JP2571375B2 - Release agent for water-soluble resist film - Google Patents
Release agent for water-soluble resist filmInfo
- Publication number
- JP2571375B2 JP2571375B2 JP62016377A JP1637787A JP2571375B2 JP 2571375 B2 JP2571375 B2 JP 2571375B2 JP 62016377 A JP62016377 A JP 62016377A JP 1637787 A JP1637787 A JP 1637787A JP 2571375 B2 JP2571375 B2 JP 2571375B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- resist film
- release agent
- water
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 5
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012493 hydrazine sulfate Substances 0.000 claims description 5
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 3
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- PFVJLGPIYRQLHP-UHFFFAOYSA-L disodium benzene-1,4-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=C(S([O-])(=O)=O)C=C1 PFVJLGPIYRQLHP-UHFFFAOYSA-L 0.000 claims description 3
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 3
- DGZLXQQLJXDRPM-UHFFFAOYSA-N naphthalene-2,6-disulfonic acid;sodium Chemical compound [Na].C1=C(S(O)(=O)=O)C=CC2=CC(S(=O)(=O)O)=CC=C21 DGZLXQQLJXDRPM-UHFFFAOYSA-N 0.000 claims description 3
- DSYVTLPHGJLVKD-UHFFFAOYSA-M sodium 1,5-dimethylcyclohexa-2,4-diene-1-sulfonate Chemical compound [Na+].C1(CC(=CC=C1)C)(C)S(=O)(=O)[O-] DSYVTLPHGJLVKD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- UTEKQAXKLLQOHW-UHFFFAOYSA-M sodium;1-aminonaphthalene-2-sulfonate Chemical compound [Na+].C1=CC=C2C(N)=C(S([O-])(=O)=O)C=CC2=C1 UTEKQAXKLLQOHW-UHFFFAOYSA-M 0.000 claims description 3
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000005028 tinplate Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、水溶性レジストフイルム用剥離剤に関す
る。Description: TECHNICAL FIELD The present invention relates to a water-soluble resist film release agent.
従来の技術及びその問題点 プリント配線板等の製造工程において、回路パターン
の作製に用いられるレジストフイルムは、メツキ処理終
了後、剥離除去することが必要である。レジストフイル
ムの剥離方法としては、フイルムの種類に依つて、剥離
剤として水溶液を用いる方法と有機溶剤を用いる方法と
が知られており、水溶液を用いる方法は、剥離剤が安価
であり、しかも廃液処理が容易である点で有利である。2. Description of the Related Art In a manufacturing process of a printed wiring board or the like, it is necessary to remove and remove a resist film used for manufacturing a circuit pattern after completion of a plating process. As a method for removing the resist film, a method using an aqueous solution and a method using an organic solvent as the release agent are known depending on the type of the film. This is advantageous in that processing is easy.
水溶液タイプの剥離剤としては、一般に水酸化ナトリ
ウム、水酸化カリウム等を２〜５重量％程度含むアルカ
リ水溶液が用いられている。しかしながら、この様なア
ルカリ水溶液によりレジストフイルムの剥離を行なう場
合には、銅板上にスズメツキやハンダメツキを行なつた
基板では、スズやハンダと、銅板との自然電極電位の差
によつて局部電池が生じ、その結果メツキ皮膜が腐食さ
れるという欠点がある。As the aqueous solution type release agent, generally, an alkaline aqueous solution containing about 2 to 5% by weight of sodium hydroxide, potassium hydroxide or the like is used. However, when the resist film is peeled off with such an alkaline aqueous solution, the local battery may be damaged due to the difference in the natural electrode potential between the tin or solder and the copper plate on a substrate on which a tin plate or a solder plate is formed on a copper plate. As a result, there is a disadvantage that the plating film is corroded.
