GB2123711A - Method of providing surface protection to articles having a metallic or ceramic surface - Google Patents

Method of providing surface protection to articles having a metallic or ceramic surface Download PDF

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Publication number
GB2123711A
GB2123711A GB08317670A GB8317670A GB2123711A GB 2123711 A GB2123711 A GB 2123711A GB 08317670 A GB08317670 A GB 08317670A GB 8317670 A GB8317670 A GB 8317670A GB 2123711 A GB2123711 A GB 2123711A
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United Kingdom
Prior art keywords
coating composition
silica
range
coating
article
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.)
Granted
Application number
GB08317670A
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GB8317670D0 (en
GB2123711B (en
Inventor
Hachiro Kushida
Toshio Murata
Nobuo Ito
Yoshitsugu Imazawa
Kenji Irie
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.)
Citizen Watch Co Ltd
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Citizen Watch Co Ltd
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 Citizen Watch Co Ltd filed Critical Citizen Watch Co Ltd
Publication of GB8317670D0 publication Critical patent/GB8317670D0/en
Publication of GB2123711A publication Critical patent/GB2123711A/en
Application granted granted Critical
Publication of GB2123711B publication Critical patent/GB2123711B/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26Silicates of the alkali metals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00Cases
    • G04B37/22Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/223Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Materials For Medical Uses (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

An article having a metallic or ceramic surface, such as a watch case, or watch strap, has its surface protected by a clear glassy coating to prevent scratching or chemical damage, applied by coating the surface with an aqueous coating composition containing waterglass dissolved therein and silica sol dispersed therein in proportions such that the molar ratio of silica to sodium oxide i.e. SiO2/Na2O, in the coating composition is in the range from 4 to 10. This is followed by drying, preferably with heating to give a clear and hard glassy thin film on the surface which is remarkably resistant to water, sweat and scratch formation and is insusceptible to staining.

