JP2012036488A - Titanium-based film removing agent - Google Patents
Titanium-based film removing agent Download PDFInfo
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- JP2012036488A JP2012036488A JP2010180530A JP2010180530A JP2012036488A JP 2012036488 A JP2012036488 A JP 2012036488A JP 2010180530 A JP2010180530 A JP 2010180530A JP 2010180530 A JP2010180530 A JP 2010180530A JP 2012036488 A JP2012036488 A JP 2012036488A
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- 229910052719 titanium Inorganic materials 0.000 title claims description 5
- 239000010936 titanium Substances 0.000 title description 97
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 8
- -1 salt fluoride compound Chemical class 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 5
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 5
- 229910010037 TiAlN Inorganic materials 0.000 claims description 12
- 229910010038 TiAl Inorganic materials 0.000 claims description 3
- 229910010041 TiAlC Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010828 elution Methods 0.000 abstract description 14
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 45
- 238000012360 testing method Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000007654 immersion Methods 0.000 description 9
- 238000007373 indentation Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 3
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XVOYSCVBGLVSOL-UHFFFAOYSA-N cysteic acid Chemical compound OC(=O)C(N)CS(O)(=O)=O XVOYSCVBGLVSOL-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Abstract
Description
本発明は、Ｔｉ系被膜の除去剤に関し、さらには、コバルトを結合相として構成される超硬質材料からなる母材表面に形成されているＴｉ系被膜を除去するための被膜除去剤に関する。 The present invention relates to a Ti-based film removing agent, and further relates to a film-removing agent for removing a Ti-based film formed on the surface of a base material made of an ultra-hard material composed of cobalt as a binder phase.
炭化タングステン（ＷＣ）などの超硬質粒子を、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）などを結合相として構成される材料は、従来から、超硬合金として知られており、超硬質材工具などに用いられている。これらの超硬質材料からなる工具は、耐摩耗性の向上および母材である超硬質材料を保護するため、硬質被膜によって母材表面をコーティングすることが行われている。特に、Ｔｉ系の硬質被膜（以下、Ｔｉ系被膜と呼ぶ）、詳しくは、Ｔｉ、ＴｉＣ、ＴｉＮ、ＴｉＣＮ、ＴｉＡｌ、ＴｉＡｌＣ、ＴｉＡｌＮ、ＴｉＡｌＣｒ、及びこれらが更に他の金属もしくは非金属元素を含有する材料、に代表されるチタニウムを含有する材料からなる硬質被膜を表面に有する切削工具は、耐摩耗性に優れるため、近年、多用されるようになってきている。 Materials composed of ultra-hard particles such as tungsten carbide (WC) with a binder phase of cobalt (Co), nickel (Ni), copper (Cu), etc. have been conventionally known as cemented carbides. Used for hard tools. In order to improve the wear resistance and protect the super-hard material which is a base material, the tool made of these super-hard materials is coated with a hard film on the surface of the base material. In particular, a Ti-based hard coating (hereinafter referred to as a Ti-based coating), more specifically, Ti, TiC, TiN, TiCN, TiAl, TiAlC, TiAlN, TiAlCr, and these further contain other metals or nonmetallic elements. In recent years, cutting tools having a hard coating made of a material containing titanium typified by a material have excellent wear resistance, and thus have been frequently used in recent years.
このような切削工具においては、使用するにしたがって、刃部表面に設けたＴｉ系被膜が他の箇所の被膜よりも早く摩耗してしまうことが起こる。このため、所定時間使用した場合に、Ｔｉ系被膜を一旦すべて除去し、刃部を研削加工して再調整した後、再びコーティングを施してＴｉ系被膜を形成し、リサイクルすることが要望される。また、上記切削工具の製造の際のＴｉ系被膜コーティング工程において、コーティングされたＴｉ系被膜が規格値から外れた場合にも、Ｔｉ系被膜をすべて除去した後、再びコーティングすることが要望される。これらの場合に、Ｔｉ系被膜を精度よく再コーティングするためには、母材への影響を抑制した薬剤（除去剤）などによってＴｉ系被膜を完全に除去する必要がある。 In such a cutting tool, as the tool is used, the Ti-based coating provided on the surface of the blade portion may wear faster than the coating at other locations. For this reason, when it is used for a predetermined time, it is desired to remove all the Ti-based film once, grind the blade part again, and then apply the coating again to form the Ti-based film and recycle it. . In addition, in the Ti-based coating coating process in manufacturing the cutting tool, even when the coated Ti-based coating deviates from the standard value, it is desired to remove the Ti-based coating and then perform coating again. . In these cases, in order to accurately recoat the Ti-based film, it is necessary to completely remove the Ti-based film with a chemical (removal agent) that suppresses the influence on the base material.
これに対し、特許文献１には、超硬合金素地（母材）の劣化を抑制した、親プロトン性溶媒、フッ化アルカリ塩、リン酸アルカリ塩、次亜硫酸アルカリ、水溶性高分子、有機酸、イミン化合物からなる界面活性剤、過酸化水素を含有してなるチタンコーティング被膜の除去剤が開示されている。 On the other hand, Patent Document 1 discloses a protophilic solvent, alkali fluoride salt, alkali phosphate salt, alkali hyposulfite, water-soluble polymer, organic acid, which suppresses deterioration of the cemented carbide substrate (base material). In addition, a surfactant made of an imine compound and a titanium coating film remover containing hydrogen peroxide are disclosed.