問題点を解決するための手段 本発明者は、上記した如き問題点に鑑みて、水溶性レ
ジストフイルムに対する剥離性能が良好であり、かつメ
ツキ皮膜の腐食を抑制できる水溶性レジストフイルム用
剥離剤を見出すべく、鋭意研究を重ねてきた。その結
果、水酸化ナトリウム及び水酸化カリウムの少なくとも
一種の化合物を含有するアルカリ水溶液中に、特定の還
元性物質を添加して得られる剥離剤を用いて、レジスト
フイルムの剥離を行なう場合には、レジストフイルムに
対する剥離性能は、非常に良好となり、しかもスズやハ
ンダメツキ皮膜の腐食を抑制することが可能となること
を見出した。また、上記した剥離剤に、更にインヒビタ
ーとして、特定のアリールスルホン酸ナトリウム及びイ
オウ化合物から選ばれた少なくとも一種の化合物を添加
した剥離剤を用いる場合には、レジストフイルムに対す
る剥離性能及びメツキ皮膜の腐食抑制効果をともにより
一層向上することを見出した。Means for Solving the Problems In view of the problems described above, the present inventor has developed a water-soluble resist film release agent that has good peeling performance for a water-soluble resist film and can suppress corrosion of a paint film. I've been working hard to find it. As a result, in an aqueous alkaline solution containing at least one compound of sodium hydroxide and potassium hydroxide, using a stripping agent obtained by adding a specific reducing substance, when peeling the resist film, It has been found that the peeling performance with respect to the resist film is very good, and it is possible to suppress the corrosion of the tin or solder plating film. Further, in the case where a release agent to which at least one compound selected from a specific sodium aryl sulfonate and a sulfur compound is added as an inhibitor is used as the above-mentioned release agent, the release performance against the resist film and the corrosion of the paint film are reduced. It has been found that the suppression effect is further improved.
即ち本発明は、以下に示す水溶性レジストフイルム用
剥離剤を提供するものである。That is, the present invention provides the following water-soluble resist film release agent.
ｉ）水酸化ナトリウム及び水酸化カリウムの少なくと
も一種20〜50g/、並びに ii）亜硫酸ナトリウム、チオ硫酸ナトリウム、ハイドロ
サルファイトナトリウム、ホルムアルデヒド、硫酸ヒド
ラジン、ヒドラジン、ジメチルアミンボラン及び次亜リ
ン酸ナトリウムの少なくとも一種からなる還元性物質0.
01〜0.3モル／ を含有する水溶液からなることを特徴とする水溶性レジ
ストフィルム用剥離剤（以下、本願第１発明という）。i) 20 to 50 g / at least one of sodium hydroxide and potassium hydroxide; and ii) at least one of sodium sulfite, sodium thiosulfate, sodium hydrosulfite, formaldehyde, hydrazine sulfate, hydrazine, dimethylamine borane and sodium hypophosphite. One kind of reducing substance 0.
A release agent for a water-soluble resist film, comprising an aqueous solution containing 01 to 0.3 mol / (hereinafter referred to as the first invention of the present application).
ｉ）水酸化ナトリウム及び水酸化カリウムの少なくと
も一種20〜50g/、 ii）亜硫酸ナトリウム、チオ硫酸ナトリウム、ハイドロ
サルファイトナトリウム、ホルムアルデヒド、硫酸ヒド
ラジン、ヒドラジン、ジメチルアミンボラン及び次亜リ
ン酸ナトリウムの少なくとも一種からなる還元性物質0.
01〜0.3モル／、並びに iii）ｐ−フェノールスルホン酸ナトリウム、ｍ−キシ
レンスルホン酸ナトリウム、1,4−ベンゼンジスルホン
酸ナトリウム、４−ヒドロキシナフタレンスルホン酸ナ
トリウム、2,6−ナフタレンジスルホン酸ナトリウム、
１−アミノ−２−ナフタレンスルホン酸ナトリウム、硫
化ナトリウム、チオ尿素、ジメチルチオ尿素、チオエチ
レングリコール、チオセミカルバジド、メチルベンゾチ
アゾール、２−メルカプトベンゾチアゾール及び２−ア
ミノチアゾールの少なくとも一種からなる化合物0.0001
〜0.05モル／ を含有する水溶液からなることを特徴とする水溶性レジ
ストフィルム用剥離剤（以下、本願第２発明という）。i) at least one of sodium hydroxide and potassium hydroxide 20 to 50 g /, ii) at least one of sodium sulfite, sodium thiosulfate, sodium hydrosulfite, formaldehyde, hydrazine sulfate, hydrazine, dimethylamine borane and sodium hypophosphite Reducing substance consisting of 0.
