CA1295888C - Paint coated metal materials - Google Patents
Paint coated metal materialsInfo
- Publication number
- CA1295888C CA1295888C CA000507657A CA507657A CA1295888C CA 1295888 C CA1295888 C CA 1295888C CA 000507657 A CA000507657 A CA 000507657A CA 507657 A CA507657 A CA 507657A CA 1295888 C CA1295888 C CA 1295888C
- Authority
- CA
- Canada
- Prior art keywords
- paint
- coated
- metal materials
- paint film
- fluorination
- 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.)
- Expired - Lifetime
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Abstract of the Disclosure:
Paint coated metal materials fluorinated on the surface of the paint film by a plasma treatment, haying excellent resistance to damages and stain as well as excellent corrosion resistance, workability, and paint adhesion. The fluorination is effected by a plasma treatment using mixture gases of fluorine or substances containing fluorine with inert gases.
Paint coated metal materials fluorinated on the surface of the paint film by a plasma treatment, haying excellent resistance to damages and stain as well as excellent corrosion resistance, workability, and paint adhesion. The fluorination is effected by a plasma treatment using mixture gases of fluorine or substances containing fluorine with inert gases.
Description
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- S P E C I F I C A T I O N
Ti tle of the Invention:
PAINT COATED METAL MATERIALS
Field of the Invention:
The present invention relates to paint coated metal materials comprising a metal substrate and a paint film applied on the metal substrate, said paint film having a surface layer containing fluorine atoms and/or perfluoro-alkyl group such as methyl fluoride, ethyl f.luoride.and...
so on introduced therein by a plasma treatment.
Related Prior Arts:
Up to now, paint coated metal materials have been ~ widely used in varlous applications including buildings, bridges, tanks, automobiles, electric appliances and so on, and their main qualities required in these fields of application are to maintain a beautiful surface appearance and to assure good corrosion resistance.
As most of the paint coated metal materials are subjected to mechanical working after the paint coating, the primary requirements of the paint film on the metal substrate are good adheslon, and good workability, particularly press formability, and the secondary requlrements are good corrosion resistance, permanent color and brightness, stain resistance, :and so on depending on the final applications of the products.
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In addition to the above requirements, it is also essential for -the paint coated metal materials that the paint film on the substrate will not be damaged during the mechanical working, especially press forming.
Once damaged, the paint film can no more function as barrier against corrosion, and the corrosion is caused and expands from where the substrate is exposed due to the damage of the paint film, thus markedly shortening the service life of the buildings, bridges, tanks, automobiles, electric appliances and so on, in which the paint coated metal materials are used.
Of the paint coated metal materials, the so-called "pre-coated thin metal sheet" in particular, which is nowadays used in roofings, automobiles and electric appliances, is subjected to severe working, especially press forming, and must show a relatively good elongation property of the paint film on the metal substrate. However, paint films which satisfy the required elongation property are generally soft so that they are easily damaged and poor in the stain resistance.
This incompatibility has long been a problem.
In recent years, as proposed in "Practical Surface Technics" (Jitsumu Hyomen Gijutsu), Vol.30, page 358, 1983, studies have been made on production of paint coated steel sheets having excellent paint film properties by application of the so-called "three-coat system by roll-coating" according to which~an undercoating for improving the adhesion with the metal substrate, an intermediate coating for improving the workability and a top coating for assuring the surface hardness are applied on the metal substrate. This three-coat , ':
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system, however, has a problem that it is technically difficult to maintain the top coat layer to a thickness less than 3 microns so that the hardness of the top coat layer deteriorates the good workability of the intermediate paint coat layer, hence it is very difficult to satisfactorily balance the incompatibility between the surface hardness and the workability which are originally sought for. This is a vital defect of the roll coating method.
Also, Japanese Laid-Open Patent Application No. Sho 59-169851 discloses "a pre-coated steel sheet pre-coated with polyvinyl chloride dispersion paint", according to which an ultraviolet ray curing type clear paint is applied on the polyvinyl chloride dispersion paint applied on the steel substrate and is cured by ultra-violet rays in order to prevent damages of the paint film during the forming of the pre-coat sheet. According to this prior art, the thickness of the ultraviolet ray curing type clear paint is as thick as 200 microns and this method ;
has been limitedly applied to the polyvinyl chloride dis-persion paint pre-coated steel sheets.