また、特許文献２には、過酸化水素と界面活性剤を含有するアルカリ性水溶液からなる、母材への悪影響を抑制した硬質被膜除去剤が開示されている。また、特許文献３には、過酸化水素、水酸化アルカリ及びアミノカルボン酸及び酒石酸塩あるいは安息香酸塩を含有してなるＴｉ系被膜剥離剤が開示されている。該剥離剤は、超硬質材料中のコバルトの溶出が抑制され、Ｔｉ系被膜の剥離時間が短いとされている。 Further, Patent Document 2 discloses a hard film removing agent that is made of an alkaline aqueous solution containing hydrogen peroxide and a surfactant and that suppresses adverse effects on the base material. Patent Document 3 discloses a Ti-based film release agent containing hydrogen peroxide, alkali hydroxide, aminocarboxylic acid, and tartrate or benzoate. The stripping agent is said to suppress elution of cobalt in the superhard material and to have a short stripping time for the Ti-based coating.
しかしながら、本発明者等の検討によれば、上記特許文献１〜３に開示された従来のＴｉ系被膜の除去剤は、いずれも過酸化水素を含むアルカリ系の被膜除去剤であり、母材へ与える影響を充分に抑制するものではなく、改善の余地があった。特に、母材がコバルトを結合相としている超硬質材料である場合に、これらの被膜除去剤を使用すると、母材中のコバルトが溶出し、これに起因して母材の表面強度が低下するため、再度Ｔｉ系被膜を施した場合に、膜剥がれが発生するといった問題点があった。 However, according to the study by the present inventors, the conventional Ti-based film removers disclosed in Patent Documents 1 to 3 are all alkaline-based film removers containing hydrogen peroxide. There is room for improvement without sufficiently suppressing the impact on In particular, when the base material is an ultra-hard material having cobalt as a binder phase, the use of these coating removers results in the dissolution of cobalt in the base material, resulting in a decrease in the surface strength of the base material. Therefore, there has been a problem that when the Ti-based film is applied again, film peeling occurs.
本発明は、上記問題を解決するためになされたものであり、母材へ与える影響をより低減させたＴｉ系被膜除去剤を提供することを目的とする。特に、その母材がコバルトを結合相とする超硬質材料である場合にも、コバルトの溶出が抑制でき、これにより従来の除去剤を使用した場合に生じていた再コーティングしたＴｉ系被膜の膜剥がれの問題を解決できるＴｉ系被膜除去剤を提供することを目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a Ti-based film removing agent that further reduces the influence on the base material. In particular, even when the base material is an ultra-hard material having a binder phase of cobalt, the elution of cobalt can be suppressed, and thus a re-coated Ti-based film that has been generated when a conventional remover is used. An object of the present invention is to provide a Ti-based film remover that can solve the problem of peeling.
本発明者等は、上記問題を解決すべく鋭意検討を重ねた結果、特定の組成を有するＴｉ系被膜除去剤が、上記問題を解決し得ることを見出して、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a Ti-based film removing agent having a specific composition can solve the above problems, and have reached the present invention.
すなわち、本発明は、（Ａ）塩化水素５〜２０質量％、（Ｂ）フッ化アンモニウム、フッ化カリウム、フッ化ナトリウム及びフッ化リチウムから選ばれる少なくとも１種類のフッ化塩化合物０．５〜１０質量％、（Ｃ）下記一般式（１）で表される化合物又はその塩を１〜１０質量％含む水溶液からなることを特徴とするＴｉ系被膜除去剤である。
ＨＳ−Ｘ1−Ｙ （１）
（式中、Ｘ1は、炭素数１〜４のカルボキシル基で置換されてもよいアルキレン基を表し、Ｙは、カルボキシル基又はアミノ基を表す。）
That is, the present invention provides (A) 5 to 20% by mass of hydrogen chloride, (B) at least one fluoride salt compound selected from ammonium fluoride, potassium fluoride, sodium fluoride and lithium fluoride 0.5 to 10% by mass, (C) A Ti-based film removing agent comprising an aqueous solution containing 1 to 10% by mass of a compound represented by the following general formula (1) or a salt thereof.
HS-X 1 -Y (1)
(Wherein, X 1 represents a alkylene group optionally substituted with a carboxyl group having 1 to 4 carbon atoms, Y represents a carboxyl group or an amino group.)
本発明によれば、母材へ与える影響を低減させたＴｉ系被膜除去剤を提供することができる。特に、本発明によれば、コバルトを結合相として構成される超硬質材料からなる母材表面に形成されているＴｉ系被膜の除去に使用した場合にも、母材中のコバルトの溶出が抑制されるので、除去後の母材表面に、再度Ｔｉ系被膜を形成した際に膜剥がれが生じない優れたＴｉ系被膜除去剤の提供が可能になる。 ADVANTAGE OF THE INVENTION According to this invention, the Ti-type film removal agent which reduced the influence which acts on a base material can be provided. In particular, according to the present invention, the elution of cobalt in the base material is suppressed even when it is used to remove the Ti-based coating formed on the surface of the base material made of an ultra-hard material composed of cobalt as a binder phase. Therefore, it is possible to provide an excellent Ti-based film removing agent that does not cause film peeling when a Ti-based film is formed again on the surface of the base material after removal.