01-0.3 mol /, and iii) sodium p-phenolsulfonate, sodium m-xylenesulfonate, sodium 1,4-benzenedisulfonate, sodium 4-hydroxynaphthalenesulfonate, sodium 2,6-naphthalenedisulfonic acid,
Compound comprising at least one of sodium 1-amino-2-naphthalenesulfonate, sodium sulfide, thiourea, dimethylthiourea, thioethylene glycol, thiosemicarbazide, methylbenzothiazole, 2-mercaptobenzothiazole and 2-aminothiazole 0.0001
A release agent for a water-soluble resist film, which comprises an aqueous solution containing up to 0.05 mol / mol (hereinafter referred to as the second invention).
本発明の剥離剤は、基板上に施した水溶性レジストフ
イルムの剥離のために用いることができ、特に銅板上に
スズメツキやハンダメツキを施したプリント配線基板上
の水溶性レジストフイルムの剥離に有効である。ここで
水溶性レジストフイルムとは、水酸化ナトリウム等のア
ルカリ性水溶液により、膨潤して基板から除去されるよ
うなレジストフイルムをいい、組成は特に限定されるも
のではない。The stripping agent of the present invention can be used for stripping a water-soluble resist film applied on a substrate, and is particularly effective for stripping a water-soluble resist film on a printed wiring board having a tin plate or a solder plate on a copper plate. is there. Here, the water-soluble resist film refers to a resist film that is swollen and removed from the substrate by an alkaline aqueous solution such as sodium hydroxide, and the composition is not particularly limited.
本願第１発明の剥離剤では、基本成分として、水酸化
ナトリウム及び水酸化カリウムの少なくとも一種の化合
物を20〜50g/程度含有するアルカリ水溶液を用いる。
水酸化ナトリウム及び水酸化カリウムの少なくとも一種
の化合物の添加量が20g/未満では剥離能力が不充分で
あり、一方50g/を上回ると、銅板上に酸化皮膜が生じ
易くなり、外観がそこなわれ、また後処理にも悪影響を
及ぼすので好ましくない。In the release agent of the first invention of the present application, an alkaline aqueous solution containing about 20 to 50 g / at least one compound of sodium hydroxide and potassium hydroxide is used as a basic component.
If the addition amount of at least one compound of sodium hydroxide and potassium hydroxide is less than 20 g /, the peeling ability is insufficient, and if it exceeds 50 g /, an oxide film is easily formed on the copper plate, and the appearance is deteriorated. In addition, it has an adverse effect on post-processing, and is therefore not preferred.
本願第１発明の剥離剤では上記したアルカリ水溶液に
特定の還元性物質を添加することが必要である。この様
な還元性物質を添加した剥離剤は、メツキ皮膜の腐食を
抑制でき、かつ、レジストフイルムに対する優れた剥離
能力を有する。還元性物質の添加量は、0.01〜0.3モル
／程度が適当であり、この範囲を下回るとメツキ皮膜
の腐食抑制効果が不足し、一方この範囲を上回ると還元
性物質の空気による接触分解が増大するので好ましくな
い。In the stripping agent of the first invention of the present application, it is necessary to add a specific reducing substance to the above-mentioned alkaline aqueous solution. The stripping agent to which such a reducing substance is added can suppress the corrosion of the plating film and has an excellent stripping ability for the resist film. The amount of the reducing substance to be added is suitably 0.01 to 0.3 mol / approximately. If the amount is less than this range, the effect of suppressing corrosion of the plating film is insufficient. If the amount exceeds this range, catalytic decomposition of the reducing substance by air increases. Is not preferred.
本願第１発明では、還元性物質として、亜硫酸ナトリ
ウム、チオ硫酸ナトリウム、ハイドロサルファイトナト
リウム、ホルムアルデヒド、硫酸ヒドラジン、ヒドラジ
ン、ジメチルアミンボラン及び次亜リン酸ナトリウムの
少なくとも一種からなる化合物を用いる。In the first invention of this application, a compound comprising at least one of sodium sulfite, sodium thiosulfate, sodium hydrosulfite, formaldehyde, hydrazine sulfate, hydrazine, dimethylamine borane, and sodium hypophosphite is used as the reducing substance.