Fuxther, it is known to fluorinate the surEace of polymers by a plasma treatment. For example, according to the report by M.Anand et al. (Polymer, 361, Vol.22, 1981), the surface of low-density polyethylene is fluorinated by using a mixture gas of;carbon tetrafluoride, or fluorlne and hellum.
The fluorination of the surface of polymer in this case is only for~the purpose of rendering the polymer surface hydro-; phobic by lntroduclng fluorine atoms into the surface layer : :: :
- S P E C I F I C A T I O N
Ti tle of the Invention:
PAINT COATED METAL MATERIALS
Field of the Invention:
The present invention relates to paint coated metal materials comprising a metal substrate and a paint film applied on the metal substrate, said paint film having a surface layer containing fluorine atoms and/or perfluoro-alkyl group such as methyl fluoride, ethyl f.luoride.and...
so on introduced therein by a plasma treatment.
Related Prior Arts:
Up to now, paint coated metal materials have been ~ widely used in varlous applications including buildings, bridges, tanks, automobiles, electric appliances and so on, and their main qualities required in these fields of application are to maintain a beautiful surface appearance and to assure good corrosion resistance.
As most of the paint coated metal materials are subjected to mechanical working after the paint coating, the primary requirements of the paint film on the metal substrate are good adheslon, and good workability, particularly press formability, and the secondary requlrements are good corrosion resistance, permanent color and brightness, stain resistance, :and so on depending on the final applications of the products.
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In addition to the above requirements, it is also essential for -the paint coated metal materials that the paint film on the substrate will not be damaged during the mechanical working, especially press forming.
Once damaged, the paint film can no more function as barrier against corrosion, and the corrosion is caused and expands from where the substrate is exposed due to the damage of the paint film, thus markedly shortening the service life of the buildings, bridges, tanks, automobiles, electric appliances and so on, in which the paint coated metal materials are used.
Of the paint coated metal materials, the so-called "pre-coated thin metal sheet" in particular, which is nowadays used in roofings, automobiles and electric appliances, is subjected to severe working, especially press forming, and must show a relatively good elongation property of the paint film on the metal substrate. However, paint films which satisfy the required elongation property are generally soft so that they are easily damaged and poor in the stain resistance.
This incompatibility has long been a problem.
In recent years, as proposed in "Practical Surface Technics" (Jitsumu Hyomen Gijutsu), Vol.30, page 358, 1983, studies have been made on production of paint coated steel sheets having excellent paint film properties by application of the so-called "three-coat system by roll-coating" according to which~an undercoating for improving the adhesion with the metal substrate, an intermediate coating for improving the workability and a top coating for assuring the surface hardness are applied on the metal substrate. This three-coat , ':
~2~
system, however, has a problem that it is technically difficult to maintain the top coat layer to a thickness less than 3 microns so that the hardness of the top coat layer deteriorates the good workability of the intermediate paint coat layer, hence it is very difficult to satisfactorily balance the incompatibility between the surface hardness and the workability which are originally sought for. This is a vital defect of the roll coating method.
Also, Japanese Laid-Open Patent Application No. Sho 59-169851 discloses "a pre-coated steel sheet pre-coated with polyvinyl chloride dispersion paint", according to which an ultraviolet ray curing type clear paint is applied on the polyvinyl chloride dispersion paint applied on the steel substrate and is cured by ultra-violet rays in order to prevent damages of the paint film during the forming of the pre-coat sheet. According to this prior art, the thickness of the ultraviolet ray curing type clear paint is as thick as 200 microns and this method ;
has been limitedly applied to the polyvinyl chloride dis-persion paint pre-coated steel sheets.
Fuxther, it is known to fluorinate the surEace of polymers by a plasma treatment. For example, according to the report by M.Anand et al. (Polymer, 361, Vol.22, 1981), the surface of low-density polyethylene is fluorinated by using a mixture gas of;carbon tetrafluoride, or fluorlne and hellum.
The fluorination of the surface of polymer in this case is only for~the purpose of rendering the polymer surface hydro-; phobic by lntroduclng fluorine atoms into the surface layer : :: :
~ ~ : ::
~ , of the polyethylene. Therefore, this prior art is completely different from the present invention with respect to the technical object as described hereinbelow.