Description

SPECIFICATION Method of providing surface protection to articles having a metallic or ceramic surface The present invention relates to a method of providing surface protection to an article having a metallic or ceramic surface, for example watch cases, or personal ornaments. The method is effective to provide protection for example against stains and scratches and involves forming a thin clear film on the surface.
An important problem with personal ornaments, such as watch cases, watch straps, bracelets, necklaces, earrings, pendants, stick pins and the like, is to maintain the beauty of appearance of the ornamental articles lastingly since these articles, which are usually made of a metal or alloy, of which the surface may be converted to a ceramic material by a suitable surface treatment, are commonly used in a contaminating environment or under conditions in which scratches or other mechanical damage are more or less unavoidable on the surface of the ornamental article even with the utmost care of the wearer and the beauty of the article once lost by stains and scratches can only be regained with difficulty.
Accordingly, several methods have been proposed to provide a protective surface film on such ornamental articles with the object of protecting the article from stains and scratches. Unfortunately, all of the hitherto proposed protective films are unsatisfactory in one or other respects. The protective surface film should satisfy the requirements not only of insusceptibility to stains and high mechanical and chemical strengths to withstand scratches and the influence of various chemicals but also of clarity to enable the beauty of the surface of the article to be seen therethrough. A further requirement of the surface film lies in ease of the process for its formation.
In particular, watch cases and watch straps made of stainless steel or a titanium based alloy are susceptible to staining by fingerprints or greasiness on the surfaces which are finished by honing treatment and the surfaces with such stains can be cleaned only with extreme difficulty so that the commercial value of such stained articles is greatly reduced due to the unpleasantness felt by the wearer. A conventional method for solving this problem is to provide a coating film to the surface with a fluorocarbon polymer-containing coating composition (see, for example, Japanese patent Kokai 52-129469) but the beauty of the ornamental article is greatly decreased thereby due to the poor clarity of the fluorocarbon polymer-containing coating film which is also somewhat defective in respect of its poor resistance against the attack of organic solvents.
Therefore, it has long been desired in the watch industry and other fields of fine metalworks to develop a convenient and reliable method for providing surface protection to an ornamental article having a metallic or ceramic surface free from the above described problems in the prior art methods.
To this end, the inventors have conducted extensive investigations with the object of solving the above described problem. These investigations have given rise to the present invention according to which surface protection is provided to an article having a metallic surface by a method which comprises the steps of: (a) coating the surface with an aqueous coating composition containing sodium silicate dissolved therein and silica sol dispersed therein in proportions such that the molar ratio of silica to sodium oxide (SiO2/Na2O) is in the range of from 4 to 10; and (b) drying the thus coated surface.
The drying is preferably effected by heating or is followed by heating at 100--2500C for a length of time of from 10 to 120 minutes to form a hard and clear glassy film on the surface.
As is understood from the above description, the essential ingredients in the aqueous coating composition are sodium silicate and silica sol. The sodium silicate is a material readily available on the market under the name of waterglass in the form of an aqueous solution and expressed by the chemical formula Na2O nSiO2, in which n is a positive number, usually, in the range from 2 to 4. Several grades of water glasses are sold on the market with varied values of the number n. For example, the No. 3 grade waterglass specified in JIS (Japanese Industrial Standard) contains 10% by weight of sodium oxide Na2O and 30% by weight of silica SiO2.On the other hand, the silica sol for the preparation of the coating composition used in the inventive method is a stable colloidal dispersion of hydrated silica in water as the dispersant and readily available on the market. Commercial products of silica sol contain several tens of %, e.g. 30%, by weight of colloidal silica depending on the grade and also contain a trace amount, usually 0.01% by weight or smaller as Na2O, of alkali as an impurity.
The aqueous coating composition used in the inventive method can be prepared by merely blending a waterglass and a silica sol in such a proportion that the molar ratio of silica to sodium oxide (SiO2/Na20) in the resultant composition is in the range from 4 to 1 0. The molar ratio can be easily calculated by knowing the solid content and the silica/sodium oxide ratio in the waterglass and the solid content of the silica sol, the trace amount of sodium oxide in the latter being neglected. It is preferable that the silica content in the thus prepared aqueous coating composition is in the range from 3 to 30% by weight in consideration of the convenience in the coating procedure as well as the thickness of the coating film on the surface of the ornamental article formed therewith.The method of coating with the aqueous coating composition is not particularly limitative and may be performed by any conventional procedures including spraying, ultrasonic atomizing spray, dipping under reduced pressure and the like.
The thus coated article is then dried and, preferably, further subjected to a heat treatment at 100 to 2500C for 10 to 120 minutes. It is of course optional or preferable that drying is performed by heating at the above mentioned temperature followed by the heat treatment for a length of time mentioned above. The solid content in the aqueous coating composition is solidified by this heating process into a clear and hard glassy coating film with good adhesion to the surface. It is preferable that the heat treatment is performed in an atmosphere of carbon dioxide or air enriched with carbon dioxide so that the time for the treatment can be greatly reduced.
