JP5923033B2 - Chromium hard coating stripping solution - Google Patents
Chromium hard coating stripping solution Download PDFInfo
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- JP5923033B2 JP5923033B2 JP2012280575A JP2012280575A JP5923033B2 JP 5923033 B2 JP5923033 B2 JP 5923033B2 JP 2012280575 A JP2012280575 A JP 2012280575A JP 2012280575 A JP2012280575 A JP 2012280575A JP 5923033 B2 JP5923033 B2 JP 5923033B2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 76
- 239000011651 chromium Substances 0.000 title claims description 75
- 238000000576 coating method Methods 0.000 title claims description 75
- 229910052804 chromium Inorganic materials 0.000 title claims description 74
- 239000011248 coating agent Substances 0.000 title claims description 69
- 239000000243 solution Substances 0.000 claims description 78
- 150000003839 salts Chemical class 0.000 claims description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 20
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 19
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 19
- 235000011007 phosphoric acid Nutrition 0.000 description 18
- 239000010410 layer Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 229910000997 High-speed steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- -1 potassium ferricyanide Chemical compound 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 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 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VEJCUEBBRSCJRP-UHFFFAOYSA-L calcium;hydron;phosphonato phosphate Chemical compound [Ca+2].OP(O)(=O)OP([O-])([O-])=O VEJCUEBBRSCJRP-UHFFFAOYSA-L 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- WRMXOVHLRUVREB-UHFFFAOYSA-N phosphono phosphate;tributylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WRMXOVHLRUVREB-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229940099402 potassium metaphosphate Drugs 0.000 description 1
- 229940098424 potassium pyrophosphate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 1
- 229940046307 sodium thioglycolate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
Description
本発明は、クロム系硬質皮膜用剥離液に関するものである。 The present invention relates to a chromium-based hard coating stripping solution.
従来より、超硬合金やサーメット、高速度鋼等を母材として用いてなる各種工具においては、耐摩耗性等の付与を目的として、その表面に対して、金属の（複合）窒化物等からなる硬質皮膜のコーティングが施されている。そのような硬質皮膜としては、これまでは、窒化チタンや窒化チタンアルミニウム等のチタン系硬質皮膜が主流であったが、最近では、耐摩耗性や耐酸化性等においてより優れたクロム系硬質皮膜の採用が進んできている（特許文献１を参照）。 Conventionally, in various tools made of cemented carbide, cermet, high speed steel, etc. as a base material, for the purpose of imparting wear resistance, etc., the surface is made of metal (composite) nitride, etc. The coating of the hard film becomes. Until now, titanium-based hard coatings such as titanium nitride and titanium nitride aluminum have been the mainstream as such hard coatings. Recently, however, chromium-based hard coatings are superior in terms of wear resistance and oxidation resistance. (See Patent Document 1).
ここで、上述の如き硬質皮膜のコーティングが施された工具であっても、度重なる使用によって表面の硬質皮膜は摩耗するため、長期間使用された工具に対しては、再度、硬質皮膜のコーティングが実施される場合がある。かかる再コーティングは、工具の表面に残存する硬質皮膜を除去（剥離）した後に実施されるため、近年では、硬質皮膜の種類に応じた除去剤（剥離液）の検討や開発等が盛んに行なわれている。 Here, even if the tool is coated with a hard coating as described above, the hard coating on the surface is worn by repeated use. May be implemented. Since such re-coating is performed after removing (peeling) the hard film remaining on the surface of the tool, in recent years, investigation and development of a remover (peeling solution) according to the type of hard film has been actively conducted. It is.
例えば、クロム系硬質皮膜は、ある一定水準を超える酸化力が付与されたアルカリ性溶液（剥離液）中に、かかる硬質皮膜がコーティングされた工具を浸漬せしめることにより、剥離可能であることが知られている（特許文献２及び特許文献３を参照）。また、特に、強力な酸化剤である過マンガン酸カリウムやフェリシアン化カリウム（例えば、株式会社ＡＤＥＫＡ製のチタピールＣＲ（商品名））を主たる成分とする溶液にあっては、かかる溶液を剥離液として用いると、工具表面にコーティングされたクロム系硬質皮膜の除去速度が非常に速いという利点がある。 For example, it is known that a chromium-based hard coating can be peeled off by immersing a tool coated with the hard coating in an alkaline solution (peeling solution) to which an oxidizing power exceeding a certain level is applied. (See Patent Document 2 and Patent Document 3). In particular, in a solution containing, as a main component, potassium permanganate or potassium ferricyanide (for example, Titapeel CR (trade name) manufactured by ADEKA Co., Ltd.), which is a strong oxidizing agent, such a solution is used as a stripping solution. And there is an advantage that the removal rate of the chromium-based hard coating coated on the tool surface is very fast.
しかしながら、上記の過マンガン酸カリウム等の強力な酸化剤を主たる成分とする溶液は、非常に強力な酸化作用を発揮するものであるため、その溶液（剥離液）中に、表面にクロム系硬質皮膜が残存する工具を浸漬せしめるに際しては、工具（母材）へのダメージを考慮して、クロム系硬質皮膜の除去が完了次第、直ちに工具を剥離液から引き揚げる必要がある。このように、強力な酸化剤を主たる成分とする溶液を剥離液として用いる場合には、剥離液中への工具の浸漬時間を非常に厳密に監理する必要がある。また、強力な酸化剤を主たる成分とする溶液を剥離液として用いると、クロム系硬質皮膜の除去後の工具表面に異物が付着する恐れがあることが知られており、そのような異物を洗浄、除去する装置や方法が必要になるという問題もある（特許文献２を参照）。 However, since the above-mentioned solution containing a strong oxidizing agent such as potassium permanganate as a main component exhibits a very strong oxidizing action, the surface of the solution (stripping solution) contains chromium-based hard When immersing the tool in which the film remains, it is necessary to lift the tool from the stripping solution as soon as the removal of the chromium hard film is completed in consideration of damage to the tool (base material). As described above, when a solution containing a strong oxidizer as a main component is used as the stripping solution, it is necessary to monitor the immersion time of the tool in the stripping solution very strictly. In addition, it is known that if a solution containing a strong oxidizer as the main component is used as the stripping solution, foreign matter may adhere to the tool surface after the removal of the chromium-based hard coating. There is also a problem that an apparatus and a method for removal are required (see Patent Document 2).