Also, it is known in the field of optical lenses and filters to apply a fluorine coating for the purpose of reducing the refractive power or preventing the reflection, and in the field of blood backs it is known to apply the same for the purpose of preventing the dissolution of plasticizers from the back material of polyvlnyl chloride res.in.
Summary of the Invent.ion:
I-t is therefore an object of the present invention to provide paint coated metal materials, which is remarkably improved in the hardness of paint film, or ln the susceptibility to damages, while maintaining excellent workability, adhesion and corrosion resistance which are inherently possessed of by the paint film by fluorinating the surface layer of the paint films such as acryl and polyester paint films applied on metal substrates.
In accordance with the~present invention, there is thus provided a paint coated material comprlsing a metal substrate and a paint film applied :
on the substrate,;the palnt film having a surface : B
.
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~2~S~8 layer containing fluorine atoms introduced thereinto as perfluoroalkyl groups including methyl fluoride and ethyl fluoride by a plasma treatment.
The conventionally known fluorination of the surface of resin articles is completely different from the fluorination of the surface of paint coated metal materials with respect to the object and results of the plasma treatment despite the similarity in the chemical reaction on the surface oE
organic substances. For example, in the case of pre-coated steel sheets, in order to satisfy the requirement of workability, soft and expandable res:i.ns are normally used for the pa.int coa~ing, but this type of resin is easily damaged and has a very poor stain resistance.
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' ' The inventiveness of the present invention is based on the discovery that when the pre-coated steel sheets having the above defects are subjected to the surface fluorination by a plasma treatment, they are converted into new pre-coated steel sheets ~hich are highly resistive against the damages and stain and yet enjoy the inherent high workability.
The above technical advantages obtained by the sur~ace fluorination by a plasma treatment can be remarka~le and significant only when the surface fluorination is applied to the pre-coated metal materials, particularly, steel sheets coated with paint. This is completely different from the surface quality modification of plastic articles of high molecular materials.
The surface fluorination oE paint coated metal m~terials, according to the present invention is produced by a process comprising applying a conventional type of paint having excellent adhesion, workability, and corrosion resistance on a metal material, curing the paint, and subjecting the surface layer of the paint f ilnt on the metal material to fluorination by use of a gas plasma of carbon tetrafluoride, ethane hexa-fluoride, perfluoropropane, a mixture of fluorine-hellium and so on.
By the surface fluorination, the surface layer of the paint film is supposed to be subjected to the reaction schematically shown in Fig. 4.
; As illustrated, not only fluorine atoms are introduced, but also a perfluoroalkyl group is introduced, although the introduction of fluorine atoms only is effective for the desired ;results. Regarding the degree of the fluorination required for .
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the desired results, any fluorination which can be detected by ESCA analysis is enough.
Brief Explanation of the Drawings:
Fig. 1 shows schematically an inner electrode type plasma apparatus for fluorination used in the present invention.
Fig. 2 shows the result of ESCA spectra of the hardness of the paint film before and after the plasma treatment.
Fig. 3 shows the result of ESCA C spectra and its water decomposition of the paint film before and after the plasma treatment.
Fig. 4 shows schematically the fluorination reaction of the surface of the paint film.
Detailed Description of the Invention:
The present invention will be described in details hereinbelow.;
Regarding the paint usable in the present invention, there is no special limitation with respect to the type or nature, and any conventional paints, such as of polyester, epoxy, vinyl, alkid, uretane, sillcone and the like, may be ~ used. These paints are applied on metal materials as desired.
; ~ As the gas used for surface fluorination of the paint film on the metal materials, fluorine, or compounds in the gas form containing fluorine atoms in their molecules, such .
;; as carbon tetrafluoride, ethane hexafluoride, perfluoropropane, and so on or~their~mixtures with inert gas, such as argon, helium and nitrogen, may be used.
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The metal materials used as substrates in the present invention may be in any form, such as thin sheets, middle gauge plates, pipes, die steel and wires.
Also, there is no special limitation with respect to the kinds or grades of the metal materials used in the present invention, and steel materials as cold rolled or hot rolled, similar steel materials further coated with zinc, aluminum, tin, nickel, copper, cobalt, iron, and other metals, their alloys, or their composite materials, aluminum plates, titanium plates and their alloy plates similarly coated may be satisfactorily used.
