JP2010502836A - New additives for chromium electrolytes - Google Patents
New additives for chromium electrolytes Download PDFInfo
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- JP2010502836A JP2010502836A JP2009527138A JP2009527138A JP2010502836A JP 2010502836 A JP2010502836 A JP 2010502836A JP 2009527138 A JP2009527138 A JP 2009527138A JP 2009527138 A JP2009527138 A JP 2009527138A JP 2010502836 A JP2010502836 A JP 2010502836A
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- 239000000654 additive Substances 0.000 title claims abstract description 63
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 27
- 239000011651 chromium Substances 0.000 title claims abstract description 27
- 239000003792 electrolyte Substances 0.000 title claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 51
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 24
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000009499 grossing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001465 metallisation Methods 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 alkyl methyl sulfonates Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Electroplating Methods And Accessories (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemically Coating (AREA)
- Primary Cells (AREA)
Abstract
本発明は，表面張力を低下させ，したがってクロム析出プロセスを改良する，クロム電解質用のフッ素界面活性剤を含まない長期間安定な添加剤に関する。 The present invention relates to a long-term stable additive free of fluorosurfactants for chromium electrolytes that reduces surface tension and thus improves the chromium deposition process.
Description
本発明は，クロム電解質用の添加剤の分野，特にクロム電解質に添加する界面活性剤の分野，およびポリマー金属化用の添加剤の分野に関する。 The present invention relates to the field of additives for chromium electrolytes, in particular the field of surfactants added to chromium electrolytes, and the field of additives for polymer metallization.
電気化学的クロムめっき法は，典型的にはクロム電解質中で高濃度の攻撃的なクロム酸により行われ，この方法に関しては，攻撃的な噴霧ミストの形成を防止するために，広範な種類の様々な添加剤が提案されている。しかしながら，一方では望ましい特性を有し，他方ではクロムめっき法における攻撃的な条件に耐えられる化合物を見いだすことは，実用上困難であることが知られている。 Electrochemical chrome plating is typically performed with a high concentration of aggressive chromic acid in the chrome electrolyte, and for this method a wide variety of types are used to prevent the formation of aggressive spray mist. Various additives have been proposed. However, it is known that it is practically difficult to find a compound that has desirable characteristics on the one hand and can withstand aggressive conditions in the chromium plating method on the other hand.
噴霧ミストを低減させるのに特に適しているものは泡沫形成性湿潤剤であり，これは，表面張力を低下させることにより，噴霧喪失を低下させるのみならず，クロム電解質のエントレインメントも非常に低下させる。この目的のため，広範な種類の様々な製品が提案されており，例としては，パーフルオロアルキルスルホン酸（ＰＦＯＡ）が挙げられる。これらの製品はまた，クロム酸の強い酸化特性に対して安定である。しかしながら，これらの使用には問題があり，多くの用途では既に禁止されている。これらのフッ素界面活性剤は，光分解，加水分解，酸化的または還元的変質を何ら受けないため，生物分解性ではない。これらは，好気的にも嫌気的にも生物分解されない。パーフルオロアルキルスルホン酸は，その物理化学的特性のため，最終代謝産物として残留し，それ以上分解されない。 Particularly suitable for reducing spray mists are foam-forming wetting agents, which not only reduce spray loss by reducing surface tension, but also greatly reduce chromium electrolyte entrainment. Let A wide variety of products have been proposed for this purpose, an example being perfluoroalkylsulfonic acid (PFOA). These products are also stable against the strong oxidizing properties of chromic acid. However, their use has problems and is already prohibited for many uses. These fluorosurfactants are not biodegradable because they do not undergo any photolysis, hydrolysis, oxidative or reductive alteration. They are not biodegraded aerobically or anaerobically. Perfluoroalkylsulfonic acid remains as a final metabolite due to its physicochemical properties and is not further degraded.
ＤＥ１０３４９４５は，添加剤としてのアルキルメチルスルホネートを提案しており，これは，界面活性剤の特性を有し，同時にクロム層の平滑化に関してプロセスを改良する効果を有すると述べられている。しかしながら，これらの添加剤は，クロムめっき法の過程で非常に短い時間の間に分解するため，実用には適していない。 DE 1034945 proposes alkyl methyl sulfonates as additives, which are stated to have surfactant properties and at the same time have the effect of improving the process with respect to the smoothing of the chromium layer. However, these additives are not suitable for practical use because they decompose in a very short time during the chromium plating process.