The clear and hard glassy film formed on the surface of the ornamental article may have sufficient clarity, hardness, water resistance, weathering resistance and strong adhesion to the surface provided that the SiO2/Na2O molar ratio in the aqueous coating composition is in the range from 4 to 10 or, preferably, from 5 to 10 or, more preferably, from 5 to 7. When this molar ratio is outside the above range, the resultant surface film cannot be imparted with satisfactory properties suitable for practical use.
Following Table 1 gives the results of the evaluation of the water resistance, clarity and staininsusceptibility of the protective surface films according to the inventive method. Thus, a stainless steelmade watchcase was coated by spraying with an aqueous coating composition with varied formulation relative to the SiO2/Na20 molar ratio by use of a waterglass containing 10% by weight of Na2O and 30% by weight of SiO2 and a silica sol containing 30% by weight of SiO2 followed by drying and heating at 1 500C for 10 minutes to form a surface coating film of about 1 to 3 ym thickness. The water resistance of the coating film was evaluated by the visual examination of the condition of permeation of water into the coating film after dipping the watchcase in water for a while.The clarity of the coating film was also evaluated by the visual comparison and the stain-insusceptibility was evaluated by the visual examination of oil stain left on the surface smeared with a silicone fluid and then wiped off with a cloth.
The results are expressed in four grades of A (excellent), B (good), C (fair) and D (poor). As is understood from the results shown in Table 1 , these three properties are simultaneously satisfied practically only when the SiO2/Na2O molar ratio is in the range from 4 to 10 or, preferably, from 5 to 1 0.
TABLE 1
Blending ratio, % by weight SiO2/Na2O Stain Water- Silica molar Water insuscepti glass sol ratio resistance Clarity bility 100 0 3.10 D A A 90 10 3.44 D A A 80 20 3.88 C A A 70 30 4.43 B A A 60 40 5.17 A A A 50 50 6.20 A A A 40 60 7.75 A A A 30 70 10.3 A C D 20 80 15.2 A D D 10 90 31.0 A D D 0 100 - B D D In particular, the glassy film formed by coating with a coating composition containing waterglass alone is very poor in the water resistance and readily destroyed by moisture such as sweat of the wearer so that no protective effect can be obtained practically. On the other hand, the coating film formed with silica sol alone is very cloudy without clarity as is shown in Table 1 so that beautifulness of the article is lost by coating with such a coating composition.
The thickness of the coating film on an ornamental article should be determined depending on the particular kind and intended use of the article although satisfactory results may be obtained usually with a film thickness in the range from 0.5 to 10 ,um. An excessively large thickness of the coating film is undesirable due to the decrease in the clarity of the coating layer although mechanical strengths of the protective film may be increased by increasing the film thickness.
Following is a further illustration of the inventive method by way of examples. In each of the following examples, coating was performed with four aqueous coating compositions having different SiO2/NaO2 molar ratios of 10, 7, 5 and 3 and the coated articles were evaluated for the water and moisture resistance, resistance against simulated perspiration, clarity, stain-insusceptibility and resistance against scratches to give the results summarized in Table 2 in the four grades of A (excellent), B (good), C (fair) and D (poor). The grade C is acceptable for practical use though dependent on the cases.The simulated perspiration test was performed by haif-dipping the respective articles for 48 hours at room temperature in an aqueous solution containing 9.9 g/liter of sodium chloride NaCI, 0.8 g/liter of sodium sulfide Na2S, 1.7 g/liter of urea (NH2)2CO, 1.7 g/liter of lactic acid CH3CH(OH)COOH and 0.2 ml/liter of concentrated ammonia water and having a pH of 3.0 3.5 followed by visual comparison of the surface conditions of the areas dipped and not dipped in the solution. The tests for the water and moisture resistance, clarity and stain-insusceptibility were undertaken in the same manner as in the tests shown in Table 1. The scratch resistance was determined by use of a Martens scratch hardness tester.As is understood from the results obtained in these examples, the protective effects obtained by coating are particularly remarkable when the SiO2/Na2O molar ratio in the aqueous coating composition is in the range from 4 to 10 or, preferably, from 5 to 10 so that the surface film formed thereby is imparted with outstandingly high resistance against scratch formation. It is of course that the method of the present invention is applicable not only to watchcases and watch straps shown in the examples but also to any other articles having a metallic or ceramic surface of which lastingness of the beautifulness of appearance is of utmost importance.
EXAMPLE 1 A watchcase made of titanium metal was subjected to a honing treatment with #100 to #300 glass beads as the abrasive followed by cleaning with air spray and then coated with- an aqueous coating composition of a varied SiO2/Na2O molar ratio by ultrasonic atomizing spray followed by drying and heating at 1 500C for 10 to 30 minutes to form a hard and clear glassy surface film having a thickness of 3 to 4 Mm.
EXAMPLE 2 A watchcase made of titanium metal was nitrided into titanium nitride on the surface by heating for 20 hours in an atmosphere of nitrogen gas at 8500C. Coating of the thus nitrided watchcases was performed with the aqueous coating compositions in substantially the same manner as in Example 1 to form a hard and glassy surface film having a thickness of 1 to 2 um.
EXAMPLE 3 A back cover member of watchcase made of a stainless steel of SUS 304 grade specified in the JIS was coated with the aqueous coating composition in substantially the same manner as in Example 1 to form a hard and glassy surface film having a thickness of 1 to 2 Mm.
EXAMPLE 4 A watch strap assembled with member pieces of SUS 304 stainless steel coated with a ceramic composite oxide mixture of 60 :40 Al203-TiO2 by flame fusion in a thickness of 30 to 40 Mm was coated with the aqueous coating composition by dipping therein under reduced pressure followed by drying and heating at 1 500C for 10 to 30 minutes to form a hard and glassy surface film of a solemn color tone having a thickness of 5 to 7 4m.
TABLE 2
SiOJNa20 Water and Simulated Overall Example molar moisture perspira- Stain-insus- Scratch evalu No. ratio resistance tion test Clarity ceptibility resistance ation 10 A A C C C C 7 7 A A A A B A 5 B C A A A C 3 C D A A A D 10 A A B B A B 7 A A A A A A 2 5 5 B B A A A B 3 C D A A A D 10 A A C C C C 7 AA A A B A 3 5 BB A A A B A 3 C D A A A D 10 7 A A B A A B 4 5 B C A A A C 3 C D A A A D