Hereinbelow, the process for producing the fluorinated paint coated metal materials according to the present invention will be described.
As for the generation of plasma, there are three types of methods: an inner electrode type, a non-electrode type, and a micro-wave type. ~n~ of these types can be used in the present invention.
: When the surface fluorination is done by uslng ~the inner electrode type using a radio frequency (13.56 MHz) power source (3) as illustrated in Fig. 1, the pre-coated metal material (1) is placed in a reactor (2) in which a vacuum of 10 3 Torr is maintained, and then the gas as mentioned before is introduced into the reactor through a conduct plpe (4) to :~ a predetermined gas pressure (about O.OI to 10 Torr). Then ::
an appropriate discharge power (30 to 400 W) i5 added to the electrodes (5) for effecting the surface fluorination of the ~: :
paint coated metal material placed on the electrode supported by the metal stool (6).
~. ' , , :
.
The degree of the fluorination of the surface layer of the paint film call be varied by selecting the types of gas or gas mixing ratio and the discharge condition and these factors are controlled depending on the final applications of the paint coated metal materials. The surface fluorination can be confirmed by the Fourier transform infrared spectrochemical analysis (FT-IR) and the X-ray photoelectron spectrochemical analysis (ESCA). As illustrated by the analysises by ESCA in Figs. 2 and 3, the fluorination reaction on the surface layer of the paint film is understood as schematically shown in Fig. 4. The resultant paint coated metal materials fluorinated on the surface layer of the paint film show remarkable improvements in the hardness of the paint Eilm layer or in the resistance to the scratches while maintaining the inherent excellent properties such as paint adhesion, workability and corrosion resistance.
Description of Preferred Embodiments:
The present invention will be better understood from the following descriptions of preferred embodiments, but should not be limited thereto.
Example 1:
~ galvanized steel pipe (100 mm in diameter, 18 cm in length) was coated with an epoxy paint by a powder coating method and the surface layer of the fllm was fluorinated by ~using a gas plasma of carbon tetrafluoride under the conditions:
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Gas flow rate 50 cm3 (STP)/min.
Gas pressure 2 Torr Discharge power 40 W
Discharge time 5 minutes The paint ~ilm qualities of the resultant paint coated steel pipe as fluorinated were determined by the pencil hardness test ~JIS K-5400, 6.14-Breaking and Scratching).
As shown in Table 1, the results show the hardness of the paint ~ilm is remarkably improved by the surficial fluorination by the plasma treatment.
Example 2:
A pre-coated steel sheet (0.6 mm in thickness, 100 mm in width, 100 mm in length) was prepared by applying a primer coat of polyester in 5~ thickness and a top coat of polyester in 20~ in thickness onto a galvanized steel sheet (20 g/m2 of zinc coat) and ~aking the paint film. The surface of this pre-coated steel sheet was fluorinated by using a gas plasma of 5% fIuorine - 95% heIium under the following conditions:
Gas flow rate 50 cm3 (STP~/min.
Gas pressure 1.8 Torr Discharge power 50 W
; Discharge time 2 minutes The paint film qualities of the resultant paint coated galvanized steel sheet were determined by the pencil :
hardness test (JIS K-5400, 6.14), the 180 bending test and the stain test. As shown ln Table 1, the results of the ` tests reveal that the hardness and the resistance to stain ~: ~ aro remarkably improved without ~acrifice of the workability.
: :
Example 3:
A colored galvanized steel sheet (0.8 mm in thickness, 100 mm in width, 100 ~m in length; zinc coat of 180 g/m ) was prepared by applying a primer coat of epoxy in 5~ in thickness and a top coat of polyester of 20~ in thickness onto a galvanized steel sheet and baking coat, and the surface of this colored galvanized steel sheet was fluorinated by using a gas plasma of carbon tetrafluoride under the following conditions:
Gas flow rate 30 cm (STP)/min.
Gas pressure 2 Torr Discharge power 60 W
Discharge time 5 minutes The paint film qualities of the resultant colored galvanized sheet were determined by the pencil hardness test (JIS K-5400, 6.14), the working test and the stain test.