本願第１発明の剥離剤を用いて水溶性レジストフイル
ムの剥離を行なう方法としては、水溶性レジストフイル
ムを施した基板に上記剥離剤を接触できる方法であれば
特に限定はなく、例えば水溶性レジストフイルムを施し
た基板を剥離剤中に浸漬する方法、水溶性レジストフイ
ルムを施した基板に剥離剤をスプレーする方法等を例示
できる。The method for stripping the water-soluble resist film using the stripping agent of the first invention of the present application is not particularly limited as long as the above-mentioned stripping agent can be brought into contact with the substrate provided with the water-soluble resist film. Examples of the method include immersing the substrate on which the film has been applied in a release agent, and spraying the release agent on the substrate on which the water-soluble resist film has been applied.
剥離剤中に基板を浸漬する方法では、例えば液温20〜
80℃程度の剥離剤を用いて、空気攪拌または機械攪拌を
行ないながら基板の浸漬を行なえばよい。In the method of immersing the substrate in the release agent, for example, the liquid temperature 20 ~
The substrate may be immersed using a release agent at about 80 ° C. while performing air stirring or mechanical stirring.
剥離剤を基板にスプレーする方法では、例えば、液温
20〜80℃程度の剥離剤を、0.5〜3kg/cm2程度の圧力で基
板に噴射すればよい。In the method of spraying the release agent on the substrate, for example,
A release agent at about 20 to 80 ° C. may be sprayed onto the substrate at a pressure of about 0.5 to 3 kg / cm 2 .
上記した剥離方法のうち、剥離剤の噴射による方法
は、処理時間が短かく、また基板にフイルム残渣が残り
難い点で有利である。Among the above-mentioned stripping methods, the method using a jet of a stripping agent is advantageous in that the processing time is short and the film residue hardly remains on the substrate.
本発明の剥離剤を用いる場合には、剥離剤中の各成分
を適宜補給して、初期濃度の70〜100％程度の範囲内に
維持することによつて剥離効果及びメツキ皮膜の腐食抑
制効果を長期間持続することができる。When the release agent of the present invention is used, the components in the release agent are appropriately replenished and the initial concentration is maintained within the range of about 70 to 100% of the initial concentration, whereby the release effect and the corrosion inhibition effect of the paint film are obtained. Can be maintained for a long time.
本願第２発明の剥離剤では、上記した本願第１発明の
剥離剤に、更に、インヒビターとして、ｐ−フェノール
スルホン酸ナトリウム、ｍ−キシレンスルホン酸ナトリ
ウム、1,4−ベンゼンジスルホン酸ナトリウム、４−ヒ
ドロキシナフタレンスルホン酸ナトリウム、2,6−ナフ
タレンジスルホン酸ナトリウム、１−アミノ−２−ナフ
タレンスルホン酸ナトリウム、硫化ナトリウム、チオ尿
素、ジメチルチオ尿素、チオエチレングリコール、チオ
セミカルバジド、メチルベンゾチアゾール、２−メルカ
プトベンゾチアゾール及び２−アミノチアゾールの少な
くとも一種からなる化合物を加える。この様なインヒビ
ターを加えた剥離剤では、水溶性レジストフィルムに対
する剥離性能がより向上するとともに、スズまたはハン
ダメッキ皮膜に対する腐食抑制効果がより一層大きくな
る。これらの化合物の添加量は、0.0001〜0.05モル／
程度が適当であり、好ましくは、0.0005〜0.02モル／
程度とする。In the release agent of the second invention of the present application, in addition to the release agent of the first invention of the present application, as inhibitors, sodium p-phenolsulfonate, sodium m-xylenesulfonate, sodium 1,4-benzenedisulfonate, 4- Sodium hydroxynaphthalene sulfonate, sodium 2,6-naphthalene disulfonic acid, sodium 1-amino-2-naphthalene sulfonate, sodium sulfide, thiourea, dimethylthiourea, thioethylene glycol, thiosemicarbazide, methylbenzothiazole, 2-mercaptobenzo A compound consisting of at least one of thiazole and 2-aminothiazole is added. The release agent to which such an inhibitor is added further improves the release performance for the water-soluble resist film and further enhances the effect of inhibiting corrosion of the tin or solder plating film. The addition amount of these compounds is 0.0001 to 0.05 mol /
The degree is appropriate, preferably 0.0005 to 0.02 mol /
Degree.
