發明之脫脂劑，顯示出高於硫酸50%以上的糊去除性能，且在應用於量產以前，於早期檢驗之試驗中，未產生鍍敷粗糙現象及防焊劑隆起(未產生發泡)。在 本發明的脫脂劑之情形，可確認在進行前處理以前被發現到的糊性雜質，在通過前處理後即已被去除之部分。 On the other hand, the degreasing agent of the present invention exhibits a paste removal performance higher than 50% of sulfuric acid by using a process capability B/D and a pretreatment apparatus for performing a spray test, and before being applied to mass production, In the early test, no plating roughness and solder bump bulging (no foaming) occurred. in In the case of the degreasing agent of the present invention, it is confirmed that the pasty impurities which were found before the pretreatment were removed were removed after the pretreatment.
將糊任意地附著在印刷基板之表面，並放置於感光防焊劑前處理藥品處理裝置之後，再以約2kgf之壓力噴霧噴射實施例1之脫脂劑進行約20秒鐘之處理後，進行水洗並加以乾燥。然後，用大小約50~100μm的Al2O3粒，以約2kgf的壓力，對前述基板進行物理性打擊約40秒鐘後，進行水洗並加以乾燥。然後，以約2kgf的壓力噴霧噴射約10%的硫酸進行約15秒鐘之處理後，進行水洗並加以乾燥。 The paste is arbitrarily attached to the surface of the printed substrate, and placed in the photosensitive flux pretreatment drug treatment device, and then sprayed with the degreaser of Example 1 at a pressure of about 2 kgf for about 20 seconds, and then washed with water. Dry it. Then, the substrate was physically hit with a pressure of about 2 kgf for about 40 seconds using Al 2 O 3 particles having a size of about 50 to 100 μm, and then washed with water and dried. Then, about 10% of sulfuric acid was spray-sprayed at a pressure of about 2 kgf for about 15 seconds, and then washed with water and dried.
其結果，可確認：形成糊性雜質之主因的丙烯酸酯、聚二甲硫醚(PDMS)成分被去除之部分。比較脫脂劑使用前、後的露銅缺陷率的結果，在使用脫脂劑後，由於除了比使用前改善了約40%(從3,080ppm變為1,820ppm)以外，而且因糊性雜質而產生的防焊劑雜質亦減少，故能夠確保信賴度。此外，也還可以確認：藉由將現有的硫酸處理變更為本發明之脫脂劑處理，可節省硫酸廢水處理費用之附加效果。 As a result, it was confirmed that the acrylate and polydimethyl sulfide (PDMS) components which are the main cause of the paste impurities were removed. Comparing the results of the copper deficiency rate before and after the use of the degreaser, after using the degreasing agent, it is improved by about 40% (from 3,080 ppm to 1,820 ppm), and is caused by paste impurities. Solder flux impurities are also reduced, so reliability can be ensured. Further, it has also been confirmed that the additional effect of the treatment cost of the sulfuric acid wastewater can be saved by changing the existing sulfuric acid treatment to the degreasing agent treatment of the present invention.
綜上所述，雖然本發明已以具體實施例揭露如上，然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。 In the above, the present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
本發明之單純變形乃至變更，也皆是當然屬於本發明之領域中者；又，本發明之保護範圍當視後附之申請專利範圍所界定者為準。 It is to be understood that the scope of the invention is defined by the scope of the appended claims.
10‧‧‧印刷基板 10‧‧‧Printing substrate
20‧‧‧電路圖案 20‧‧‧ circuit pattern
Claims (13)
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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 |
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| TW201425568A true TW201425568A (en) | 2014-07-01 |
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| JP (1) | JP5763129B2 (en) |
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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 |
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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 | Detergent 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 | Surface cleaning/conditioning agent for copper-clad laminate |
| 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 | Plating preliminary processing equipment for lead frame |
| JP2944518B2 (en) * | 1996-07-16 | 1999-09-06 | 富山日本電気株式会社 | Copper and copper alloy surface treatment agent |
| KR100429152B1 (en) * | 1999-12-22 | 2004-04-28 | 주식회사 포스코 | a method of manufacturing a surface-treated steel sheet with superior weldability for welded can |
| JP2007335856A (en) * | 2006-05-19 | 2007-12-27 | Sanyo Chem Ind Ltd | Detergent for electronics material |
| JP5113423B2 (en) | 2007-05-28 | 2013-01-09 | ディバーシー株式会社 | Stripping composition for floor polish and stripping removal method using the same |
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| JP5763129B2 (en) | 2015-08-12 |
| JP2014122416A (en) | 2014-07-03 |
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