WO1983003253A1 - A non-abrasive metal cleaning agent - Google Patents

A non-abrasive metal cleaning agent Download PDF

Info

Publication number
WO1983003253A1
WO1983003253A1 PCT/SE1983/000075 SE8300075W WO8303253A1 WO 1983003253 A1 WO1983003253 A1 WO 1983003253A1 SE 8300075 W SE8300075 W SE 8300075W WO 8303253 A1 WO8303253 A1 WO 8303253A1
Authority
WO
WIPO (PCT)
Prior art keywords
polish
weight
copper
cleaning agent
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/SE1983/000075
Other languages
French (fr)
Inventor
Jan-Olof Bertil Eriksson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to AT83900857T priority Critical patent/ATE15221T1/en
Priority to DE8383900857T priority patent/DE3360642D1/en
Publication of WO1983003253A1 publication Critical patent/WO1983003253A1/en
Priority to DK503783A priority patent/DK503783A/en
Priority to NO834032A priority patent/NO163016C/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/04Aqueous dispersions

Definitions

  • the present invention relates to a non-abrasive metal polish or cleaning agent for objects, particularly for cl eaning and shining
  • polishes have long been usual to polish household objects having copper and silver surfaces and also different chromium-coated objects, with one abrasive-containing polish or the other, the discolouring film being worn away to a greater or lesser extent, often together with a rela ⁇ tively substantial layer of the actual surface metal.
  • these polishes often contain dissolving agents, such as ammonia water or carboxylic acid.
  • dissolving agents such as ammonia water or carboxylic acid.
  • SE-C-167770 describes a polish or cleaning agent in paste form in which the dissolving, agent is sulphuric acid and which also contains a thiourine sub ⁇ stance, which is said to act as a reductant which facilitates removal of oxide films.
  • the invention is based on the surprising synergistic effect obtained when the dissolving agent used in the cleaning agent or polish is nitric acid and when an inhibiting com ⁇ ponent of thiourea or a deriative thereof is present at the same time, in a weight surplus relative to the acid.
  • the polish according to the invention is characterized in that it comprises an aqueous solution containing 1 - 3% by weight nitric acid and 5 - 10% by weight of thiourea or a derivative thereof.
  • the amount of nitric acid above is calculated as 100% HNO , and hence the amount of nitric acid -charged must be adapted to the concentration of the acid.
  • 20 ml of concentrated nitric acid must be added to 1000 ml of water.
  • the dis ⁇ solving effect is substantially lowered, while at concentrations above 3% by weight, the dissolving effect begins to be troublesome, even when an increased amount of organic substance is used.
  • the or ⁇ ganic-substance concentration is also critical, and contents beneath 5% by weight result in the undesirable dissolving of the metal, while contents above about 10% by weight have no additonal effect whatsoever, since the solution is then saturated, and hence any ex ⁇ cess is quite without effect, both economically and technically.
  • the com ⁇ ponent is first stirred into a suitable quantity of water, the water having a temperature of about 60°C.
  • the acid is added.
  • O ⁇ .fPI has none of these negative effects, meaning that the polish can be in contact with the surfaces being cleaned for as long as is required to dissolve the tarnishing coatings, without risk of any metal being dissolved.
  • polish according to the invention has the following advantages over known metal cleaning and polishing substances
  • contact time is not critical, and hence can be selected as re ⁇ quired without risk of attack on the metal;
  • the invention can be modified within the scope of the claims, by adding thereto perfumes or substances which colour the solution in a desired manner. Further, it may be necessary to add a wetting agent, to enable the polish to be more residly rinsed-off after treatment.
  • the polish is pre ⁇ ferably applied to the dirty surface with a wad of cotton wool, and

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Agent non-abrasif de nettoyage ou de polissage de métaux, notamment pour des objets et ornements ménagers ayant des surfaces en cuivre, argent, ou chrome, ou en tout alliage composé de ces métaux, séparés ou tous ensemble. Cet agent de polissage se caractérise en ce qu'il comprend une solution aqueuse contenant 1-3 % en poids d'acide nitrique et 5-10 % en poids de thiourée ou d'un de ses dérivés.Non-abrasive agent for cleaning or polishing metals, in particular for household objects and ornaments having surfaces in copper, silver, or chromium, or in any alloy composed of these metals, separated or all together. This polishing agent is characterized in that it comprises an aqueous solution containing 1-3% by weight of nitric acid and 5-10% by weight of thiourea or of a derivative thereof.