添加量が0.0001モル／を下回ると添加効果が不足
し、一方0.05モル／を上回ると剥離剤中での酸化・還
元反応で沈殿が生じ易くなるので好ましくない。If the amount is less than 0.0001 mol /, the effect of the addition is insufficient. On the other hand, if it exceeds 0.05 mol /, precipitation tends to occur due to oxidation / reduction reaction in the release agent, which is not preferable.
本願第２発明の剥離剤を用いて水溶性レジストフイル
ムの剥離を行なう方法は、本願第１発明の剥離剤による
剥離法と同様でよい。The method for stripping the water-soluble resist film using the stripping agent of the second invention of the present application may be the same as the stripping method using the stripping agent of the first invention of the present application.
発明の効果 本発明の剥離剤は、水溶性レジストフイルムに対する
剥離性能が良好であり、かつスズ、ハンダ等のメツキ皮
膜に対する腐食性が少ない。Effects of the Invention The stripping agent of the present invention has good stripping performance for a water-soluble resist film, and has low corrosiveness to tin or solder plating.
実 施 例 以下、実施例を示して本発明を更に詳細に説明する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ 銅張基板上に、水溶性ドライフイルム（商標名:ALPHO
1150T、日本合成化学（株）製）を用いて回路パター
ンを形成し、次いでスズメツキまたはハンダメツキを約
２μｍ厚に形成した。続いて、水酸化ナトリウム（95
％）を35g/含有し、更に下記第１表に示す還元製物質
を含有する水溶液からなる剥離剤を、温度50℃、スプレ
ー圧1.5kg/cm2の条件で下記基板に３分間スプレーし
て、レジストフイルムの剥離を行なつた。その結果、い
ずれの剥離剤を用いた場合にも基板上のレジストフイル
ムはほぼ完全に剥離された。処理前後のスズメツキまた
はハンダメツキ皮膜の断面を金属顕微鏡を用いて観察す
ることによつて、メツキ皮膜の腐食速度を求めた結果を
第１表に示す。Example 1 A water-soluble dry film (trade name: ALPHO) was placed on a copper-clad substrate.
A circuit pattern was formed using 1150T (manufactured by Nippon Synthetic Chemical Co., Ltd.), and then a tin plate or a solder plate was formed to a thickness of about 2 μm. Subsequently, sodium hydroxide (95
%) And a release agent consisting of an aqueous solution containing a substance to be reduced shown in Table 1 below at a temperature of 50 ° C. and a spray pressure of 1.5 kg / cm 2 for 3 minutes. Then, the resist film was peeled off. As a result, the resist film on the substrate was almost completely removed when any of the release agents was used. Table 1 shows the results obtained by observing the cross section of the tinplate or the soldercoat before and after the treatment using a metallographic microscope to determine the corrosion rate of the tinplate.
実施例２ 下記第２表に示す還元性物質を用いる以外は、実施例
１と同様にして、銅張基板上のレジストフイルムを剥離
したところ、いずれの剥離液を用いた場合にも、銅板基
板上のレジストフイルムはほぼ完全に剥離された。メツ
キ皮膜の腐食速度を実施例１と同様にして測定した結果
を第２表に示す。 Example 2 The resist film on the copper-clad substrate was peeled off in the same manner as in Example 1 except that the reducing substances shown in Table 2 below were used. The upper resist film was almost completely peeled off. Table 2 shows the results of measuring the corrosion rate of the plating film in the same manner as in Example 1.