以下に好ましい実施の形態を挙げて本発明をさらに詳細に説明する。本発明は、Ｔｉ系被膜を超硬質材料表面から除去するための除去剤に関するが、具体的には、下記の（Ａ）、（Ｂ）及び（Ｃ）の３成分を必須成分として含むことを特徴とする。すなわち、（Ａ）成分として塩化水素を５〜２０質量％、（Ｂ）成分として、フッ化アンモニウム、フッ化カリウム、フッ化ナトリウム、フッ化リチウムから選ばれる少なくとも１種類のフッ化塩化合物を０．５〜１０質量％、（Ｃ）成分として、下記一般式（１）で表される化合物又はその塩を１〜１０質量％含む水溶液である。
ＨＳ−Ｘ1−Ｙ （１）
（式中、Ｘ1は、炭素数１〜４のカルボキシル基で置換されてもよいアルキレン基を表し、Ｙは、カルボキシル基又はアミノ基を表す。）
必要に応じて、本発明の効果を阻害しない範囲で、上記に加えて添加剤を含有してもよい。本発明のＴｉ系被膜除去剤は、上記（Ａ）〜（Ｃ）の成分と、必要に応じて使用される添加剤とを含有し、残りは水で調整される。
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The present invention relates to a remover for removing a Ti-based film from the surface of an ultra-hard material. Specifically, the present invention includes the following three components (A), (B) and (C) as essential components. Features. That is, at least one fluoride salt compound selected from ammonium fluoride, potassium fluoride, sodium fluoride, and lithium fluoride is used as component (A). It is an aqueous solution containing 1 to 10% by mass of the compound represented by the following general formula (1) or a salt thereof as the component (C).
HS-X 1 -Y (1)
(Wherein, X 1 represents a alkylene group optionally substituted with a carboxyl group having 1 to 4 carbon atoms, Y represents a carboxyl group or an amino group.)
If necessary, an additive may be contained in addition to the above as long as the effects of the present invention are not impaired. The Ti-type film removing agent of the present invention contains the components (A) to (C) and additives used as necessary, and the remainder is adjusted with water.
本発明のＴｉ系被膜除去剤に含まれる（Ａ）成分である塩化水素は、（Ｂ）成分であるフッ化塩化合物と共にＴｉ系被膜を溶解し、実質的に除去する役割を果たしている。また、（Ａ）成分である塩化水素は、母材である超硬質材料の腐食を抑制する効果を有している。特に母材がコバルトを結合相とする超硬質材料の場合、母材中のコバルトの溶出を抑制する効果が高い。（Ａ）成分の含有量は、５〜２０質量％、好ましくは、５〜１５質量％である。（Ａ）成分の含有量が下限よりも少ないと、母材である超硬質材料の腐食が大きくなり、Ｔｉ系被膜を除去後に、母材表面に再度形成したＴｉ系被膜が膜剥がれを起こすおそれがある。一方、（Ａ）成分の含有量を上限より多くしても、母材の腐食抑制に対するより高い向上効果が得られず、逆にＴｉ系被膜を除去する処理時間が長くなる等の不具合を生じる。 Hydrogen chloride as the component (A) contained in the Ti-based film removing agent of the present invention plays a role of dissolving and substantially removing the Ti-based film together with the fluoride compound as the (B) component. Moreover, the hydrogen chloride which is (A) component has the effect which suppresses corrosion of the super-hard material which is a base material. In particular, when the base material is an ultra-hard material having cobalt as a binder phase, the effect of suppressing the elution of cobalt in the base material is high. (A) Content of a component is 5-20 mass%, Preferably, it is 5-15 mass%. If the content of the component (A) is less than the lower limit, the corrosion of the superhard material that is the base material becomes large, and the Ti-based film formed again on the surface of the base material after the Ti-based film is removed may cause film peeling. There is. On the other hand, even if the content of the component (A) is increased from the upper limit, a higher improvement effect on the corrosion inhibition of the base material cannot be obtained, and conversely, the processing time for removing the Ti-based film becomes longer. .
本発明のＴｉ系被膜除去剤において、（Ｂ）成分であるフッ化塩化合物は、Ｔｉ系被膜を溶解し、実質的に除去する役割を果たしている。（Ｂ）成分であるフッ化塩化合物は、フッ化アンモニウム、フッ化カリウム、フッ化ナトリウム、フッ化リチウムから選ばれるが、これらは１種類でもよく、２種類以上を混合して用いてもよい。これらの中でもフッ化アンモニウムは、Ｔｉ系被膜の除去時間が短く、母材の腐食抑制効果が良好なので、より好ましい。（Ｂ）成分の含有量は、０．５〜１０質量％、好ましくは１．０〜７．５質量％である。（Ｂ）成分の含有量が下限よりも少ないと、Ｔｉ系被膜の除膜時間が長くなり、それに伴って、すでにＴｉ系被膜が除去された部分から母材である超硬質材料の腐食が進行し、母材の腐食量が大きくなるといった不具合が生じる。一方、（Ｂ）の含有量が上限よりも多いと、Ｔｉ系被膜の除去が急激に進みすぎ、母材の腐食が大きくなるといった不具合が生じる。 In the Ti-based film removing agent of the present invention, the fluoride salt compound as the component (B) plays a role of dissolving and substantially removing the Ti-based film. The fluoride salt compound as component (B) is selected from ammonium fluoride, potassium fluoride, sodium fluoride, and lithium fluoride. These may be used alone or in combination of two or more. . Among these, ammonium fluoride is more preferable because the removal time of the Ti-based film is short and the corrosion inhibition effect of the base material is good. (B) Content of a component is 0.5-10 mass%, Preferably it is 1.0-7.5 mass%. When the content of the component (B) is less than the lower limit, the time required for removing the Ti-based film becomes longer, and accordingly, the corrosion of the super-hard material as the base material proceeds from the portion where the Ti-based film has already been removed. However, there is a problem that the amount of corrosion of the base material increases. On the other hand, when the content of (B) is larger than the upper limit, the removal of the Ti-based film proceeds too rapidly, resulting in a problem that the corrosion of the base material increases.