As shown in Table 1, the results show that the hardness and the resistance to stain are remarkably improved without lowering the wor~ability.
Example 4:
A Zn-Ni alloy coated steel sheet (0.7 mm in thickness, 100 mm in width, 100 mm in length; alloy coat of 15 g/m2) was coated with acryl paint and baked, and the surface of this paint coated sheet was fluorinated by using a gas plasma of 5~ 1uorine-95 % helium under the following conditions:
Gas flow rate 50 cm3 (5TP)/min.
Gas pre-ssure 2 Torr Discharge power 60 W
Discharge time one~minute ~2~
The paint film qualities of the resultant paint coated steel sheet were determined by the pencil hardness test (JIS K-5400, 6.14), and -the 180 bending test.
As shown in Table 1, the hardness and the stain resistance are remarkably improved by the plasma treatment without lowering the workability.
Example 5:
A galvanic Zn-Wi alloy coated steel sheet (0.8 mm in thickness, 100 mm in width, 100 mm in length; alloy coat of 2,0 g/m2) was coated with a primer coat of epoxy alkid resin paint of 5~ in thickness and baked, then further applied with a top coat of urethane resin paint of 20~
in thickness and again baked. The surface of the resultant paint coated sheet was fluorinated by using a gas plasma of 6~ fluorine-94% helium under the following conditions:
Gas flow rate 40 cm ~STP)/min.
Gas pressure 2 ~orr Dis-charge power 50 W
Discharge time one-minute The paint film qualities of the resultant paint coated galvanic Zn-Ni alloy coated steel sheet were determined by the pencil hardness test (JIS K-5400, 6.14) and the sta1n test.
As shown ln Table 1, the hardness and the resistance to stain are remarkably improved by the plasma treatment.
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A pre-coated steel sheet was prepared by applying 2 primer coat of ~poxy paint of 5~ in tilickness and a top coat of polyester paint of 20~ in thickness onto a galvanized steel sheet (zinc coat of 20 g/m ) and baking the pain coating. The surface of the paint coated steel sheet thus prepared was fluorinated by using a gas plasma of ethane hexafluoride under the following conditions:
Gas flow rate 3 to 10 cm (STP)/min.
Gas pressure: 0.035 Torr Discharge power 300 W
Discharge time 5 seconds The paint film qualities of the resultant pai.nt coated steel sheet were determined by the pencil hardness test (JIS K-5400, 6.14) and the 180 bending test and the ; stain test. The results are shown in Table 1.
The above embodiments are described limitedly to the steel materials, but similar results can be obtained when metal materials mentioned hereinbefore other than steel are used.
The paint coated metal materials according to the present invention has remarkable advantages that the surface hardness of the paint film, resistance to damages, as well as stain resistance are markedly improved without lowering the excellent properties inherent to the paint film by introduction of fluorine or a perfluoroalkyl group such as methyl fluoride, and ethyl fluoride into the surface ~ ~ layer of the palnt film. Therefore, the paint coated ; ~ ~ metal materials according to the present invention lS very ~;
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useful as a pre-coa~ed metal sheet for roofings, walls, automobiles and electric appliances, and also can be advan-tageously used as a paint coated metal material fo~ general purposes such as buildings, bridges, and tanks and can greatly contribute to elongate the service life of these constructions and articles.
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~ , of the polyethylene. Therefore, this prior art is completely different from the present invention with respect to the technical object as described hereinbelow.
Also, it is known in the field of optical lenses and filters to apply a fluorine coating for the purpose of reducing the refractive power or preventing the reflection, and in the field of blood backs it is known to apply the same for the purpose of preventing the dissolution of plasticizers from the back material of polyvlnyl chloride res.in.
Summary of the Invent.ion:
I-t is therefore an object of the present invention to provide paint coated metal materials, which is remarkably improved in the hardness of paint film, or ln the susceptibility to damages, while maintaining excellent workability, adhesion and corrosion resistance which are inherently possessed of by the paint film by fluorinating the surface layer of the paint films such as acryl and polyester paint films applied on metal substrates.
In accordance with the~present invention, there is thus provided a paint coated material comprlsing a metal substrate and a paint film applied :
on the substrate,;the palnt film having a surface : B
.