ところで、各種工具への硬質皮膜の再コーティングに際して、表面に残存する硬質皮膜の除去工程に要する時間は、硬質皮膜の種類や厚さ等によって異なるのであり、また、工具の所有者（工具の使用者、管理者等。以下、それらを総合的に「ユーザー」という。）における事情（工具のストック数等）によっても、除去工程に供する時間は異なる。具体的には、これまではチタン系硬質皮膜をコーティングした工具を用いており、その再コーティングを、専用の剥離液を用いて比較的長い時間（例えば６〜２４時間）をかけて実施していたユーザーにおいては、チタン系硬質皮膜からクロム系硬質皮膜へと切り替えた場合、必ずしも硬質皮膜の除去時間の短縮が歓迎されるとは限らないのである。そのような場合に、クロム系硬質皮膜の除去を、チタン系硬質皮膜を除去する際と同様の時間をかけて、前述の如き強力な酸化剤を含む剥離液を用いて実施すると、工具（母材）が腐蝕したり、工具表面に異物が付着する等の問題が生ずる恐れがある。 By the way, when re-coating the hard coating on various tools, the time required for the process of removing the hard coating remaining on the surface varies depending on the type and thickness of the hard coating, and the tool owner (use of the tool) The time for the removal process varies depending on the circumstances (the number of tool stocks, etc.) in the following. Specifically, a tool coated with a titanium-based hard coating has been used so far, and the re-coating has been performed over a relatively long time (for example, 6 to 24 hours) using a special stripping solution. However, when switching from a titanium-based hard coating to a chromium-based hard coating, shortening of the removal time of the hard coating is not always welcomed. In such a case, when the removal of the chromium-based hard coating is performed using the stripping solution containing the strong oxidizing agent as described above over the same time as the removal of the titanium-based hard coating, There is a risk of problems such as corrosion of the material) and foreign matter adhering to the tool surface.
その一方で、クロム系硬質皮膜を除去可能な酸化能を有する酸化剤として、ペルオキソ二硫酸又はその塩類のアルカリ性水溶液が知られている。かかるペルオキソ二硫酸又はその塩類を酸化剤として使用した場合、前述の過マンガン酸カリウム等の非常に強力な酸化剤と比較すると、酸化反応が緩やかであるため、ペルオキソ二硫酸又はその塩類のアルカリ性水溶液を剥離液として用いた場合、かかる剥離液中に工具を長時間、浸漬せしめても、工具（母材）の腐蝕が発生し難いという利点がある。また、クロム系硬質皮膜の除去に伴ってペルオキソ二硫酸又はその塩類が消耗し、その際に生成する物質が、剥離液に易溶性の硫酸塩であるところから、工具表面への異物の付着を抑制することも出来る。 On the other hand, an alkaline aqueous solution of peroxodisulfuric acid or a salt thereof is known as an oxidizing agent having an oxidizing ability capable of removing the chromium-based hard film. When such peroxodisulfuric acid or a salt thereof is used as an oxidizing agent, since the oxidation reaction is slow compared with the above-mentioned very strong oxidizing agent such as potassium permanganate, an alkaline aqueous solution of peroxodisulfuric acid or a salt thereof is used. Is used as a stripping solution, there is an advantage that even if the tool is immersed in the stripping solution for a long time, corrosion of the tool (base material) hardly occurs. In addition, peroxodisulfuric acid or its salts are consumed along with the removal of the chromium-based hard coating, and the substances generated at that time are sulfates that are readily soluble in the stripping solution. It can also be suppressed.
しかしながら、ペルオキソ二硫酸又はその塩類のみを含むアルカリ性水溶液にあっては、過マンガン酸カリウム等の強力な酸化剤を主たる成分とする溶液と比較すると、クロム系硬質皮膜に対する剥離性能が劣るものであるため、クロム系硬質皮膜の除去（剥離）に長時間を要したり、長時間の浸漬によっても剥離が完了しない恐れがあり、実用化には問題がある。 However, in an alkaline aqueous solution containing only peroxodisulfuric acid or a salt thereof, the peeling performance for a chromium-based hard film is inferior compared with a solution containing a strong oxidizing agent such as potassium permanganate as a main component. For this reason, it may take a long time to remove (peel) the chromium-based hard film, or the peeling may not be completed even by long-time immersion, which is problematic for practical use.