本発明のＴｉ系被膜除去剤における（Ｃ）成分は、先に示した一般式（１）で表される化合物又はその塩であり、これらは１種類又は２種類以上混合して使用される。本発明者らの検討によれば、この（Ｃ）成分を含有させることによって、母材の腐食を抑制するより高い効果が得られるＴｉ系被膜除去剤となる。特に、母材がコバルトを結合相とする超硬質材料を処理した場合に、母材表面からのコバルトの溶出を抑制する高い効果を得ることができる。上記一般式（１）で表される化合物の具体例としては、下記化合物Ｎｏ．１〜化合物Ｎｏ．１６が挙げられる。 The component (C) in the Ti-based film removing agent of the present invention is the compound represented by the general formula (1) or a salt thereof shown above, and these are used alone or in combination of two or more. According to the study by the present inventors, the inclusion of the component (C) provides a Ti-based film remover that can obtain a higher effect of suppressing the corrosion of the base material. In particular, when an ultra-hard material whose base material has cobalt as a binder phase is processed, a high effect of suppressing the elution of cobalt from the surface of the base material can be obtained. Specific examples of the compound represented by the general formula (1) include the following compound No. 1-Compound No. 1 16 is mentioned.
上記一般式（１）で表される化合物の中でも、下記一般式（２）で表される化合物及びその塩は、母材の腐食を抑制する効果、特に、母材がコバルトを結合相とする超硬質材料である場合に、コバルトの溶出抑制効果に優れているので、（Ｃ）成分として、より好ましい。
ＨＳ−Ｘ2−ＮＨ2 （２）
（式中、Ｘ2は、カルボキシル基で置換されてもよい炭素数２〜４のアルキレン基を表す。）
Among the compounds represented by the general formula (1), the compound represented by the following general formula (2) and the salt thereof have an effect of suppressing the corrosion of the base material, in particular, the base material has cobalt as a binder phase. Since it is excellent in the elution suppression effect of cobalt when it is a super-hard material, it is more preferable as (C) component.
HS-X 2 -NH 2 (2 )
(In the formula, X 2 represents an alkylene group having 2 to 4 carbon atoms which may be substituted with a carboxyl group.)
上記一般式（１）で表される化合物の具体例として挙げた上記１６種の化合物のうち、化合物Ｎｏ．１〜化合物Ｎｏ．９が上記一般式（２）に相当する。 Of the 16 compounds listed as specific examples of the compound represented by the general formula (1), compound No. 1-Compound No. 1 9 corresponds to the above general formula (2).
上記、一般式（１）又は一般式（２）で表される化合物の塩としては、アミノ基と塩を形成したもの、例えば、塩酸塩、酢酸塩、炭酸塩、硝酸塩、又はＣＯＯＨ基と塩を形成したもの、例えば、アンモニウム塩、ナトリウム塩、カリウム塩、リチウム塩等が挙げられる。 The salt of the compound represented by the general formula (1) or the general formula (2) is a salt formed with an amino group, for example, hydrochloride, acetate, carbonate, nitrate, or COOH group and salt. For example, ammonium salts, sodium salts, potassium salts, lithium salts and the like can be mentioned.
本発明のＴｉ系被膜除去剤に含有させる（Ｃ）成分の、より好ましい化合物としては、下記のものが挙げられる。化合物Ｎｏ．１（２−アミノエタンチオール）、該化合物Ｎｏ．１の塩酸塩、該化合物Ｎｏ．１の酢酸塩、該化合物Ｎｏ．１の炭酸塩、該化合物Ｎｏ．１の硝酸塩、化合物Ｎｏ．９（システイン酸）、該化合物Ｎｏ．９の塩酸塩、該化合物Ｎｏ．９の酢酸塩、該化合物Ｎｏ．９の炭酸塩、該化合物Ｎｏ．９の硝酸塩、該化合物Ｎｏ．９のアンモニウム塩、該化合物Ｎｏ．９のナトリウム塩、該化合物Ｎｏ．９のカリウム塩、化合物Ｎｏ．９のリチウム塩である。対イオンの影響の排除及びコストの観点から、さらに好ましいのは、化合物Ｎｏ．１、化合物Ｎｏ．１の塩酸塩、化合物Ｎｏ．９、化合物Ｎｏ．９の塩酸塩である。 The following are mentioned as a more preferable compound of (C) component contained in the Ti type | system | group film removal agent of this invention. Compound No. 1 (2-aminoethanethiol), the compound no. No. 1 hydrochloride, Compound No. 1 1, acetate no. 1, carbonate no. 1 nitrate, compound no. 9 (cysteic acid), the compound no. No. 9 hydrochloride, the compound no. 9, acetate no. No. 9 carbonate, the compound no. 9 nitrate, the compound no. No. 9 ammonium salt, the compound no. No. 9 sodium salt, compound no. No. 9 potassium salt, compound no. 9 lithium salt. From the viewpoint of eliminating the influence of counter ions and cost, compound No. 1 is more preferable. 1, compound no. 1 hydrochloride, compound no. 9, compound no. 9 hydrochloride.
本発明のＴｉ系被膜除去剤における（Ｃ）成分の含有量は、１〜１０質量％、好ましくは、２．５〜７．５質量％である。（Ｃ）成分の含有量が下限よりも少ないと、母材の腐食を抑制する効果、特に母材がコバルトを結合相とする超硬質材料の場合に、母材中のコバルトの溶出を抑制する効果が充分に得られない。一方、（Ｃ）成分の含有量を上限より多くしても、母材に対する腐食抑制のさらなる向上効果が得られず、逆にＴｉ系被膜の除去速度が低下し、処理時間が長くなる等の不具合を生じる。 Content of (C) component in Ti type | system | group film removal agent of this invention is 1-10 mass%, Preferably, it is 2.5-7.5 mass%. When the content of the component (C) is less than the lower limit, the effect of suppressing the corrosion of the base material, particularly, when the base material is an ultra-hard material having cobalt as a binder phase, the elution of cobalt in the base material is suppressed. The effect cannot be obtained sufficiently. On the other hand, even if the content of the component (C) is increased from the upper limit, a further improvement effect of inhibiting corrosion on the base material cannot be obtained, and on the contrary, the removal rate of the Ti-based film is reduced, and the processing time is increased. It causes a defect.