Claims (7)

1. A method of providing surface protection to an article having a metallic or ceramic surface which comprises the steps of: (a) coating the surface with an aqueous coating composition containing sodium silicate dissolved therein and silica sol dispersed therein in proportions such that the molar ratio of silica to sodium oxide (SiO2/Na2O) in the aqueous coating composition is in the range of from 4 to 10; and (b) drying the thus coated surface.
2. A method according to claim 1, wherein the molar ratio of silica to sodium oxide is in the range of from 5 to 10.
3. A method according to claim 1 or claim 2, wherein the content of silica in the aqueous coating composition is in the range from 3 to 30% by weight.
4. A method according to any one of claims 1 to 3, wherein the drying of the coated surface in step (b) is performed by, or is followed by, heating the coated article at a temperature in the range of from 100 to 2500C for a length of time of from 10 to 120 minutes.
5. A method according to any one of the preceding claims, wherein the coating in step (a) is performed in such a way as to give a coating thickness in the range of from 0.5 to 10 Mm after step (b).
6. A method according to claim 4 or claim 5 when dependent on claim 4, wherein the heating of the coated article is performed in an atmosphere of carbon dioxide or air enriched with carbon dioxide.
7. A method according to claim 1, substantially as described with reference to any one of Examples 1 to 4 herein.
GB08317670A 1982-07-13 1983-06-29 Method of providing surface protection to articles having a metallic or ceramic surface Expired GB2123711B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57121879A JPS5913076A (en) 1982-07-13 1982-07-13 Surface treatment of personal ornament such as watchcase

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GB8317670D0 GB8317670D0 (en) 1983-08-03
GB2123711A true GB2123711A (en) 1984-02-08
GB2123711B GB2123711B (en) 1985-11-20