したがって，本発明は，上述の欠点の少ないクロム電解質用の添加剤を見いだすことを目的とする。 Accordingly, the object of the present invention is to find an additive for chromium electrolytes with less of the above-mentioned drawbacks.
この目的は，請求項１記載の添加剤により達成される。すなわち，本発明は，添加剤，特にクロム電解質用の平滑添加剤を提供し，この添加剤は，０．１ｇ／ｌの添加剤および２５０ｇ／ｌのクロム酸を含むクロム酸溶液が，３０ｍＮ／ｍ以下の表面張力を有し，かつ，２７０ｇ／ｌのクロム酸を含むクロム酸溶液中で，０．１ｇ／ｌの添加剤が４５℃で，および６０００Ａｈの通電（ｃｈａｒｇｅ ｐａｓｓａｇｅ）で４時間以上の安定性を有することを特徴とする。 This object is achieved by the additive according to claim 1. That is, the present invention provides an additive, particularly a smoothing additive for chromium electrolytes, which comprises a chromic acid solution containing 0.1 g / l additive and 250 g / l chromic acid, at 30 mN / l. In a chromic acid solution having a surface tension of less than m and containing 270 g / l of chromic acid, 0.1 g / l of additive is at 45 ° C. and over 6000 Ah charge passage for 4 hours or more It is characterized by having the following stability.
本発明において“添加剤”との用語は，個々の物質および物質の混合物のいずれにも関連しうることに留意すべきである。ただし，読みやすさおよび明確性の理由から，本明細書中では“添加剤”は単数として表記する。用いられる添加剤が物質の混合物である場合，それぞれの場合において，物質の混合物は記述される特性をもつが，混合物の個々の成分もまた記述される特性をもつことを意味する。 It should be noted that in the present invention the term “additive” can relate to both individual substances and mixtures of substances. However, for reasons of readability and clarity, “additive” is referred to as a singular in this specification. If the additive used is a mixture of substances, it means in each case that the mixture of substances has the properties described, but that the individual components of the mixture also have the characteristics described.
本発明の文脈においては，“安定性”とは，クロム電解質の化学的に厳しい条件下で，表面張力に関して添加剤の効力が持続することを意味する。 In the context of the present invention, “stability” means that the additive's efficacy with respect to surface tension persists under the chemically severe conditions of the chromium electrolyte.
特に，本発明の文脈においては，所定の期間にわたる“安定性”とは，その期間の間に表面張力が５ｍＮ／ｍより大きく増加しないことを意味する。 In particular, in the context of the present invention, “stability” over a period of time means that the surface tension does not increase more than 5 mN / m during that period.
特に，本発明の文脈においては，“クロム電解質”，および／または“クロム酸作業溶液”とは，触媒および／またはさらに別の酸を含むクロム電解質またはクロム酸溶液を意味すると理解される。 In particular, in the context of the present invention, “chromium electrolyte” and / or “chromic acid working solution” are understood to mean a chromium electrolyte or chromic acid solution containing a catalyst and / or further acids.
驚くべきことに，本発明の最多用途であるクロムめっき法作業用のクロム酸溶液にかかる添加剤を加えたときに，下記の利点の少なくとも１つ，通常は２以上を達成しうることが見いだされた：
− 本発明の添加剤を使用すると，クロム電解質の作業が持続的に改良される。
− 添加剤の使用は，顕著により小さいガスバブルの形成につながり，これは有害物質の放出の劇的な低下を伴う。
− 同様に，エントレインメント喪失を顕著に低下させることができる。
− プロセスによって異なるが，添加剤を用いると多くの用途において電解質の分散性が改良される。
− 添加剤は，硬度，網目状亀裂，構造などの層特性に関しても，層の特性に有害な影響を与えない。
Surprisingly, it has been found that at least one of the following advantages, usually two or more, can be achieved when the additive is added to the chromic acid solution for the most versatile chrome plating process of the present invention. Was:
-The use of the additive according to the invention continuously improves the work of the chromium electrolyte.
-Use of additives leads to the formation of significantly smaller gas bubbles, which is accompanied by a dramatic reduction in the release of harmful substances.