また、特許文献４にて提案の、硬質皮膜の除去速度向上に効果があるとされるヒドロキシ・カルボネート系有機酸アルカリ塩（例えば、グルコン酸ナトリウム）、エチレン・ジアミン・酢酸アルカリ塩（例えば、エチレンジアミン四酢酸ナトリウム）や、チオグリコール酸アルカリ塩（例えば、チオグリコール酸ナトリウム）等は、ペルオキソ二硫酸又はその塩類のアルカリ性水溶液中では速やかに酸化され、分解してしまうことから、ペルオキソ二硫酸又はその塩類のアルカリ性水溶液に添加し、クロム系硬質皮膜に対する剥離性の向上を図ることは出来ないのである。 Further, a hydroxy carbonate organic acid alkali salt (for example, sodium gluconate), ethylene / diamine / acetic acid alkali salt (for example, ethylenediamine) proposed in Patent Document 4 and effective for improving the removal rate of the hard film. Sodium tetraacetate) and alkali thioglycolic acid salts (for example, sodium thioglycolate) are rapidly oxidized and decomposed in an alkaline aqueous solution of peroxodisulfuric acid or a salt thereof. It cannot be added to an alkaline aqueous solution of salts to improve the peelability of the chromium hard film.
ここにおいて、本発明は、かかる事情を背景にして為されたものであって、その解決すべき課題とするところは、長時間浸漬せしめても工具（母材）の腐蝕が効果的に抑制され、また、クロム系硬質皮膜の除去速度を比較的容易に調整することが出来、更には、被膜除去後の工具表面への異物の付着が発生し難い、クロム系硬質皮膜用剥離液を提供することにある。 Here, the present invention has been made in the background of such circumstances, and the problem to be solved is that the corrosion of the tool (base material) is effectively suppressed even when immersed for a long time. Also, it is possible to adjust the removal rate of the chrome-based hard coating relatively easily, and further provide a peeling solution for the chrome-based hard coating that hardly causes foreign matter to adhere to the tool surface after the removal of the coating. There is.
そして、本発明は、そのような課題を解決すべく、縮合リン酸及び／又はその塩を０．１〜２０重量％、ペルオキソ二硫酸及び／又はその塩を０．１〜１５重量％の割合において含み、ｐＨが１３．５以上に調製されたアルカリ性水溶液からなるクロム系硬質皮膜用剥離液を、その要旨とするものである。 In order to solve such a problem, the present invention provides 0.1 to 20% by weight of condensed phosphoric acid and / or a salt thereof, and 0.1 to 15% by weight of peroxodisulfuric acid and / or a salt thereof. And a chrome-based hard coating stripping solution made of an alkaline aqueous solution having a pH of 13.5 or more.
なお、本発明に従うクロム系硬質皮膜用剥離液にあっては、好ましくは、前記縮合リン酸が、ピロリン酸、トリポリリン酸、テトラポリリン酸、ペンタポリリン酸、メタリン酸及びヘキサメタリン酸からなる群より選択される一種又は二種以上である。 In the chromium-based hard film remover according to the present invention, preferably, the condensed phosphoric acid is selected from the group consisting of pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, metaphosphoric acid and hexametaphosphoric acid. 1 type or 2 types or more.
また、本発明に従うクロム系硬質皮膜用剥離液にあっては、望ましくは、前記ペルオキソ二硫酸の塩が、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸カリウム及びペルオキソ二硫酸アンモニウムからなる群より選択される一種又は二種以上である。 Moreover, in the chromium-based hard film stripping solution according to the present invention, desirably, the salt of peroxodisulfuric acid is selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate, or Two or more types.
このように、本発明に従うクロム系硬質皮膜用剥離液にあっては、縮合リン酸及び／又はその塩と、ペルオキソ二硫酸及び／又はその塩を、各々、所定の割合において含み、且つ、ｐＨが１３．５以上に調製されたアルカリ性水溶液にて構成されるものであるところから、クロム系硬質皮膜がコーティングされた工具を、かかる硬質皮膜を除去（剥離）すべく、本発明の剥離液中に長時間浸漬せしめても、工具（母材）の腐蝕が効果的に抑制されることとなるのである。また、本発明に係るクロム系硬質皮膜用剥離液は、クロム系硬質皮膜の除去速度を比較的容易に調整することが可能なものとなっており、更には、被膜除去（剥離）後の工具表面への異物の付着が発生し難い剥離液ともなっているのである。 As described above, the chromium hard film stripping solution according to the present invention contains condensed phosphoric acid and / or a salt thereof, and peroxodisulfuric acid and / or a salt thereof in a predetermined ratio, and has a pH value. In the stripping solution of the present invention, a tool coated with a chromium-based hard coating is removed (peeled) from a tool coated with a chrome-based hard coating. Even if immersed in a long time, corrosion of the tool (base material) is effectively suppressed. Further, the chromium hard coating stripping solution according to the present invention can adjust the removal rate of the chromium hard coating relatively easily, and further, the tool after coating removal (stripping). It is also a stripping solution in which foreign matter does not easily adhere to the surface.
本発明に従うクロム系硬質皮膜用剥離液は、縮合リン酸及び／又はその塩と、ペルオキソ二硫酸及び／又はその塩を、必須の構成成分として含有するものである。なお、本明細書及び特許請求の範囲において、クロム系硬質皮膜とは、耐摩耗性の向上等を目的として各種工具の表面に設けられる皮膜であって、単層若しくは二以上の層から構成され、かかる層の少なくとも一以上がクロムを含むものを意味する。 The stripping solution for a chromium-based hard coating according to the present invention contains condensed phosphoric acid and / or a salt thereof and peroxodisulfuric acid and / or a salt thereof as essential components. In the present specification and claims, the chromium-based hard coating is a coating provided on the surface of various tools for the purpose of improving wear resistance and the like, and is composed of a single layer or two or more layers. , Meaning that at least one of the layers contains chromium.