Description

A NOH-ABBASIVE METAL CLEANING AGENT
The present invention relates to a non-abrasive metal polish or cleaning agent for objects, particularly for cl eaning and shining
. i household objects and ornaments, which objects have surfaces of copper, silver or chromium or of any alloy which is comprised pre- dominently of any of these metals, either separately or together.
Objects which have copper silver or chromium surfaces and which are exposed to contaminated air, for example air in large built-up areas or industrial areas, or in the vicinity of such areas, quickly become coated with a discolouring film of various reaction products. At first, this film dulls the surfaces of the objects, and then changes their colour to a darker hue.
It has long been usual to polish household objects having copper and silver surfaces and also different chromium-coated objects, with one abrasive-containing polish or the other, the discolouring film being worn away to a greater or lesser extent, often together with a rela¬ tively substantial layer of the actual surface metal. In addition to an abrasive, these polishes often contain dissolving agents, such as ammonia water or carboxylic acid. For example, SE-C-167770 describes a polish or cleaning agent in paste form in which the dissolving, agent is sulphuric acid and which also contains a thiourine sub¬ stance, which is said to act as a reductant which facilitates removal of oxide films. In SE-C-196019 there is described a polish in which the dissolving agent used is carbonic acid. This gives the polish a better effect, especially on silver surfaces, which grow dull when using polishes based on sulphuric acid. One serious disadvantage with l carbonic-acid based polishes, is that the metal surfaces must be rubbed vigourously, particularly in the case of heavily tarnished surfaces. In recent years polishes of the aforementioned kind have been pro¬ posed which lack any form of abrasive and which, in liquid form, are applied to the metal surfaces and there left for a certain length of time, whereafter the polish is rinsed from the surfaces with water, optionally together with a detergent. One such liquid polish, which is based on phosphoric acid, is today sold for polishing silver sur¬ faces. According to the treatment prescribed, the silver surfaces are first immersed in the pol sh solution, and then removed and rinsed. One disadvantage with this polish is that if highly polished, relatively resistant surfaces are desired, it is restricted to silver surfaces. Another, more serious disadvantage is that the length of time over which the object is immersed is critical, since excessive immersion times have negative secondary effects, which mainly mani¬ fest themselves in the form of irregular surface finishes. By polish is meant in this case a shine-improving agent requiring no abrasive. Another commercially available polish of this kind, intended for copper, is based on oxalic acid in combination with a detergent. This polish has a limited use, and can only be used satisfactorily on copper surfaces which are only slightly discoloured.
It has now been found possible to produce a metal cleaning agent which is capable of producing highly polished surfaces while es¬ caping the disadvantages and limitations associated v/ith known polishes of this kind. The invention is based on the surprising synergistic effect obtained when the dissolving agent used in the cleaning agent or polish is nitric acid and when an inhibiting com¬ ponent of thiourea or a deriative thereof is present at the same time, in a weight surplus relative to the acid. The polish according to the invention is characterized in that it comprises an aqueous solution containing 1 - 3% by weight nitric acid and 5 - 10% by weight of thiourea or a derivative thereof. The amount of nitric acid above is calculated as 100% HNO , and hence the amount of nitric acid -charged must be adapted to the concentration of the acid. Thus, in order to obtain the desired concentration, 20 ml of concentrated nitric acid must be added to 1000 ml of water.
At nitric acid concentrations beneath about 1% by weight, the dis¬ solving effect is substantially lowered, while at concentrations above 3% by weight, the dissolving effect begins to be troublesome, even when an increased amount of organic substance is used. The or¬ ganic-substance concentration is also critical, and contents beneath 5% by weight result in the undesirable dissolving of the metal, while contents above about 10% by weight have no additonal effect whatsoever, since the solution is then saturated, and hence any ex¬ cess is quite without effect, both economically and technically.