-Similarly, loss of entrainment can be significantly reduced.
-Depending on the process, the use of additives improves the dispersibility of the electrolyte in many applications.
-Additives do not have a detrimental effect on layer properties, even with regard to layer properties such as hardness, network cracks and structure.
０．１ｇ／ｌの添加剤および２５０ｇ／ｌのクロム酸を含むクロム酸溶液は，好ましくは２８ｍＮ／ｍ以下の，さらに好ましくは２５ｍＮ以下の表面張力を有する。 A chromic acid solution containing 0.1 g / l additive and 250 g / l chromic acid preferably has a surface tension of 28 mN / m or less, more preferably 25 mN or less.
０．１ｇ／ｌの添加剤および４００ｇ／ｌのクロム酸を含むクロム酸溶液は，好ましくは，３５ｍＮ／ｍ以下の，さらに好ましくは３０ｍＮ／ｍ以下の表面張力を有する。 A chromic acid solution containing 0.1 g / l additive and 400 g / l chromic acid preferably has a surface tension of 35 mN / m or less, more preferably 30 mN / m or less.
４５℃で０．１ｇ／ｌの添加剤および２７０ｇ／ｌのクロム酸を含むクロム電解質は，好ましくは，８時間以上の，さらに好ましくは１２時間以上の安定性を有する。 A chromium electrolyte containing 0.1 g / l additive and 270 g / l chromic acid at 45 ° C. preferably has a stability of 8 hours or more, more preferably 12 hours or more.
本発明の好ましい態様においては，添加剤はフッ素界面活性剤を含まない。このことは，特に，添加剤が有機フッ素化合物を全く含まないか，または添加剤中の有機フッ素化合物の割合が検出限界未満であることを意味することが理解される。 In a preferred embodiment of the invention, the additive does not contain a fluorosurfactant. This is understood in particular to mean that the additive contains no organofluorine compound or that the proportion of the organofluorine compound in the additive is below the detection limit.
本発明の好ましい態様においては，添加剤は生物分解性である。このことは，特に，ＯＥＣＤ分類にしたがって，８日後のスクリーニング試験において，添加剤の９９．５％以上，好ましくは９９．８％以上が分解されていることを意味することが理解される。このような添加剤は，多くの用途において，環境汚染を防止するための費用を最小にするか，あるいは完全に不要とすることに寄与する。 In a preferred embodiment of the invention, the additive is biodegradable. This is understood to mean that, in particular, according to the OECD classification, 99.5% or more, preferably 99.8% or more of the additives are degraded in the screening test after 8 days. Such additives contribute to minimizing or eliminating the need to prevent environmental pollution in many applications.
０．１ｇ／ｌの添加剤および２５０ｇ／ｌのクロム酸を含むクロム電解質は，好ましくは，３０Ａ／ｄｍ２以上６０Ａ／ｄｍ２未満，さらに好ましくは４０Ａ／ｄｍ２以上５０Ａ／ｄｍ２未満の電流密度を有する。 The chromium electrolyte containing 0.1 g / l additive and 250 g / l chromic acid preferably has a current of 30 A / dm 2 or more and less than 60 A / dm 2 , more preferably 40 A / dm 2 or more and less than 50 A / dm 2. Has a density.
０．２ｇ／ｌの添加剤および３５０−４００ｇ／ｌのクロム酸を含むクロム電解質は，好ましくは，５Ａ／ｄｍ２以上２５Ａ／ｄｍ２未満，さらに好ましくは８Ａ／ｄｍ２以上２０Ａ／ｄｍ２未満の電流密度を有する。 The chromium electrolyte containing 0.2 g / l additive and 350-400 g / l chromic acid is preferably 5 A / dm 2 or more and less than 25 A / dm 2 , more preferably 8 A / dm 2 or more and less than 20 A / dm 2 Current density of
本発明の好ましい態様においては，添加剤は，長鎖アルキルモノスルホン酸，長鎖アルキルジスルホン酸，長鎖アルキルポリスルホン酸，長鎖アルキルモノスルホン酸の塩，長鎖アルキルジスルホン酸の塩，長鎖アルキルポリスルホン酸の塩，およびこれらの混合物からなる群より選択される物質を含む。 In a preferred embodiment of the present invention, the additive comprises a long-chain alkyl monosulfonic acid, a long-chain alkyl disulfonic acid, a long-chain alkyl polysulfonic acid, a long-chain alkyl monosulfonic acid salt, a long-chain alkyl disulfonic acid salt, a long-chain A substance selected from the group consisting of salts of alkylpolysulfonic acids and mixtures thereof.