また、本発明のＴｉ系被膜除去剤には、上記（Ａ）〜（Ｃ）成分のほかに、本発明の効果を阻害することのない範囲で、周知の添加剤を配合することができる。当該添加剤としては、Ｔｉ系被膜除去剤の安定化剤、上記（Ａ）〜（Ｃ）各成分の可溶化剤、ｐＨ調整剤、比重調整剤、粘度調整剤、濡れ性改善剤、キレート剤等が挙げられる。これらを使用する場合の濃度は、一般に、０．００１質量％〜１０質量％の範囲である。 In addition to the above components (A) to (C), a well-known additive can be blended with the Ti-based film removing agent of the present invention as long as the effects of the present invention are not impaired. Examples of the additive include a stabilizer for a Ti-based film removing agent, a solubilizer for each of the above components (A) to (C), a pH adjuster, a specific gravity adjuster, a viscosity adjuster, a wettability improver, and a chelating agent. Etc. When using these, the density | concentration is generally the range of 0.001 mass%-10 mass%.
本発明のＴｉ系被膜除去剤は、Ｔｉ系硬質被膜がコーティングされた超硬質材料からなる切削工具における硬質被膜の除去、その後に行う再被覆に対し効果的である。Ｔｉ系被膜としては、例えばＴｉ、ＴｉＣ、ＴｉＮ、ＴｉＣＮ、ＴｉＡｌ、ＴｉＡｌＣ、ＴｉＡｌＮ、ＴｉＡｌＣｒなどを挙げることができ、また、これらが更に他の金属もしくは非金属元素（例えば、Ｗ、Ｍｏ、Ｓｉ、Ｏ、Ｂなど）を含有する材料も例示することができる。本発明のＴｉ系被膜除去剤は、これらのＴｉ系被膜の中でも、特にＴｉＡｌＮ被膜の除去に有用である。 The Ti-based film removing agent of the present invention is effective for removal of a hard film in a cutting tool made of an ultra-hard material coated with a Ti-based hard film and subsequent re-coating. Examples of the Ti-based film include Ti, TiC, TiN, TiCN, TiAl, TiAlC, TiAlN, TiAlCr, and the like, and these may further include other metal or non-metallic elements (for example, W, Mo, Si, Examples thereof include materials containing O, B, and the like. Among these Ti-based coatings, the Ti-based coating remover of the present invention is particularly useful for removing a TiAlN coating.
上記のＴｉ系被膜が施される超硬質材料からなる母材としては、一般に知られる超硬合金、例えば、炭化タングステン（ＷＣ）に代表される超硬質粒子を、コバルト、ニッケル、銅等を結合相として構成される材料が挙げられる。超硬質材料を構成する超硬質粒子として、上記炭化タングステンの他に、炭化タンタル（ＴａＣ）、炭化ニオブ（ＮｂＣ）、炭化珪素（ＳｉＣ）、炭化ジルコニウム（ＺｒＣ）、炭化チタン（ＴｉＣ）、炭化ハフニウム（ＨｆＣ）、炭化バナジウム（ＶＣ）等が添加される場合もある。本発明のＴｉ系被膜除去剤は、コバルトの溶出抑制効果に特に優れるので、これらの超硬質粒子を、コバルトを結合相として形成した構成の超硬質材料を母材とする場合に、特に有用である。 As a base material made of a super hard material to which the Ti-based film is applied, generally known super hard alloy, for example, super hard particles represented by tungsten carbide (WC), cobalt, nickel, copper, etc. are combined. Examples include materials that are configured as phases. In addition to the above tungsten carbide, as the ultrahard particles constituting the ultrahard material, tantalum carbide (TaC), niobium carbide (NbC), silicon carbide (SiC), zirconium carbide (ZrC), titanium carbide (TiC), hafnium carbide (HfC), vanadium carbide (VC), or the like may be added. Since the Ti-based film removing agent of the present invention is particularly excellent in the effect of suppressing the dissolution of cobalt, it is particularly useful when these ultra-hard particles are based on an ultra-hard material having a structure in which cobalt is formed as a binder phase. is there.
本発明のＴｉ系被膜除去剤を用いて母材表面に形成されたＴｉ系被膜を除去するには、対象となる部材を本発明のＴｉ系被膜除去剤に浸漬、或いは該部材に除去剤をスプレー等すればよい。浸漬処理の条件としては、被膜を除去する対象となる部材の形状や、Ｔｉ系被膜の膜厚などによって異なるので、これらに応じて適宜選択すればよい。例えば、浸漬時にＴｉ系被膜除去剤の温度があまり低温であるとＴｉ系被膜の除去効率が悪くなり、温度があまり高いと該除去剤の自己反応により除去剤の濃度が急速に変わるおそれがあるので、浸漬処理の際に使用するＴｉ系被膜除去剤の温度は、好ましくは１０〜８０℃、より好ましくは２０〜６０℃の範囲とするとよい。なお、浸漬処理の際に、反応熱によりＴｉ系被膜除去剤の温度は上昇するので、必要に応じて温度が上記範囲内となるように制御するとよい。 In order to remove the Ti-based film formed on the surface of the base material using the Ti-based film remover of the present invention, the target member is immersed in the Ti-based film remover of the present invention, or the remover is applied to the member. What is necessary is just to spray. The conditions for the immersion treatment vary depending on the shape of the member from which the coating is removed, the thickness of the Ti-based coating, and the like. For example, if the temperature of the Ti-based film removing agent is too low during immersion, the removal efficiency of the Ti-based film is deteriorated, and if the temperature is too high, the concentration of the removing agent may change rapidly due to the self-reaction of the removing agent. Therefore, the temperature of the Ti-based film removing agent used in the immersion treatment is preferably 10 to 80 ° C, more preferably 20 to 60 ° C. In addition, since the temperature of Ti type | system | group film removal agent rises by the heat of reaction in the case of immersion treatment, it is good to control so that temperature may be in the said range as needed.