~ . ` .
~2~S~8 layer containing fluorine atoms introduced thereinto as perfluoroalkyl groups including methyl fluoride and ethyl fluoride by a plasma treatment.
The conventionally known fluorination of the surface of resin articles is completely different from the fluorination of the surface of paint coated metal materials with respect to the object and results of the plasma treatment despite the similarity in the chemical reaction on the surface oE
organic substances. For example, in the case of pre-coated steel sheets, in order to satisfy the requirement of workability, soft and expandable res:i.ns are normally used for the pa.int coa~ing, but this type of resin is easily damaged and has a very poor stain resistance.
.
, : ::
- 4a -' !
' `
.
' ' The inventiveness of the present invention is based on the discovery that when the pre-coated steel sheets having the above defects are subjected to the surface fluorination by a plasma treatment, they are converted into new pre-coated steel sheets ~hich are highly resistive against the damages and stain and yet enjoy the inherent high workability.
The above technical advantages obtained by the sur~ace fluorination by a plasma treatment can be remarka~le and significant only when the surface fluorination is applied to the pre-coated metal materials, particularly, steel sheets coated with paint. This is completely different from the surface quality modification of plastic articles of high molecular materials.
The surface fluorination oE paint coated metal m~terials, according to the present invention is produced by a process comprising applying a conventional type of paint having excellent adhesion, workability, and corrosion resistance on a metal material, curing the paint, and subjecting the surface layer of the paint f ilnt on the metal material to fluorination by use of a gas plasma of carbon tetrafluoride, ethane hexa-fluoride, perfluoropropane, a mixture of fluorine-hellium and so on.
By the surface fluorination, the surface layer of the paint film is supposed to be subjected to the reaction schematically shown in Fig. 4.
; As illustrated, not only fluorine atoms are introduced, but also a perfluoroalkyl group is introduced, although the introduction of fluorine atoms only is effective for the desired ;results. Regarding the degree of the fluorination required for .
:
I B _ 5 _ ~, ...... , . , :
. .
.
- ~ .
.
8~
the desired results, any fluorination which can be detected by ESCA analysis is enough.
Brief Explanation of the Drawings:
Fig. 1 shows schematically an inner electrode type plasma apparatus for fluorination used in the present invention.
Fig. 2 shows the result of ESCA spectra of the hardness of the paint film before and after the plasma treatment.
Fig. 3 shows the result of ESCA C spectra and its water decomposition of the paint film before and after the plasma treatment.
Fig. 4 shows schematically the fluorination reaction of the surface of the paint film.
Detailed Description of the Invention:
The present invention will be described in details hereinbelow.;
Regarding the paint usable in the present invention, there is no special limitation with respect to the type or nature, and any conventional paints, such as of polyester, epoxy, vinyl, alkid, uretane, sillcone and the like, may be ~ used. These paints are applied on metal materials as desired.
; ~ As the gas used for surface fluorination of the paint film on the metal materials, fluorine, or compounds in the gas form containing fluorine atoms in their molecules, such .
;; as carbon tetrafluoride, ethane hexafluoride, perfluoropropane, and so on or~their~mixtures with inert gas, such as argon, helium and nitrogen, may be used.
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The metal materials used as substrates in the present invention may be in any form, such as thin sheets, middle gauge plates, pipes, die steel and wires.
Also, there is no special limitation with respect to the kinds or grades of the metal materials used in the present invention, and steel materials as cold rolled or hot rolled, similar steel materials further coated with zinc, aluminum, tin, nickel, copper, cobalt, iron, and other metals, their alloys, or their composite materials, aluminum plates, titanium plates and their alloy plates similarly coated may be satisfactorily used.
Hereinbelow, the process for producing the fluorinated paint coated metal materials according to the present invention will be described.
As for the generation of plasma, there are three types of methods: an inner electrode type, a non-electrode type, and a micro-wave type. ~n~ of these types can be used in the present invention.
: When the surface fluorination is done by uslng ~the inner electrode type using a radio frequency (13.56 MHz) power source (3) as illustrated in Fig. 1, the pre-coated metal material (1) is placed in a reactor (2) in which a vacuum of 10 3 Torr is maintained, and then the gas as mentioned before is introduced into the reactor through a conduct plpe (4) to :~ a predetermined gas pressure (about O.OI to 10 Torr). Then ::
an appropriate discharge power (30 to 400 W) i5 added to the electrodes (5) for effecting the surface fluorination of the ~: :
paint coated metal material placed on the electrode supported by the metal stool (6).