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JP (1) JPS5913076A (en)
CH (1) CH653515GA3 (en)
DE (1) DE3324935A1 (en)
GB (1) GB2123711B (en)
HK (1) HK78986A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2582643A1 (en) * 1985-05-29 1986-12-05 Preci Coat Sa Process for protecting the surface of an object by the application of a layer of glass and object obtained by this process
EP0368101A1 (en) * 1988-11-08 1990-05-16 Citizen Watch Co. Ltd. Surface-coated metallic ornamental article and method for the preparation thereof
EP0477362A1 (en) * 1990-03-28 1992-04-01 Ceram Tech International, Limited Room temperature curable surface coatings and method of producing and applying same
EP0842910A2 (en) * 1996-11-14 1998-05-20 Bayerisches Zentrum für Angewandte Energieforschung e.V. ZAE Bayern Binder based on waterglass solution, process for its preparation and its utilisation
US7981830B2 (en) 2005-04-22 2011-07-19 Uhde Gmbh Catalyst-coated support, method for producing the same, reactor comprising the same and use thereof
WO2018095048A1 (en) * 2016-11-23 2018-05-31 叶卫斌 Application of water-soluble silicon glaze

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6282986A (en) * 1985-10-08 1987-04-16 樋口 貞男 Apparatus for sending and polishing pinball
JP2010540778A (en) * 2007-10-05 2010-12-24 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー Improved metal protection

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1485169A (en) * 1973-12-20 1977-09-08 Exxon Research Engineering Co Quick-curing water-resistant silica-or silicate-containing coatings and process of preparing same

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
US2588828A (en) * 1948-12-11 1952-03-11 Johns Manville Composition for and method of producing coated cement surfaces and the product resulting therefrom
DE1015298B (en) * 1954-03-19 1957-09-05 Degussa Process for the surface treatment of metals by applying layers of silicate
US3868258A (en) * 1973-05-31 1975-02-25 Idemitsu Kosar Kabushiki Kaish Fireproofing composition and method
US4120938A (en) * 1973-08-25 1978-10-17 Dynamit Nobel Aktiengesellschaft Aqueous solutions of alkali polysilicates
JPS52129469A (en) * 1976-03-24 1977-10-29 Seiko Epson Corp Wristwatch case

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1485169A (en) * 1973-12-20 1977-09-08 Exxon Research Engineering Co Quick-curing water-resistant silica-or silicate-containing coatings and process of preparing same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2582643A1 (en) * 1985-05-29 1986-12-05 Preci Coat Sa Process for protecting the surface of an object by the application of a layer of glass and object obtained by this process
EP0368101A1 (en) * 1988-11-08 1990-05-16 Citizen Watch Co. Ltd. Surface-coated metallic ornamental article and method for the preparation thereof
EP0477362A1 (en) * 1990-03-28 1992-04-01 Ceram Tech International, Limited Room temperature curable surface coatings and method of producing and applying same
EP0477362A4 (en) * 1990-03-28 1993-01-13 Ceram Tech International, Limited Room temperature curable surface coatings and method of producing and applying same
US5330794A (en) * 1990-03-28 1994-07-19 Ceram Tech International, Ltd. Room temperature curable surface coatings and methods of producing and applying same
EP0842910A2 (en) * 1996-11-14 1998-05-20 Bayerisches Zentrum für Angewandte Energieforschung e.V. ZAE Bayern Binder based on waterglass solution, process for its preparation and its utilisation
EP0842910A3 (en) * 1996-11-14 1998-12-16 Bayerisches Zentrum für Angewandte Energieforschung e.V. ZAE Bayern Binder based on waterglass solution, process for its preparation and its utilisation
US7981830B2 (en) 2005-04-22 2011-07-19 Uhde Gmbh Catalyst-coated support, method for producing the same, reactor comprising the same and use thereof
US8227034B2 (en) 2005-04-22 2012-07-24 Evonik Degussa Gmbh Catalyst-coated support, method for producing the same, reactor comprising the same and use thereof
WO2018095048A1 (en) * 2016-11-23 2018-05-31 叶卫斌 Application of water-soluble silicon glaze

Also Published As

Publication number Publication date
GB8317670D0 (en) 1983-08-03
HK78986A (en) 1986-10-24
JPS6319229B2 (en) 1988-04-21
DE3324935A1 (en) 1984-01-19
JPS5913076A (en) 1984-01-23
CH653515GA3 (en) 1986-01-15
GB2123711B (en) 1985-11-20

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Effective date: 19980629