この文脈において，“長鎖”とは，Ｃ４およびそれ以上を意味することが理解される。長鎖アルキルラジカルは，好ましくは分枝していないが，分枝鎖のアルキル−モノ−，−ジ−および−ポリ−スルホン酸およびこれらの塩を使用することも可能である。 In this context, “long chain” is understood to mean C 4 and above. Long chain alkyl radicals are preferably not branched, but it is also possible to use branched chain alkyl-mono-, -di- and -poly-sulfonic acids and their salts.
本発明の好ましい態様において用いられる塩は，アルカリ金属塩，アルカリ土類金属塩，ＮＨ４ ＋塩，ＮＲ４ ＋塩（Ｒ＝アルキル）およびこれらの混合物である。 Salts used in preferred embodiments of the present invention are alkali metal salts, alkaline earth metal salts, NH 4 + salts, NR 4 + salts (R = alkyl) and mixtures thereof.
本発明の好ましい態様においては，添加剤は，少なくとも１つの成分として，化合物ＣＨ３（ＣＨ２）ｎＳＯ３Ｈまたはその塩（ｎは１０以上１８以下である）を含む。実用上は，これらの化合物はしばしば特に高い安定性を有しており，この観点において好ましい。 In a preferred embodiment of the present invention, the additive contains the compound CH 3 (CH 2 ) n SO 3 H or a salt thereof (n is 10 or more and 18 or less) as at least one component. In practice, these compounds often have a particularly high stability and are preferred in this respect.
より好ましくは，添加剤は，少なくとも１つの成分として，化合物ＣＨ３（ＣＨ２）ｎＳＯ３Ｈまたはその塩（ｎは１２以上１７以下である）を含み；さらに好ましくは，添加剤は，少なくとも１つの成分として，化合物ＣＨ３（ＣＨ２）ｎＳＯ３Ｈまたはその塩（ｎは１４以上１６以下である）を含む。 More preferably, the additive comprises, as at least one component, the compound CH 3 (CH 2 ) n SO 3 H or a salt thereof (n is 12 or more and 17 or less); more preferably, the additive is at least One component includes the compound CH 3 (CH 2 ) n SO 3 H or a salt thereof (n is 14 or more and 16 or less).
本発明はまた，本発明の添加剤をクロム電解質における平滑剤として使用することに関する。本発明の好ましい態様においては，添加剤の濃度は，０．０５ｇ／ｌ以上２０ｇ／ｌ以下であり，より好ましくは０．１ｇ／ｌ以上１０ｇ／ｌ以下であり，最も好ましくは１ｇ／ｌ以上３ｇ／ｌ以下である。 The invention also relates to the use of the additive of the invention as a smoothing agent in a chromium electrolyte. In a preferred embodiment of the present invention, the concentration of the additive is 0.05 g / l or more and 20 g / l or less, more preferably 0.1 g / l or more and 10 g / l or less, and most preferably 1 g / l or more. 3 g / l or less.
本発明はまた，本発明の添加剤をポリマー媒染剤における添加剤として使用することに関する。本発明者らは，驚くべきことに，本発明の添加剤は，クロム電解質においてのみならずポリマー金属化の前処理においても用いることができることを見いだした。これらの媒染剤においては，添加剤は湿潤効果を有し，クロム酸含有媒染剤の表面張力を低下させることができる。クロム酸ミスト形成およびエントレインメントに対する有益な効果は，クロム電解質について上述した効果に匹敵する。 The invention also relates to the use of the additive of the invention as an additive in a polymer mordant. The inventors have surprisingly found that the additive of the present invention can be used not only in chromium electrolytes but also in pretreatment of polymer metallization. In these mordants, the additive has a wetting effect and can reduce the surface tension of the chromic acid-containing mordant. The beneficial effects on chromate mist formation and entrainment are comparable to those described above for chromium electrolytes.