The good effect obtained with the polish according to the invention must be ascribed to the surprising positive co-action between the specific dissolving component active in the polish, and the weight- -surplus amount of the organic sulphur and nitrogen compound added thereto; in this respect thiourea type compounds have been found particularly effective. This could be due to the comparatively superior chemical ability of nitric acid to dissolve such dis¬ colouring coatings on metal surfaces as coating of oxidic sul¬ phate, carbonates or sulphides forming on copper, silver and chrom¬ ium surfaces.The acid is relatively inert with respect to the ac¬ tual metal itself, so as to be more favourable to the metal than are previously known metal polishes, which should be particularly obvious since the polish contains no abrasive substances capable of attacking the metal when using the polish.
When manufacturing the polish according to the invention, the com¬ ponent is first stirred into a suitable quantity of water, the water having a temperature of about 60°C. When the organic substance has dissolved completely, the acid is added. EXAMPLE
For the purpose of comparing the effect obtained with known polishes with the effect obtained with the polish or cleaning agent according to the invention in treating copper objects discoloured to varying extents, pieces of copper which were only slightly tarnished and very dark, heavily tarnished copper coins were placed in bowls, which were numbered from 1 to 3 and which contained:
1) an aqueous solution of oxalic acid and detergent. This is a product sold at present for treating copper;
2) an aqueous solution of sulphuric acid and-thiourea; and
3) a solution according to the invention containing nitric acid and thiourea.
The following observations were subsequently made. The polish or shine of the slightly tarnished copper pieces was improved in all bowls, althouth the improvement obtained in bowl 1 was much smaller than that obtained in bowls 2 and 3. In the case of the highly dis¬ coloured, brown coins, there was no discernible improvement in the coins placed in bowl 1. After a time lapse of about 60 seconds, a white coating formed on the surfaces of the coins in bowl 2, where¬ after the copper was attacked and began to darken. In bowl 3, con¬ taining polish according to the invention, the surface of the now shiny coins did not become coated, and there was no discernible browning or dissolving of the metal.
The test shows that present day commercially available polishes for cleaning copper objects without vigorous polishing and rubbing being required, have no visible effect on highly browned surfaces. It has also been shown that the choice of acid in the polish is critical. Thus, sulphuric acid causes the surfaces of the object being cleaned to be coated with a white substance and, similar to phosphoric acid, is liable to dissolve metal from the surfaces of the object when said object remains immersed in the polish solution for a prolonged length of time, as previously indicated. The polish according to the invention
Oϊ.fPI has none of these negative effects, meaning that the polish can be in contact with the surfaces being cleaned for as long as is required to dissolve the tarnishing coatings, without risk of any metal being dissolved.
Similar results were obtained when test treating silver coins and also chromium-coated objects.
By way of summary, it can be pointed out that the polish according to the invention has the following advantages over known metal cleaning and polishing substances;
1) acts rapidly;
2) contact time is not critical, and hence can be selected as re¬ quired without risk of attack on the metal;
3) no rubbing, polishing or metal manual action required, other than in the exceptional case of very old, heavily tarnished objects;
4) no visible "dirt residues" are formed;
5) intensive odours are much less noticeable; and
6) can be used for both copper and silver surfaces without requiring the use of abrasives.
As will be understood, the invention can be modified within the scope of the claims, by adding thereto perfumes or substances which colour the solution in a desired manner. Further, it may be necessary to add a wetting agent, to enable the polish to be more residly rinsed-off after treatment.
When using the polish according to the invention, the polish is pre¬ ferably applied to the dirty surface with a wad of cotton wool, and
1 - 1 left to work until the required shine is obtained, whereafter the object is rinsed with luke-warm water and a washing-up liquid. It is recommended that gloves are worn when applying the polish.