Ｔｉ系被膜除去剤によってＴｉ系被膜を部材表面から除去する際の、上記浸漬時間は、特に限定されるものではなく、該被膜が除去されるまでの時間行えばよい。例えば、通常の切削工具などの部材に設けられているＴｉ系被膜は、その膜厚が１〜１０μｍであるが、この場合であれば、該部材の本発明のＴｉ系被膜除去剤への浸漬時間を数十分〜十数時間とすればよい。なお、本発明のＴｉ系被膜除去剤は、母材に対する腐食抑制効果が高く、母材への影響が極めて少ないので、被膜除去後に時間が経過して浸漬時間が過剰となっても、例えば、母材中のコバルトの溶出が小さい。このため、浸漬処理における浸漬時間の管理がし易いといった利点もある。また、本発明のＴｉ系被膜除去剤は水溶液であるので、浸漬処理後に水などで容易に洗浄でき、その後に再度、Ｔｉ系被膜を形成すればよいので容易にリサイクル等することが可能である。 The immersion time when the Ti-based film is removed from the member surface by the Ti-based film removing agent is not particularly limited, and may be a time until the film is removed. For example, a Ti-based film provided on a member such as a normal cutting tool has a film thickness of 1 to 10 μm. In this case, the member is immersed in the Ti-based film removing agent of the present invention. What is necessary is just to make time into tens of minutes-dozens of hours. In addition, the Ti-based film removing agent of the present invention has a high corrosion inhibitory effect on the base material, and has very little influence on the base material. Elution of cobalt in the base material is small. For this reason, there also exists an advantage that the immersion time in an immersion process is easy to manage. In addition, since the Ti-based film removing agent of the present invention is an aqueous solution, it can be easily washed with water after the immersion treatment, and after that, a Ti-based film may be formed again, so that it can be easily recycled. .
以下、実施例及び比較例により本発明を詳細に説明するが、これらによって本発明が限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these.
［実施例１〜１２］
（Ａ）成分として塩化水素を９．０質量％、（Ｂ）成分としてフッ化アンモニウムを４．０質量％、さらに、（Ｃ）成分として表１に記載したそれぞれの化合物を、それぞれの量で使用して、全体が１００質量％となるように残りを水で調整し、Ｔｉ系被膜除去剤Ｎｏ．１〜Ｎｏ．１２をそれぞれに調製した。そして、これらを実施例１〜１２のＴｉ系被膜除去剤とした。
[Examples 1 to 12]
(A) 9.0% by mass of hydrogen chloride as the component, 4.0% by mass of ammonium fluoride as the (B) component, and each compound listed in Table 1 as the (C) component in respective amounts. And the rest is adjusted with water so that the whole is 100% by mass. 1-No. 12 were prepared for each. And these were made into the Ti-type film removal agent of Examples 1-12.
［比較例１〜５］
過酸化水素を１７質量％、水酸化ナトリウムを２質量％とし、全体が１００質量％となるように残りを水で調整して比較用組成物１を調製し、比較例１の除去剤とした。また、塩化水素を９．０質量％、フッ化アンモニウムを４．０質量％とし、全体が１００質量％となるように残りを水で調整して、比較例２の除去剤とした。該除去剤は、実施例と（Ｃ）成分を含有しない点で異なる。さらに、塩化水素を９．０質量％、フッ化アンモニウムを４．０質量％、さらに表２に記載した、従来の除去剤に使用されているそれぞれの化合物を、それぞれの量で使用して、全体が１００質量％となるように残りを水で調整し、比較用組成物３〜５をそれぞれ調製した。そして、これらを比較例３〜５の除去剤とした。
[Comparative Examples 1-5]
Hydrogen peroxide was 17% by mass, sodium hydroxide was 2% by mass, and the remainder was adjusted with water so that the total would be 100% by mass. . In addition, the removal agent of Comparative Example 2 was prepared by adjusting 9.0% by mass of hydrogen chloride and 4.0% by mass of ammonium fluoride, and adjusting the remainder with water so that the total was 100% by mass. The remover differs from the examples in that it does not contain the component (C). Further, 9.0% by mass of hydrogen chloride, 4.0% by mass of ammonium fluoride, and each of the compounds used in the conventional remover described in Table 2 are used in respective amounts. The remainder was adjusted with water so that the whole would be 100% by mass, and comparative compositions 3 to 5 were prepared. And these were made into the removal agent of Comparative Examples 3-5.