本発明はまた，少なくとも１つの成分として化合物：
ＣＨ３（ＣＨ２）ｎＳＯ３Ｈ
［式中，ｎは１０以上１８以下であり，より好ましくはｎは１２以上１７以下であり，さらに好ましくはｎは１４以上１６以下である］
またはその塩，またはこれらの混合物を含む添加剤をポリマー媒染剤中の添加剤として使用することに関する。
The present invention also provides a compound as at least one component:
CH 3 (CH 2 ) n SO 3 H
[Wherein, n is 10 or more and 18 or less, more preferably n is 12 or more and 17 or less, and more preferably n is 14 or more and 16 or less]
Or the use of an additive comprising a salt thereof or a mixture thereof as an additive in a polymer mordant.
本発明にしたがって用いるべき上述の成分，および特許請求され実施例に記載されている成分は，そのサイズ，三次元構造，材料の選択および技術的設計について特別の条件はなく，使用の技術分野で知られる選択基準を非限定的に用いることができる。 The above-mentioned components to be used in accordance with the present invention, and those claimed and described in the examples, have no special requirements for their size, three-dimensional structure, material selection and technical design, and in the technical field of use. Known selection criteria can be used without limitation.
本発明の主題のさらなる詳細な説明，特徴および利点は，従属項ならびに下記の本発明の実施例から明らかである。実施例は本発明の添加剤の１つの使用法を詳細に説明するが，これは純粋に例示的なものであり，限定ではない。 Further details, features and advantages of the inventive subject matter are evident from the dependent claims and from the following examples of the invention. The examples illustrate in detail the use of one of the additives of the present invention, but this is purely exemplary and not limiting.
実施例Ｉ：
４００ｇ／ｌのクロム酸，５ｇ／ｌのリン酸，３ｇ／ｌの硝酸カリウム，３ｇ／ｌのアルカリ土類フッ化物（例えば，セリウム，ランタン），および本発明の添加剤として２ｇ／ｌのペンタデカンスルホン酸ナトリウムを入れた浴中で，温度２０−２５℃および電流密度２０Ａ／ｄｍ２で，黒クロムコーティングを行った。
Example I:
400 g / l chromic acid, 5 g / l phosphoric acid, 3 g / l potassium nitrate, 3 g / l alkaline earth fluoride (eg cerium, lanthanum), and 2 g / l pentadecanesulfone as an additive of the present invention Black chromium coating was performed in a bath containing sodium acid at a temperature of 20-25 ° C. and a current density of 20 A / dm 2 .
本発明の添加剤を加えることにより，表面張力を２９．８ｍＮ／ｍまで低下させることができた。 By adding the additive of the present invention, the surface tension could be reduced to 29.8 mN / m.
続く実験においては，析出したクロム層が非常に均一な外観を有することが認められた。特に，電解質の分散性が改良された。いくつかのシートを試験したところ，ハルセルによる対応する試験によれば，いくつかのシートではクロム層の分散性が平均で１．０−１．５ｃｍ改良された。 In subsequent experiments, it was found that the deposited chromium layer had a very uniform appearance. In particular, the dispersibility of the electrolyte has been improved. Several sheets were tested and, according to the corresponding test by Hullcell, some sheets improved the dispersibility of the chromium layer on average by 1.0-1.5 cm.
材料および方法
表面張力は，Ｋ８張力計（Ｋｒｕｅｓｓ Ｈａｍｂｕｒｇ）を用いて測定した。ユニットはＤｕＮｏｕｙリング法により動作させた。リングによって液体薄層を引き上げる力を測定した。リングと表面が接触しているかぎり液体を持ち上げる。トーションバランスを用いて，白金リングを持ち上げるのに必要な力を測定した。この力はリングが液体から遠くに引かれれば引かれるほど大きくなる。最大の力を適用した点において，液体薄層が壊れた時，力が平衡しており，ここから液体の表面張力を計算することができる。リングの形態は製造元による装置特異的検量線を用いて考慮に入れた。
Materials and Methods The surface tension was measured using a K8 tensiometer (Kruess Hamburg). The unit was operated by the DuNouy ring method. The force pulling up the thin liquid layer by the ring was measured. Lift the liquid as long as the ring and surface are in contact. Using the torsion balance, the force required to lift the platinum ring was measured. This force increases as the ring is pulled away from the liquid. At the point where the maximum force is applied, when the liquid thin layer breaks, the force is balanced, from which the surface tension of the liquid can be calculated. The form of the ring was taken into account using a manufacturer specific calibration curve by the manufacturer.