実施例３ 水酸化ナトリウム（95％）35g/及び亜硫酸ナトリウ
ム0.02モル／を含有する水溶液に、更に下記第３表に
示すアリールスルホン酸ナトリウムを加えて、剥離剤を
得た。この剥離剤を用いる以外は、実施例１と同様にし
て銅張基板上のレジストフイルムを剥離したところ、レ
ジストフイルムはほぼ完全に剥離された。メツキ皮膜の
腐食速度を実施例１と同様にして測定した結果を第３表
に示す。 Example 3 To an aqueous solution containing 35 g / sodium hydroxide (95%) and 0.02 mol / sodium sulfite, sodium arylsulfonate shown in Table 3 below was further added to obtain a release agent. When the resist film on the copper-clad substrate was peeled off in the same manner as in Example 1 except that this release agent was used, the resist film was almost completely peeled off. Table 3 shows the results of measuring the corrosion rate of the plating film in the same manner as in Example 1.
実施例４ 水酸化ナトリウム（95％）35g/及び亜硫酸ナトリウ
ム0.02モル／を含有する水溶液に、更に下記第４表に
示すイオウ化合物を加えて、剥離剤を得た。この剥離剤
を用いる以外は、実施例１と同様にして銅張基板上のレ
ジストフイルムを剥離したところ、レジストフイルムは
ほぼ完全に剥離された。メツキ皮膜の腐食速度を実施例
１と同様にして測定した結果を第４表に示す。 Example 4 A sulfur compound shown in Table 4 was further added to an aqueous solution containing 35 g / sodium hydroxide (95%) and 0.02 mol / sodium sulfite to obtain a release agent. When the resist film on the copper-clad substrate was peeled off in the same manner as in Example 1 except that this release agent was used, the resist film was almost completely peeled off. Table 4 shows the results of measuring the corrosion rate of the paint film in the same manner as in Example 1.
実施例５ 水酸化ナトリウム（95％）35g/及び亜硫酸ナトリウ
ム0.02モル／を含有する水溶液に、更に下記第５表に
示すアリールスルホン酸ナトリウム及びイオウ化合物を
加えて、剥離剤を得た。この剥離剤を用いる以外は、実
施例１と同様にして銅張基板上のレジストフイルムを剥
離したところ、レジストフイルムはほぼ完全に剥離され
た。メツキ皮膜の腐食速度を実施例１と同様にして測定
した結果を第５表に示す。 Example 5 To an aqueous solution containing 35 g of sodium hydroxide (95%) and 0.02 mol / of sodium sulfite, sodium arylsulfonate and a sulfur compound shown in Table 5 below were further added to obtain a release agent. When the resist film on the copper-clad substrate was peeled off in the same manner as in Example 1 except that this release agent was used, the resist film was almost completely peeled off. Table 5 shows the results of measuring the corrosion rate of the plating film in the same manner as in Example 1.
実施例６ 水酸化ナトリウムに代えて、水酸化カリウム（85重量
％）50g/を用いる以外は、実施例１〜５と同様にし
て、銅張基板上のレジストフイルムを剥離したところ、
レジストフイルムは、ほぼ完全に剥離され、またスズメ
ツキ皮膜及びハンダメツキ皮膜の腐食速度は実施例１〜
５と同様であつた。 Example 6 A resist film on a copper-clad substrate was peeled off in the same manner as in Examples 1 to 5, except that 50 g / potassium hydroxide (85% by weight) was used instead of sodium hydroxide.
The resist film was almost completely peeled off, and the corrosion rates of the tin-plated film and the solder-plated film were measured in Examples 1 to 3.
Same as 5.
実施例７ 水溶性ドライフイルム（商標名:ALPHO 1150T、日本
合成化学（株）製）を用いて銅張基板の全面にレジスト
フイルムを形成した。次いで、水酸化ナトリウム35g/
水溶液に下記第６表に示す還元性物質を添加した剥離剤
を用いて、実施例１と同様にしてレジストフイルムの剥
離を行なつた。その後、銅張基板をよく水洗し、続い
て、0.5％硝酸銀溶液に２分間浸漬して、基板表面に銀
を析出させた。銀の析出した面積を下記第６表に示す。Example 7 A resist film was formed on the entire surface of a copper-clad substrate using a water-soluble dry film (trade name: ALPHO 1150T, manufactured by Nippon Synthetic Chemical Co., Ltd.). Then, sodium hydroxide 35g /
The resist film was stripped in the same manner as in Example 1 using a stripping agent obtained by adding a reducing substance shown in Table 6 below to the aqueous solution. Thereafter, the copper-clad substrate was thoroughly washed with water and subsequently immersed in a 0.5% silver nitrate solution for 2 minutes to precipitate silver on the substrate surface. The area where silver was deposited is shown in Table 6 below.