［評価例１］
大きさが１．２ｃｍ×１．２ｃｍ×５ｍｍの、コバルトを結合相とした、ＷＣ、ＴｉＣ、ＮｂＣの超硬質材料からなる母材（Ｗ；６７質量％、Ｔｉ；７．９質量％、Ｎｂ；７．５質量％、Ｃ；７．０質量％、Ｃｏ；９．６質量％）の片面に、硬質被膜としてＴｉＡｌＮ被膜（質量比；Ａｌ：Ｔｉ＝２：１）を３μｍの厚みでコーティングしたものを、テストピースとして用意した。そして上記のテストピースを、実施例１〜１２の各Ｔｉ系被膜除去剤中に、それぞれ浸漬して、硬質被膜を除去した。表１に記載した処理時間は、それぞれ硬質被膜が除去されたと判断して浸漬を終了した時間である。各除去剤中から取り出したＴｉ系被膜を除去後の各テストピースについて、表面のＥＤＸ分析によりコバルトの量（質量％）を測定した。そして、測定した結果を表１中に示した。ＥＤＸ分析の測定条件は、加速電圧を２０ｋＶ、Ｗ．Ｄ．（Working Distance）を１５ｍｍとした。なお、同様の条件で、ＴｉＡｌＮ被膜を形成しない状態の母材表面について測定したところ、母材表面のコバルト量は９．６質量％であった。
[Evaluation Example 1]
Base material made of an ultra-hard material of WC, TiC, NbC having a size of 1.2 cm × 1.2 cm × 5 mm and using cobalt as a binder phase (W: 67 mass%, Ti: 7.9 mass%, Nb 7.5% by mass, C: 7.0% by mass, Co: 9.6% by mass) A TiAlN coating (mass ratio; Al: Ti = 2: 1) as a hard coating is coated at a thickness of 3 μm on one side. This was prepared as a test piece. And said test piece was each immersed in each Ti type | system | group film removal agent of Examples 1-12, and the hard film was removed. The treatment time described in Table 1 is the time when the immersion was completed after determining that the hard coating was removed. About each test piece after removing the Ti-type film taken out from each removing agent, the amount (mass%) of cobalt was measured by EDX analysis of the surface. The measured results are shown in Table 1. The measurement conditions for the EDX analysis are an acceleration voltage of 20 kV, W.V. D. (Working Distance) was 15 mm. In addition, when it measured about the base material surface of the state which does not form a TiAlN film on the same conditions, the amount of cobalt of the base material surface was 9.6 mass%.
上記と同様に、実施例の評価に用いたと同じテストピースを、先に得た比較例１〜５の各比較用組成物中に、表２に記載の処理時間浸漬してＴｉ系被膜を除去した。Ｔｉ系被膜を除去した後、それぞれのテストピースについて、実施例の場合と同様の条件で、表面のＥＤＸ分析によりコバルトの量（質量％）を測定した。そして、測定した結果を表２中に示した。 Similarly to the above, the same test piece as used in the evaluation of the examples was immersed in the comparative compositions of Comparative Examples 1 to 5 previously obtained, and the Ti-based coating was removed by immersing the treatment time described in Table 2. did. After removing the Ti-based film, the amount (mass%) of cobalt was measured by EDX analysis of the surface of each test piece under the same conditions as in the example. The measured results are shown in Table 2.
表１に示したように、本発明の実施例のＴｉ系被膜除去剤を用いた場合は、いずれも、Ｔｉ系被膜の除去後、硬質被膜処理によって生じることが懸念される母材表面のコバルト量の減少量が小さく、除去剤の使用によって生じる母材表面からのコバルトの溶出が抑制されていることが確認された。一方、表２に示したように、比較用組成物を用いてＴｉ系被膜を除去した部材は、Ｔｉ系被膜の除去後の母材表面におけるコバルト量が０、或いは、コバルト量が大きく減少しており、コバルトが溶出し、母材表面にほとんどコバルトが存在していなかった。 As shown in Table 1, in the case of using the Ti-based film remover of the examples of the present invention, in all cases, the cobalt on the surface of the base material, which may be caused by the hard film treatment after the removal of the Ti-based film. It was confirmed that the amount of decrease in the amount was small and elution of cobalt from the base material surface caused by the use of the removing agent was suppressed. On the other hand, as shown in Table 2, in the member from which the Ti-based film was removed using the comparative composition, the amount of cobalt on the base material surface after the removal of the Ti-based film was 0, or the amount of cobalt was greatly reduced. Cobalt eluted and almost no cobalt was present on the surface of the base material.
また、ＴｉＡｌＮ被膜を形成しない状態の母材、実施例１０のＴｉ系被膜除去剤でＴｉ系被膜を除去した後のテストピース、比較例１又は２の従来のＴｉ系被膜除去剤でＴｉ系被膜を除去した後のテストピース、のそれぞれについて、電子顕微鏡で表面を観察した。図１〜４に、３０００倍のＳＥＭ写真をそれぞれ示した。 In addition, the base material in a state where no TiAlN film is formed, the test piece after removing the Ti film with the Ti film remover of Example 10, and the Ti film with the conventional Ti film remover of Comparative Example 1 or 2 About each of the test piece after removing, the surface was observed with an electron microscope. 1 to 4 show 3000 times SEM photographs.
図２に示すように、実施例１０のＴｉ系被膜除去剤でＴｉ系被膜を除去した後のテストピースの表面は、結合相であるコバルトの溶出が僅かであることが観察された。一方、比較例１および２のＴｉ系被膜除去剤でＴｉ系被膜を除去した後のテストピース表面は、図３、４に示されるように、超硬質材料の母材から、結合相であるコバルトの溶出が大きく、隙間が多く、粒子が浸食されて丸みを帯びている様子が観察された。 As shown in FIG. 2, it was observed that the surface of the test piece after removing the Ti-based film with the Ti-based film remover of Example 10 showed a slight elution of cobalt as a binder phase. On the other hand, the surface of the test piece after the Ti-based film was removed with the Ti-based film remover of Comparative Examples 1 and 2, as shown in FIGS. A large amount of elution was observed, and there were many gaps, and particles were eroded and rounded.