電流密度は，電流計を用いて電流を測定し，既知の表面形状のクロムめっきされるべき部材を基準として測定した。 The current density was measured by using an ammeter to measure the current and using a member having a known surface shape to be chrome plated as a reference.
電解質の分散性は，ハルセル中の電解質を用いる試験の後に，シートの評価により判定した。クロム層の分散は，シートをテストランに通した後にシート上の被覆された表面の拡がりを測定することにより判定した。測定は定規を用いて行った。一般に，信頼性のある平均値を得るために，数枚のシートを被覆し，同じ条件で測定した。
The dispersibility of the electrolyte was determined by evaluating the sheet after a test using the electrolyte in the hull cell. The dispersion of the chromium layer was determined by measuring the spread of the coated surface on the sheet after passing the sheet through a test run. The measurement was performed using a ruler. In general, to obtain a reliable average value, several sheets were coated and measured under the same conditions.
Claims (9)
Use of the additive according to any one of claims 1-6 as an additive in a polymer mordant for pretreatment of polymer metallization.
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|---|---|---|---|
| DE102006042076.4 | 2006-09-05 | ||
| DE102006042076A DE102006042076A1 (en) | 2006-09-05 | 2006-09-05 | A new additive for chromium electrolytes |
| PCT/EP2007/059308 WO2008028932A1 (en) | 2006-09-05 | 2007-09-05 | Additive for chromic acid applications |
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| JP5588677B2 JP5588677B2 (en) | 2014-09-10 |
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| US (2) | US20080142372A1 (en) |
| EP (1) | EP2061916A1 (en) |
| JP (1) | JP5588677B2 (en) |
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| AU (1) | AU2007293648A1 (en) |
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| DE102011102052A1 (en) | 2011-05-19 | 2012-11-22 | Anke Gmbh & Co. Kg | Wetting agent for electrolytic application and its use |
| US9771661B2 (en) * | 2012-02-06 | 2017-09-26 | Honeywell International Inc. | Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates |
| TWI456093B (en) * | 2012-06-26 | 2014-10-11 | Dexnano Chemicals Co Ltd | Method for black chromium oxide and black chromium oxide electroplating layer thereof |
| ES2766775T3 (en) * | 2013-09-05 | 2020-06-15 | Macdermid Enthone Inc | Aqueous electrolyte composition that has reduced air emission |
| US10087540B2 (en) | 2015-02-17 | 2018-10-02 | Honeywell International Inc. | Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same |
| CN105177640A (en) * | 2015-08-04 | 2015-12-23 | 重庆立道表面技术有限公司 | Efficient high-performance and high-hardness chromium plating process |
| CN110565124A (en) * | 2019-08-05 | 2019-12-13 | 宣城金诺模塑科技有限公司 | Chromium plating solution for automobile ornaments and electroplating method thereof |
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- 2007-09-05 MX MX2009002410A patent/MX2009002410A/en unknown
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- 2007-09-05 AU AU2007293648A patent/AU2007293648A1/en not_active Abandoned
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| JP5588677B2 (en) | 2014-09-10 |
| DE102006042076A1 (en) | 2008-03-20 |
| BRPI0716255A2 (en) | 2013-09-03 |
| MX2009002410A (en) | 2009-05-28 |
| WO2008028932A1 (en) | 2008-03-13 |
| US20080142372A1 (en) | 2008-06-19 |
| NO20091361L (en) | 2009-05-28 |
| EA200970249A1 (en) | 2009-08-28 |
| RS20090102A (en) | 2010-08-31 |
| SG174763A1 (en) | 2011-10-28 |
| EA016032B1 (en) | 2012-01-30 |
| CA2662238A1 (en) | 2008-03-13 |
| EP2061916A1 (en) | 2009-05-27 |
| KR20090075677A (en) | 2009-07-08 |
| US20110290658A1 (en) | 2011-12-01 |
| IL197411A0 (en) | 2009-12-24 |
| ZA200901539B (en) | 2010-02-24 |
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