Claims

1. A non-abrasive metal polish or cleaning agent for objects, partic¬ ularly household objects and ornaments, having surfaces of copper, silver or chromium or of any alloy which is comprised predominently of any of these metals either separately or together, characterized in that the polish comprises an aqueous solution containing 1 - 3% by weight nitric acid, and 5 - 10% by weight thiourea or a derivative thereof.
2. A polish according to Claim 1, characterized in that the aqueous solution contains about 2% by weight nitric acid and about 8% by weight thiourea.
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0-. v IΛ WIP
PCT/SE1983/000075 1982-03-12 1983-03-08 A non-abrasive metal cleaning agent Ceased WO1983003253A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AT83900857T ATE15221T1 (en) 1982-03-12 1983-03-08 NON-ABRASIVE METAL CLEANER.
DE8383900857T DE3360642D1 (en) 1982-03-12 1983-03-08 A non-abrasive metal cleaning agent
DK503783A DK503783A (en) 1982-03-12 1983-11-03 Non-abrasive metal cleanser
NO834032A NO163016C (en) 1982-03-12 1983-11-04 NON-RUBBER CLEANING, SOIL AND CHROME CLEANER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8201546 1982-03-12
SE8201546-2820312 1982-03-12

Publications (1)

Publication Number Publication Date
WO1983003253A1 true WO1983003253A1 (en) 1983-09-29

Family

ID=20346237

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1983/000075 Ceased WO1983003253A1 (en) 1982-03-12 1983-03-08 A non-abrasive metal cleaning agent

Country Status (6)

Country Link
US (1) US4561895A (en)
EP (1) EP0102986B1 (en)
AU (1) AU1334783A (en)
DE (1) DE3360642D1 (en)
DK (1) DK503783A (en)
WO (1) WO1983003253A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0265578A1 (en) * 1986-10-30 1988-05-04 Jan-Olof Eriksson A non-abrasive polish or cleaning composition and process for its preparation

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200831710A (en) * 2006-09-25 2008-08-01 Mec Co Ltd Metal removing solution and metal removing method using the same
US20150211130A1 (en) * 2013-01-07 2015-07-30 Nitto Boseki Co., Ltd Anti-corrosive agent for washing of metal with acid, detergent solution composition, and method for washing of metal
CN107400892A (en) * 2017-07-26 2017-11-28 江苏盐城环保科技城重金属防治研究中心 A kind of processing method of fine silver product surface discoloration
CN107475731A (en) * 2017-07-26 2017-12-15 江苏盐城环保科技城重金属防治研究中心 A kind of method for removing proof gold product surface erythema

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2132511A (en) * 1934-06-23 1938-10-11 Henkel & Cie Gmbh Cleaning composition and method
GB722255A (en) * 1951-05-11 1955-01-19 Design And Res Ct For The Gold Improvements in or relating to the removal of tarnish from silver
DE968189C (en) * 1941-10-21 1958-01-23 Josefine Jorde Geb Jorde Cleaning and polishing agents and cleaning baths for precious metals

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3196113A (en) * 1965-07-20 Removal of flux from brazed aluminum assemblies
US3228816A (en) * 1962-02-21 1966-01-11 Rohr Corp Process and composition for cleaning and polishing aluminum and its alloys
US4397753A (en) * 1982-09-20 1983-08-09 Circuit Chemistry Corporation Solder stripping solution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2132511A (en) * 1934-06-23 1938-10-11 Henkel & Cie Gmbh Cleaning composition and method
DE968189C (en) * 1941-10-21 1958-01-23 Josefine Jorde Geb Jorde Cleaning and polishing agents and cleaning baths for precious metals
GB722255A (en) * 1951-05-11 1955-01-19 Design And Res Ct For The Gold Improvements in or relating to the removal of tarnish from silver

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0265578A1 (en) * 1986-10-30 1988-05-04 Jan-Olof Eriksson A non-abrasive polish or cleaning composition and process for its preparation

Also Published As

Publication number Publication date
EP0102986B1 (en) 1985-08-28
DK503783D0 (en) 1983-11-03
EP0102986A1 (en) 1984-03-21
AU1334783A (en) 1983-10-24
US4561895A (en) 1985-12-31
DE3360642D1 (en) 1985-10-03
DK503783A (en) 1983-11-03

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