先ず、縮合リン酸やその塩は、金属イオン封鎖能（溶解金属の分散能）や、金属表面の洗浄作用等の界面活性作用に優れた物質であり、また、ペルオキソ二硫酸又はその塩が存在するアルカリ性水溶液中においても、長期間に亘って安定的に存在することが可能である。このような特性を有する縮合リン酸やその塩を、ペルオキソ二硫酸やその塩と共に配合してクロム系硬質皮膜用剥離液を構成することにより、縮合リン酸やその塩が、ペルオキソ二硫酸又はその塩を含む、ｐＨが１３．５以上に調製されたアルカリ性水溶液に対して、クロム系硬質皮膜への浸透性を効果的に付与し、その結果、ペルオキソ二硫酸やその塩が皮膜の内部にまで充分に浸透することとなり、工具との界面に存在するクロム成分に直接作用して酸化クロムを生成し、その生成した酸化クロムがアルカリ反応によって溶出せしめられ、以て、皮膜を浮き上がらせるようにして剥離（除去）せしめることとなるのである。 First, condensed phosphoric acid and its salts are substances with excellent surface activity such as sequestering ability (dissolving ability of dissolved metal) and metal surface cleaning, and peroxodisulfuric acid or its salt exists. Even in an alkaline aqueous solution, it can exist stably over a long period of time. Condensed phosphoric acid or a salt thereof having such characteristics is blended with peroxodisulfuric acid or a salt thereof to constitute a chromium-based hard coating stripping solution. Effectively imparts permeability to chromium-based hard coatings to alkaline aqueous solutions containing salt and having a pH adjusted to 13.5 or higher. As a result, peroxodisulfuric acid and salts thereof can reach the inside of the coating. It penetrates sufficiently, and it acts directly on the chromium component existing at the interface with the tool to produce chromium oxide, and the produced chromium oxide is eluted by an alkaline reaction, so that the film floats up. It will be peeled off (removed).
本発明のクロム系硬質皮膜用剥離液における縮合リン酸やその塩としては、従来より公知のものであれば、何れのものであっても使用することが可能である。具体的には、縮合リン酸としては、ピロリン酸、トリポリリン酸、テトラポリリン酸、ペンタポリリン酸、メタリン酸やヘキサメタリン酸等を例示することが出来る。また、縮合リン酸の塩としては、前述の縮合リン酸の塩、具体的には、ピロリン酸二水素ナトリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、ピロリン酸二水素カルシウム、ピロリン酸第二鉄、ピロリン酸銅、ピロリン酸亜鉛、トリポリリン酸ナトリウム、テトラポリリン酸ナトリウム、ペンタポリリン酸ナトリウム、メタリン酸ナトリウム、メタリン酸水素ナトリウム、メタリン酸カリウム、ヘキサメタリン酸ナトリウム、ヘキサメタリン酸カリウム等を、例示することが出来る。本発明に従うクロム系硬質皮膜用剥離液においては、これら縮合リン酸及びその塩の中から一種又は二種以上のものが適宜に選択されて、使用される。 As the condensed phosphoric acid and the salt thereof in the chromium-based hard coating stripping solution of the present invention, any known phosphoric acid or salt thereof can be used. Specifically, examples of condensed phosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid. The condensed phosphoric acid salt includes the above-mentioned condensed phosphoric acid salts, specifically, sodium dihydrogen pyrophosphate, sodium pyrophosphate, potassium pyrophosphate, calcium dihydrogen pyrophosphate, ferric pyrophosphate, pyrroline. Examples include copper oxide, zinc pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium pentapolyphosphate, sodium metaphosphate, sodium hydrogenphosphate, potassium metaphosphate, sodium hexametaphosphate, potassium hexametaphosphate, and the like. In the peeling solution for chromium-based hard coating according to the present invention, one or two or more of these condensed phosphoric acids and salts thereof are appropriately selected and used.
本発明に従うクロム系硬質皮膜用剥離液においては、上述した縮合リン酸及び／又はその塩は、０．１〜２０重量％の割合において、好ましくは０．５〜２．５重量％の割合において、含有せしめられる。縮合リン酸及び／又はその塩の含有量が少なすぎると、上述した効果が十分に発揮されない恐れがあり、その一方、縮合リン酸及び／又はその塩の含有量が多すぎると、後述するペルオキソ二硫酸及び／又はその塩とクロム系硬質皮膜との反応を阻害し、結果としてクロム系硬質皮膜の除去（剥離）速度が低下する恐れがあるからである。 In the peeling solution for chromium-based hard coating according to the present invention, the above-described condensed phosphoric acid and / or salt thereof is in a proportion of 0.1 to 20% by weight, preferably in a proportion of 0.5 to 2.5% by weight. , To be included. If the content of the condensed phosphoric acid and / or salt thereof is too small, the above-described effects may not be sufficiently exhibited. On the other hand, if the content of the condensed phosphoric acid and / or salt thereof is too large, the peroxo described later This is because the reaction between disulfuric acid and / or a salt thereof and the chromium-based hard coating may be inhibited, and as a result, the removal (peeling) rate of the chromium-based hard coating may be reduced.