［評価例２］
ＴｉＡｌＮ被膜をコーティングしていない母材に、ＰＶＤ法により、ＴｉＡｌＮ被膜（質量比；Ａｌ：Ｔｉ＝２：１）を３μｍコーティングしたものを、未処理のテストピースとした。また、上記で行った実施例１０のＴｉ系被膜除去剤によるＴｉ系被膜の除去テストで得られたテストピースに、ＰＶＤ法により、再度、ＴｉＡｌＮ被膜（質量比；Ａｌ：Ｔｉ＝２：１）を３μｍコーティングしたものを、再被膜テストピース１とした。また、上記で行った比較例２の除去剤によるＴｉ系被膜の除去テストで得られたテストピースに、ＰＶＤ法により、再度、ＴｉＡｌＮ被膜（質量比；Ａｌ：Ｔｉ＝２：１）を３μｍコーティングしたものを、再被膜テストピース２とした。これらの各テストピースについて、ロックウェル圧痕試験（条件；荷重１５０ｋｇ、圧痕径３００μｍ）を行い、試験後の圧痕の様子を６０倍の光学顕微鏡により観察した。図５〜７に、それぞれの圧痕の様子を示した。
[Evaluation Example 2]
An untreated test piece was prepared by coating a base material not coated with a TiAlN film with a 3 μm TiAlN film (mass ratio; Al: Ti = 2: 1) by the PVD method. Further, the TiAlN coating (mass ratio; Al: Ti = 2: 1) was again applied to the test piece obtained by the Ti-based coating removal test using the Ti-based coating remover of Example 10 performed by the PVD method. Was coated with 3 μm as a re-coating test piece 1. Further, the TiAlN coating (mass ratio: Al: Ti = 2: 1) is again coated with 3 μm by the PVD method on the test piece obtained by the Ti-based coating removal test using the removing agent of Comparative Example 2 performed above. This was used as a re-coating test piece 2. Each of these test pieces was subjected to a Rockwell indentation test (conditions: load 150 kg, indentation diameter 300 μm), and the state of the indentation after the test was observed with a 60 × optical microscope. The state of each indentation was shown in FIGS.
図５及び６に示されるように、再被膜テストピース１には、除去処理を経ていない未処理のテストピースと同様に、圧痕境界部に膜剥がれは存在しなかった。これに対し、図７に示されるように、比較例の除去剤を用いた再被膜テストピース２では、圧痕境界部周辺部に膜剥がれが確認された。表１及び２に示すように、比較例２の除去剤を用いた場合は、除去後の母材表面のコバルトが溶出してしまったのに対して、実施例１０のＴｉ系被膜除去剤を用いた場合は、母材表面のコバルトの溶出が抑制されたことが確認されている。このことから、再被膜テストピース１では、Ｔｉ系被膜除去剤による母材表面のコバルトの溶出が抑制され、これにより被膜の除去後の母材の表面強度の低下を抑制することができ、この結果、再コーティングされたＴｉ系被膜の膜剥がれを防止できたと考えられる。 As shown in FIGS. 5 and 6, in the re-coating test piece 1, there was no film peeling at the indentation boundary as in the untreated test piece that had not been subjected to the removal treatment. On the other hand, as shown in FIG. 7, in the re-coating test piece 2 using the removing agent of the comparative example, film peeling was confirmed in the periphery of the indentation boundary. As shown in Tables 1 and 2, when the remover of Comparative Example 2 was used, cobalt on the surface of the base material after removal was eluted, whereas the Ti-based film remover of Example 10 was used. When used, it was confirmed that elution of cobalt on the surface of the base material was suppressed. From this, in the re-coating test piece 1, the elution of cobalt on the surface of the base material by the Ti-based film removing agent is suppressed, thereby suppressing the decrease in the surface strength of the base material after the removal of the coating. As a result, it is considered that the film peeling of the re-coated Ti-based film could be prevented.
Claims (4)
ＨＳ−Ｘ1−Ｙ （１）
（式中、Ｘ1は、炭素数１〜４のカルボキシル基で置換されてもよいアルキレン基を表し、Ｙは、カルボキシル基又はアミノ基を表す。） (A) Hydrogen chloride 5 to 20% by mass, (B) 0.5 to 10% by mass of at least one fluoride salt compound selected from ammonium fluoride, potassium fluoride, sodium fluoride and lithium fluoride, (C A Ti-based film remover comprising an aqueous solution containing 1 to 10% by mass of a compound represented by the following general formula (1) or a salt thereof.
HS-X 1 -Y (1)
(Wherein, X 1 represents a alkylene group optionally substituted with a carboxyl group having 1 to 4 carbon atoms, Y represents a carboxyl group or an amino group.)
ＨＳ−Ｘ2−ＮＨ2 （２）
（式中、Ｘ2は、カルボキシル基で置換されてもよい炭素数２〜４のアルキレン基を表す。） The Ti-type film removing agent according to claim 1, wherein the general formula (1) is a compound represented by the following general formula (2) or a salt thereof.
HS-X 2 -NH 2 (2 )
(In the formula, X 2 represents an alkylene group having 2 to 4 carbon atoms which may be substituted with a carboxyl group.)
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| KR20170022097A (en) | 2015-08-19 | 2017-03-02 | 동우 화인켐 주식회사 | ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME |
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| KR102469936B1 (en) * | 2015-08-19 | 2022-11-23 | 동우 화인켐 주식회사 | ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME |
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