第６表から、還元性物質の添加によつて、レジストフ
イルムに対する剥離性能が向上することが判る。 Table 6 shows that the addition of a reducing substance improves the peeling performance of the resist film.
Claims (2)
の少なくとも一種20〜50g/、並びに ii）亜硫酸ナトリウム、チオ硫酸ナトリウム、ハイドロ
サルファイトナトリウム、ホルムアルデヒド、硫酸ヒド
ラジン、ヒドラジン、ジメチルアミンボラン及び次亜リ
ン酸ナトリウムの少なくとも一種からなる還元性物質0.
01〜0.3モル／ を含有する水溶液からなることを特徴とする水溶性レジ
ストフィルム用剥離剤。1. i) 20 to 50 g / at least one of sodium hydroxide and potassium hydroxide; and ii) sodium sulfite, sodium thiosulfate, sodium hydrosulfite, formaldehyde, hydrazine sulfate, hydrazine, dimethylamine borane and Reducing substance consisting of at least one of sodium phosphate 0.
A release agent for a water-soluble resist film, comprising an aqueous solution containing from 01 to 0.3 mol / mol.
の少なくとも一種20〜50g/、 ii）亜硫酸ナトリウム、チオ硫酸ナトリウム、ハイドロ
サルファイトナトリウム、ホルムアルデヒド、硫酸ヒド
ラジン、ヒドラジン、ジメチルアミンボラン及び次亜リ
ン酸ナトリウムの少なくとも一種からなる還元性物質0.
01〜0.3モル／、並びに iii）ｐ−フェノールスルホン酸ナトリウム、ｍ−キシ
レンスルホン酸ナトリウム、1,4−ベンゼンジスルホン
酸ナトリウム、４−ヒドロキシナフタレンスルホン酸ナ
トリウム、2,6−ナフタレンジスルホン酸ナトリウム、
１−アミノ−２−ナフタレンスルホン酸ナトリウム、硫
化ナトリウム、チオ尿素、ジメチルチオ尿素、チオエチ
レングリコール、チオセミカルバジド、メチルベンゾチ
アゾール、２−メルカプトベンゾチアゾール及び２−ア
ミノチアゾールの少なくとも一種からなる化合物0.0001
〜0.05モル／ を含有する水溶液からなることを特徴とする水溶性レジ
ストフィルム用剥離剤。2. i) 20 to 50 g / at least one of sodium hydroxide and potassium hydroxide; ii) sodium sulfite, sodium thiosulfate, sodium hydrosulfite, formaldehyde, hydrazine sulfate, hydrazine, dimethylamine borane and phosphorus hypophosphite Reducing substance consisting of at least one kind of sodium acid
01-0.3 mol /, and iii) sodium p-phenolsulfonate, sodium m-xylenesulfonate, sodium 1,4-benzenedisulfonate, sodium 4-hydroxynaphthalenesulfonate, sodium 2,6-naphthalenedisulfonic acid,
Compound comprising at least one of sodium 1-amino-2-naphthalenesulfonate, sodium sulfide, thiourea, dimethylthiourea, thioethylene glycol, thiosemicarbazide, methylbenzothiazole, 2-mercaptobenzothiazole and 2-aminothiazole 0.0001
A release agent for a water-soluble resist film, comprising an aqueous solution containing from 0.05 to 0.05 mol /.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62016377A JP2571375B2 (en) | 1987-01-27 | 1987-01-27 | Release agent for water-soluble resist film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62016377A JP2571375B2 (en) | 1987-01-27 | 1987-01-27 | Release agent for water-soluble resist film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63183445A JPS63183445A (en) | 1988-07-28 |
| JP2571375B2 true JP2571375B2 (en) | 1997-01-16 |
Family
ID=11914597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62016377A Expired - Lifetime JP2571375B2 (en) | 1987-01-27 | 1987-01-27 | Release agent for water-soluble resist film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2571375B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101238966B1 (en) * | 2008-12-02 | 2013-03-04 | 파나소닉 주식회사 | Method for manufacturing circuit board, and circuit board obtained using the manufacturing method |
| KR101286867B1 (en) * | 2008-04-30 | 2013-07-17 | 파나소닉 주식회사 | Method of producing circuit board by additive method, and circuit board and multilayer circuit board obtained by the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6000411A (en) * | 1990-11-05 | 1999-12-14 | Ekc Technology, Inc. | Cleaning compositions for removing etching residue and method of using |