一方、ペルオキソ二硫酸及び／又はその塩は、本発明に従うクロム系硬質皮膜用剥離液においては、クロム系硬質皮膜を分解する酸化剤として機能する。前述したように、ペルオキソ二硫酸及び／又はその塩は、クロム系硬質皮膜を除去可能な酸化能を有する酸化剤として知られているが、ペルオキソ二硫酸及び／又はその塩のみを含むアルカリ性水溶液は、クロム系硬質皮膜に対する除去（剥離）性能が劣るという問題があった。そこで、縮合リン酸及び／又はその塩を併用し、且つ、溶液のｐＨを１３．５以上に調製することにより、本発明に従うクロム系硬質皮膜用剥離液は、１）長時間浸漬せしめても、工具（母材）の腐蝕が効果的に抑制され、２）クロム系硬質皮膜の除去速度を比較的容易に調整することが可能ならしめられ、３）被膜除去（剥離）後の工具表面への異物の付着が発生し難い、という効果を享受することが可能ならしめられたのである。 On the other hand, peroxodisulfuric acid and / or a salt thereof functions as an oxidizing agent that decomposes the chromium hard film in the chromium hard film peeling solution according to the present invention. As described above, peroxodisulfuric acid and / or a salt thereof is known as an oxidizing agent having an oxidizing ability capable of removing a chromium-based hard film, but an alkaline aqueous solution containing only peroxodisulfuric acid and / or a salt thereof is used. There was a problem that the removal (peeling) performance with respect to the chromium-based hard film was inferior. Therefore, by using condensed phosphoric acid and / or a salt thereof in combination and adjusting the pH of the solution to 13.5 or higher, the chromium hard coating stripping solution according to the present invention can be soaked for 1) for a long time. Corrosion of the tool (base material) is effectively suppressed, 2) It is possible to adjust the removal rate of the chromium-based hard film relatively easily, and 3) To the tool surface after film removal (peeling) It has become possible to enjoy the effect that the adhesion of foreign matter is difficult to occur.
本発明のクロム系硬質皮膜用剥離液におけるペルオキソ二硫酸やその塩としては、従来より公知のものであれば、何れのものであっても使用することが可能である。ペルオキソ二硫酸の塩としては、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸カリウム及びペルオキソ二硫酸アンモニウム等を例示することが出来る。それらペルオキソ二硫酸の塩及びペルオキソ二硫酸の中から、一種又は二種以上のものが適宜に選択されて、使用される。 Any peroxodisulfuric acid or salt thereof in the peeling solution for chromium-based hard coating of the present invention can be used as long as it is conventionally known. Examples of peroxodisulfuric acid salts include sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate. One or more of these peroxodisulfuric acid salts and peroxodisulfuric acid are appropriately selected and used.
また、本発明に従うクロム系硬質皮膜用剥離液においては、上述したペルオキソ二硫酸及び／又はその塩は、０．１〜１５重量％の割合において含有せしめられる。含有量が少なすぎると、酸化剤としての効果が充分に発揮されない恐れがあり、一方で、含有量が多すぎると、剥離液中にペルオキソ二硫酸及び／又はその塩が完全に溶けきらない恐れや、皮膜除去（剥離）中に工具（母材）表面に析出する恐れがあるからである。 Moreover, in the peeling solution for chromium-based hard coatings according to the present invention, the above-mentioned peroxodisulfuric acid and / or salt thereof is contained in a proportion of 0.1 to 15% by weight. If the content is too small, the effect as an oxidizing agent may not be sufficiently exhibited. On the other hand, if the content is too large, peroxodisulfuric acid and / or its salt may not be completely dissolved in the stripping solution. This is because there is a risk of precipitation on the surface of the tool (base material) during film removal (peeling).
そして、本発明においては、上述の如き、縮合リン酸及び／又はその塩とペルオキソ二硫酸及び／又はその塩とが、各々、所定割合において含有せしめられると共に、更に、溶液全体のｐＨが１３．５以上に調製されて、クロム系硬質皮膜用剥離液とされるのである。このように溶液（剥離液）のｐＨを１３．５以上に調製することによって、ペルオキソ二硫酸及び／又はその塩によるクロム系硬質皮膜の除去（剥離）が効果的に進行可能なものとなっているのである。 In the present invention, as described above, condensed phosphoric acid and / or a salt thereof and peroxodisulfuric acid and / or a salt thereof are contained in a predetermined ratio, respectively, and the pH of the whole solution is 13. It is adjusted to 5 or more, and is used as a chrome-based hard coating stripping solution. Thus, by adjusting the pH of the solution (peeling solution) to 13.5 or more, the removal (peeling) of the chromium-based hard film with peroxodisulfuric acid and / or a salt thereof can effectively proceed. It is.
なお、本発明において、溶液（剥離液）のｐＨを調製する手法としては、公知の各種手法の何れをも採用することが可能であるが、有利には、水酸化カリウムや水酸化ナトリウム等の強アルカリを所定量、溶液（剥離液）に添加することによって、溶液（剥離液）のｐＨを調製することが可能である。 In the present invention, as a method for adjusting the pH of the solution (stripping solution), any of various known methods can be adopted. However, advantageously, potassium hydroxide, sodium hydroxide or the like can be used. It is possible to adjust the pH of the solution (stripping solution) by adding a predetermined amount of strong alkali to the solution (stripping solution).
本発明に従うクロム系硬質皮膜用剥離液はアルカリ性水溶液からなるものであることから、その調製（製造）の際には、従来より一般的なアルカリ性水溶液を調製する場合と同様の手法が採用される。具体的には、所定量の水に、縮合リン酸及び／又はその塩と、ペルオキソ二硫酸及び／又はその塩とを、除去（剥離）するクロム系硬質皮膜の組成や厚さ等に応じて決定された各々の添加量に従って添加し、更に、溶液（剥離液）全体のｐＨが１３．５以上となるような適量の水酸化カリウムや水酸化ナトリウム等の強アルカリを添加し、全体を撹拌、混合することにより、調製（製造）することが可能である。 Since the stripping solution for a chromium-based hard coating according to the present invention is composed of an alkaline aqueous solution, the same method as that used for preparing a conventional alkaline aqueous solution is employed in the preparation (production). . Specifically, in a predetermined amount of water, depending on the composition and thickness of the chromium-based hard film that removes (peels) the condensed phosphoric acid and / or salt thereof and peroxodisulfuric acid and / or salt thereof. Add according to each determined addition amount, and then add an appropriate amount of strong alkali such as potassium hydroxide or sodium hydroxide so that the pH of the whole solution (stripping solution) is 13.5 or more, and stir the whole It is possible to prepare (manufacture) by mixing.
そして、本発明に従うクロム系硬質皮膜用剥離液にあっては、除去（剥離）対象であるクロム系硬質皮膜の組成や厚さ、更には層の重なり方等に応じて、縮合リン酸及び／又はその塩の添加量等を適宜に調整することにより、クロム系硬質皮膜の除去（剥離）速度を、所望とする実用的なものに制御することが可能ならしめられるのであり、これにより、過度の工具（母材）腐蝕や工具（母材）表面への異物の付着を効果的に抑制することが出来るのである。 And, in the peeling solution for chromium-based hard coating according to the present invention, depending on the composition and thickness of the chromium-based hard coating to be removed (peeled), and how the layers overlap, etc., condensed phosphoric acid and / or Alternatively, it is possible to control the removal (peeling) rate of the chromium-based hard coating to a desired practical one by appropriately adjusting the addition amount of the salt, etc. Thus, corrosion of the tool (base material) and adhesion of foreign matter to the surface of the tool (base material) can be effectively suppressed.
なお、本発明のクロム系硬質皮膜用剥離液を用いて、クロム系硬質皮膜の除去（剥離）を行なう際の処理温度は、高温ほどクロム系硬質皮膜の除去（剥離）速度は向上するものの、６５℃を超えると、縮合リン酸塩の分解により除去（剥離）速度が低下する恐れがあるため、６５℃以下であることが好ましい。その一方、処理温度が低すぎると、クロム系硬質皮膜の除去（剥離）速度が遅く、皮膜の除去（剥離）が充分に進行しない恐れがあるため、２５℃以上であることが好ましい。 In addition, although the processing temperature at the time of removing (peeling) the chromium-based hard coating using the release liquid for chromium-based hard coating of the present invention is higher, the removal (peeling) rate of the chromium-based hard coating is improved, If it exceeds 65 ° C., the removal (peeling) speed may decrease due to decomposition of the condensed phosphate, and therefore it is preferably 65 ° C. or less. On the other hand, if the treatment temperature is too low, the removal (peeling) rate of the chromium-based hard coating is slow, and the removal (peeling) of the coating may not proceed sufficiently.
以下に、本発明の実施例を幾つか示し、本発明を更に具体的に明らかにすることとするが、本発明が、そのような実施例の記載によって、何等の制約をも受けるものでないことは、言うまでもないところである。また、本発明には、以下の実施例の他にも、更には上記した具体的記述以外にも、本発明の趣旨を逸脱しない限りにおいて、当業者の知識に基づいて、種々なる変更、修正、改良等が加え得るものであることが、理解されるべきである。 Some examples of the present invention will be shown below to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. Needless to say. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements and the like can be added.
先ず、母材としての高速度鋼ＳＫＤの片面に、下記表１〜表６の各々に明示されたクロム系硬質皮膜がコーティングされてなる、大きさが１２．７ｍｍ×１２．７ｍｍ、厚さが約５ｍｍの試料を準備した。なお、母材（高速度鋼ＳＫＤ）にコーティングされたクロム系硬質皮膜は、何れも２層構造であり、皮膜全体の厚さ（２層合計の厚さ）は８μｍであった。下記表１〜表６において、下層とは、クロム系硬質皮膜を構成する２層のうち、母材の表面と接する層を意味し、上層とは、下層の上側の面（母材の表面と接する面とは反対側の面）に設けられた層を、それぞれ示すものである。また、下記表中の「ＴｉＣｒＡｌＳｉＹＮ」はＴｉ、Ｃｒ、Ａｌ、Ｓｉ及びＹの複合窒化物より構成される層であることを、また「ＡｌＣｒＮ」はＡｌ及びＣｒの複合窒化物より構成される層であることを、更に「ＴｉＣｒＡｌＮ」はＴｉ、Ｃｒ及びＡｌの複合窒化物より構成される層であることを、更にまた「ＣｒＮ」はＣｒ窒化物より構成される層であることを、各々、示すものである。 First, on one side of the high-speed steel SKD as the base material, a chromium hard film specified in each of the following Tables 1 to 6 is coated, the size is 12.7 mm × 12.7 mm, the thickness is A sample of about 5 mm was prepared. The chromium-based hard coating coated on the base material (high speed steel SKD) has a two-layer structure, and the total thickness of the coating (total thickness of the two layers) was 8 μm. In Tables 1 to 6, the lower layer means a layer in contact with the surface of the base material among the two layers constituting the chromium-based hard coating, and the upper layer means the upper surface of the lower layer (the surface of the base material). The layers provided on the surface opposite to the contact surface) are respectively shown. In the table below, “TiCrAlSiYN” is a layer composed of a composite nitride of Ti, Cr, Al, Si and Y, and “AlCrN” is a layer composed of a composite nitride of Al and Cr. Further, “TiCrAlN” is a layer composed of a composite nitride of Ti, Cr and Al, and “CrN” is a layer composed of Cr nitride, respectively. It is shown.
準備された試料を、下記表１〜表６に示す条件にて調製されたクロム系硬質皮膜用剥離液：４５ｍＬに、下記表に示す各条件に従って浸漬せしめることにより、クロム系硬質皮膜の除去（剥離）試験を行なった。なお、以下の実施例及び比較例において使用された剥離液は、何れも、ペルオキソ二硫酸ナトリウムを７．５重量％の割合において含有するものであり、また、ｐＨは１４に調製されたものである。 Removal of the chromium-based hard film by immersing the prepared sample in 45 mL of a release solution for chromium-based hard film prepared under the conditions shown in Tables 1 to 6 according to the conditions shown in the following table ( A peel test was performed. The stripping solutions used in the following examples and comparative examples each contain sodium peroxodisulfate in a proportion of 7.5% by weight, and the pH was adjusted to 14. is there.