| US5279771A (en) * | 1990-11-05 | 1994-01-18 | Ekc Technology, Inc. | Stripping compositions comprising hydroxylamine and alkanolamine |
| US6121217A (en) | 1990-11-05 | 2000-09-19 | Ekc Technology, Inc. | Alkanolamine semiconductor process residue removal composition and process |
| US6242400B1 (en) | 1990-11-05 | 2001-06-05 | Ekc Technology, Inc. | Method of stripping resists from substrates using hydroxylamine and alkanolamine |
| US6110881A (en) * | 1990-11-05 | 2000-08-29 | Ekc Technology, Inc. | Cleaning solutions including nucleophilic amine compound having reduction and oxidation potentials |
| EP0578507B1 (en) * | 1992-07-09 | 2005-09-28 | Ekc Technology, Inc. | Cleaning solutions including nucleophilic amine compound having reduction and oxidation potentials |
| US6326130B1 (en) * | 1993-10-07 | 2001-12-04 | Mallinckrodt Baker, Inc. | Photoresist strippers containing reducing agents to reduce metal corrosion |
| WO1996029849A1 (en) * | 1995-03-20 | 1996-09-26 | Hitachi, Ltd. | Method and device for manufacturing printed wiring board |
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| WO2010064602A1 (en) * | 2008-12-02 | 2010-06-10 | パナソニック電工株式会社 | Method for manufacturing circuit board, and circuit board obtained using the manufacturing method |
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| US8698003B2 (en) | 2008-12-02 | 2014-04-15 | Panasonic Corporation | Method of producing circuit board, and circuit board obtained using the manufacturing method |
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| WO2011052207A1 (en) * | 2009-10-30 | 2011-05-05 | パナソニック電工株式会社 | Circuit board and manufacturing method thereof |
| EP2496061A4 (en) | 2009-10-30 | 2014-01-08 | Panasonic Corp | PRINTED CIRCUIT BOARD AND SEMICONDUCTOR DEVICE COMPRISING A COMPONENT MOUNTED ON A PRINTED CIRCUIT BOARD |
| US9332642B2 (en) | 2009-10-30 | 2016-05-03 | Panasonic Corporation | Circuit board |
| JP5465512B2 (en) * | 2009-10-30 | 2014-04-09 | パナソニック株式会社 | Circuit board manufacturing method |
| CN105573071A (en) * | 2015-05-26 | 2016-05-11 | 叶旖婷 | Efficient and environment-friendly film-stripping solution capable of keeping copper surface bright and concentrated solution of film-stripping solution |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS499301A (en) * | 1972-05-29 | 1974-01-26 | ||
| JPS5435122B2 (en) * | 1973-03-01 | 1979-10-31 | ||
| JPS5267629A (en) * | 1975-12-03 | 1977-06-04 | Hitachi Ltd | Method for removing posi-type photoresist |
-
1987
- 1987-01-27 JP JP62016377A patent/JP2571375B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101286867B1 (en) * | 2008-04-30 | 2013-07-17 | 파나소닉 주식회사 | Method of producing circuit board by additive method, and circuit board and multilayer circuit board obtained by the method |
| KR101238966B1 (en) * | 2008-12-02 | 2013-03-04 | 파나소닉 주식회사 | Method for manufacturing circuit board, and circuit board obtained using the manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63183445A (en) | 1988-07-28 |
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