また、処理後の各剥離液中の金属含有量をＩＣＰ−ＡＥＳ分析で測定すると共に、剥離液に浸漬後の試料表面に残存するクロム系硬質皮膜の状態（残存面積及び厚さ）をＣＣＤカメラにて観察し、硬質皮膜の除去（剥離）の進行度を総合的に判断して、百分率（０〜１００％）で表わした。試験結果を、下記表１〜表６に併せて示す。 In addition, the metal content in each stripping solution after treatment is measured by ICP-AES analysis, and the state (residual area and thickness) of the chromium-based hard film remaining on the sample surface after being immersed in the stripping solution is determined by a CCD camera. The degree of progress of removal (peeling) of the hard coating was comprehensively judged and expressed as a percentage (0 to 100%). The test results are shown in Tables 1 to 6 below.
−実施例１〜実施例３−
縮合リン酸塩の添加割合を同一（０．５重量％）として、添加する縮合リン酸塩の種類を変えた３種類の剥離液を準備し、クロム系硬質皮膜の除去（剥離）試験を行なった。下記表１から明らかなように、縮合リン酸塩の種類による有意差は認められず、何れの縮合リン酸塩を含む剥離液についても、６時間の処理（浸漬）により、クロム系硬質皮膜の除去が完了した。
Example 1 to Example 3
Prepare three types of stripping solutions with different condensed phosphate addition ratios (0.5% by weight) and change the type of condensed phosphate to be added, and perform a chromium hard coating removal (peeling) test. It was. As is apparent from Table 1 below, no significant difference was observed depending on the type of condensed phosphate, and the stripping solution containing any condensed phosphate was subjected to treatment (immersion) for 6 hours, resulting in a chromium-based hard coating. Removal is complete.
−実施例４、比較例１−
縮合リン酸塩たるヘキサメタリン酸ナトリウムによる効果を確認すべく、ヘキサメタリン酸ナトリウムを０．５重量％の割合において含む剥離液と、ヘキサメタリン酸ナトリウムを含まない剥離液とを準備し、それら剥離液を用いて、処理温度：２５℃、処理時間：１５時間の条件にて、クロム系硬質皮膜の除去（剥離）試験を行なった。下記表２より明らかなように、処理時間（１５時間）経過後において、ヘキサメタリン酸ナトリウムを添加していない剥離液（比較例１）を用いた場合は、皮膜除去の進行度が７０％に止まったのに対して、本発明の如く、ヘキサメタリン酸ナトリウムを０．５重量％の割合にて含有する剥離液（実施例４）にあっては、クロム系硬質皮膜が完全に除去されたことを確認した。
Example 4 and Comparative Example 1
In order to confirm the effect of sodium hexametaphosphate, which is a condensed phosphate, a stripping solution containing sodium hexametaphosphate at a ratio of 0.5% by weight and a stripping solution not containing sodium hexametaphosphate were prepared, and these stripping solutions were used. Then, the removal (peeling) test of the chromium-based hard coating was performed under the conditions of a processing temperature of 25 ° C. and a processing time of 15 hours. As is apparent from Table 2 below, when a stripping solution (Comparative Example 1) to which sodium hexametaphosphate has not been added is used after the processing time (15 hours) has elapsed, the degree of progress of film removal remains at 70%. On the other hand, in the stripping solution (Example 4) containing sodium hexametaphosphate at a ratio of 0.5% by weight as in the present invention, the chromium hard film was completely removed. confirmed.
−実施例１、実施例５、実施例６−
縮合リン酸塩たるヘキサメタリン酸ナトリウムを０．５重量％の割合にて含む剥離液を用いて、処理温度を変えてクロム系硬質皮膜の除去（剥離）試験を行ない、皮膜除去が完了する時間を確認した。下記表３から明らかなように、処理温度が４０℃の場合には６時間で、６０℃の場合には３時間で、それぞれ、皮膜除去が完了することが認められたが、処理温度を７０℃とした場合には、途中で反応が停止し、皮膜除去が不完全な状態で終了することが認められた。これは、ヘキサメタリン酸ナトリウム及び／又はペルオキソ二硫酸ナトリウムの分解により生じたリン酸及び／又は硫酸が、ｐＨ調製のために添加された水酸化ナトリウムと反応して、剥離液のｐＨが１３．５未満に低下したことに起因するものと想定される。
-Example 1, Example 5, Example 6-
Using a stripping solution containing 0.5% by weight of sodium hexametaphosphate, which is a condensed phosphate, the removal (peeling) test of the chromium-based hard film is performed at different treatment temperatures, and the time for film removal is completed. confirmed. As is apparent from Table 3 below, it was found that the film removal was completed in 6 hours when the treatment temperature was 40 ° C. and 3 hours when the treatment temperature was 60 ° C., respectively. When it was set to ° C., it was confirmed that the reaction stopped halfway and the film removal was completed in an incomplete state. This is because phosphoric acid and / or sulfuric acid generated by decomposition of sodium hexametaphosphate and / or sodium peroxodisulfate reacts with sodium hydroxide added for pH adjustment, and the pH of the stripping solution is 13.5. It is assumed that it is caused by lowering below.
−実施例７、実施例８、比較例２−
縮合リン酸塩たるヘキサメタリン酸ナトリウムを含まない剥離液（比較例２）と、ヘキサメタリン酸ナトリウムを０．５重量％の割合において含む剥離液（実施例７）及び２．５重量％の割合において含む剥離液（実施例８）を用いて、縮合リン酸塩の添加量の相違が皮膜除去効果に及ぼす影響を、処理温度：４０℃、処理時間：４時間の条件に従ってクロム系硬質皮膜の除去（剥離）試験を実施することにより、確認した。下記表４から明らかなように、ヘキサメタリン酸ナトリウムを含まない剥離液（比較例２）にあっては、皮膜除去の進行度が５０％に止まったのに対して、ヘキサメタリン酸ナトリウムを０．５重量％の割合において含む剥離液（実施例７）にあっては、皮膜除去の進行度は８０％に達し、また、ヘキサメタリン酸ナトリウムを２．５重量％の割合において含む剥離液（実施例８）にあっては、皮膜除去の進行度が６０％であることが認められた。
-Example 7, Example 8, Comparative Example 2-
A stripping solution not containing sodium hexametaphosphate as a condensed phosphate (Comparative Example 2), a stripping solution containing sodium hexametaphosphate in a proportion of 0.5% by weight (Example 7) and a proportion of 2.5% by weight Using the stripper (Example 8), the effect of the difference in the amount of condensed phosphate added on the film removal effect was determined by removing the chromium-based hard film according to the conditions of treatment temperature: 40 ° C., treatment time: 4 hours ( It was confirmed by carrying out a peeling test. As apparent from Table 4 below, in the stripping solution not containing sodium hexametaphosphate (Comparative Example 2), the degree of progress of film removal was only 50%, whereas sodium hexametaphosphate was reduced to 0.5%. In the case of the stripping solution (Example 7) containing in a proportion by weight%, the degree of progress of film removal reaches 80%, and the stripping solution (Example 8) containing sodium hexametaphosphate in a proportion of 2.5% by weight. ), It was confirmed that the progress of film removal was 60%.
−実施例９、比較例３−
ヘキサメタリン酸ナトリウムの含有割合を多くした場合に皮膜除去に与える影響を、ヘキサメタリン酸ナトリウムを１５．５重量％の割合において含む剥離液（実施例９）と、ヘキサメタリン酸ナトリウムを２４．３重量％の割合において含む剥離液（比較例３）とを用いて、処理温度：４０℃、処理時間：１５時間の条件に従ってクロム系硬質皮膜の除去（剥離）試験を実施することにより、確認した。下記表５から明らかなように、ヘキサメタリン酸ナトリウムを１５．５重量％の割合において含む剥離液（実施例９）にあっては、皮膜除去の進行度が１００％であったのに対して、ヘキサメタリン酸ナトリウムを２４．３重量％の割合において含む剥離液（比較例３）においては、皮膜除去の進行度が７５％に止まることが認められた。
-Example 9, Comparative Example 3-
The effect on film removal when the content of sodium hexametaphosphate is increased is as follows. A stripping solution (Example 9) containing sodium hexametaphosphate in a proportion of 15.5% by weight, and 24.3% by weight of sodium hexametaphosphate. It confirmed by performing the removal (peeling) test of a chromium type hard film according to the conditions of processing temperature: 40 degreeC and processing time: 15 hours using peeling liquid (comparative example 3) contained in a ratio. As apparent from Table 5 below, in the stripping solution (Example 9) containing sodium hexametaphosphate in a proportion of 15.5% by weight, the progress of the film removal was 100%, In the stripping solution (Comparative Example 3) containing sodium hexametaphosphate at a ratio of 24.3% by weight, it was confirmed that the progress of film removal was 75%.
−実施例１０〜実施例１２−
クロム系硬質皮膜が、上記した実施例及び比較例で使用した試料とは異なる試料を用いて、縮合リン酸塩たるヘキサメタリン酸ナトリウムの含有割合及び処理温度を適宜、調整して、クロム系硬質皮膜の除去（剥離）試験を実施し、硬質皮膜の除去が完了するまでの時間を任意に制御可能か否かを確認した。下記表６から明らかなように、各実施例毎に設定した時間にて、クロム系硬質皮膜の除去が完了することが認められた。
-Example 10-Example 12-
The chromium-based hard coating is prepared by appropriately adjusting the content ratio and the processing temperature of sodium hexametaphosphate, which is a condensed phosphate, using a sample whose chromium-based hard coating is different from the samples used in the above examples and comparative examples. A removal (peeling) test was conducted to confirm whether or not the time until the removal of the hard coating was completed can be arbitrarily controlled. As apparent from Table 6 below, it was confirmed that the removal of the chromium-based hard coating was completed in the time set for each example.
上記した実施例から明らかなように、本発明に従うクロム系硬質皮膜用剥離液にあっては、縮合リン酸塩及び／又はその塩の含有割合や処理温度等を適宜、調整することにより、クロム系硬質皮膜の除去に要する時間を、所望とされる実用的な時間の範囲内に制御することが可能であることが認められる。また、上記した何れの実施例においても、クロム系硬質皮膜の除去後の母材表面に、異物の付着は認められなかったのである。
As is clear from the above-described examples, in the chromium-based hard coating stripping solution according to the present invention, the chromium phosphate is removed by appropriately adjusting the content of condensed phosphate and / or its salt, the treatment temperature, and the like. It can be seen that the time required to remove the system hard coating can be controlled within a desired practical time range. Further, in any of the above-described examples, no foreign matter was observed on the surface of the base material after the removal of the chromium-based hard coating.
Claims (3)
The chromium-based hard coating film according to claim 1 or 2, wherein the salt of peroxodisulfuric acid is one or more selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate. Stripping solution.
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