~. ' , , :
.
The degree of the fluorination of the surface layer of the paint film call be varied by selecting the types of gas or gas mixing ratio and the discharge condition and these factors are controlled depending on the final applications of the paint coated metal materials. The surface fluorination can be confirmed by the Fourier transform infrared spectrochemical analysis (FT-IR) and the X-ray photoelectron spectrochemical analysis (ESCA). As illustrated by the analysises by ESCA in Figs. 2 and 3, the fluorination reaction on the surface layer of the paint film is understood as schematically shown in Fig. 4. The resultant paint coated metal materials fluorinated on the surface layer of the paint film show remarkable improvements in the hardness of the paint Eilm layer or in the resistance to the scratches while maintaining the inherent excellent properties such as paint adhesion, workability and corrosion resistance.
Description of Preferred Embodiments:
The present invention will be better understood from the following descriptions of preferred embodiments, but should not be limited thereto.
Example 1:
~ galvanized steel pipe (100 mm in diameter, 18 cm in length) was coated with an epoxy paint by a powder coating method and the surface layer of the fllm was fluorinated by ~using a gas plasma of carbon tetrafluoride under the conditions:
; ~ - 8 -B
Gas flow rate 50 cm3 (STP)/min.
Gas pressure 2 Torr Discharge power 40 W
Discharge time 5 minutes The paint ~ilm qualities of the resultant paint coated steel pipe as fluorinated were determined by the pencil hardness test ~JIS K-5400, 6.14-Breaking and Scratching).
As shown in Table 1, the results show the hardness of the paint ~ilm is remarkably improved by the surficial fluorination by the plasma treatment.
Example 2:
A pre-coated steel sheet (0.6 mm in thickness, 100 mm in width, 100 mm in length) was prepared by applying a primer coat of polyester in 5~ thickness and a top coat of polyester in 20~ in thickness onto a galvanized steel sheet (20 g/m2 of zinc coat) and ~aking the paint film. The surface of this pre-coated steel sheet was fluorinated by using a gas plasma of 5% fIuorine - 95% heIium under the following conditions:
Gas flow rate 50 cm3 (STP~/min.
Gas pressure 1.8 Torr Discharge power 50 W
; Discharge time 2 minutes The paint film qualities of the resultant paint coated galvanized steel sheet were determined by the pencil :
hardness test (JIS K-5400, 6.14), the 180 bending test and the stain test. As shown ln Table 1, the results of the ` tests reveal that the hardness and the resistance to stain ~: ~ aro remarkably improved without ~acrifice of the workability.
: :
Example 3:
A colored galvanized steel sheet (0.8 mm in thickness, 100 mm in width, 100 ~m in length; zinc coat of 180 g/m ) was prepared by applying a primer coat of epoxy in 5~ in thickness and a top coat of polyester of 20~ in thickness onto a galvanized steel sheet and baking coat, and the surface of this colored galvanized steel sheet was fluorinated by using a gas plasma of carbon tetrafluoride under the following conditions:
Gas flow rate 30 cm (STP)/min.
Gas pressure 2 Torr Discharge power 60 W
Discharge time 5 minutes The paint film qualities of the resultant colored galvanized sheet were determined by the pencil hardness test (JIS K-5400, 6.14), the working test and the stain test.
As shown in Table 1, the results show that the hardness and the resistance to stain are remarkably improved without lowering the wor~ability.
Example 4:
A Zn-Ni alloy coated steel sheet (0.7 mm in thickness, 100 mm in width, 100 mm in length; alloy coat of 15 g/m2) was coated with acryl paint and baked, and the surface of this paint coated sheet was fluorinated by using a gas plasma of 5~ 1uorine-95 % helium under the following conditions:
Gas flow rate 50 cm3 (5TP)/min.
Gas pre-ssure 2 Torr Discharge power 60 W
Discharge time one~minute ~2~
The paint film qualities of the resultant paint coated steel sheet were determined by the pencil hardness test (JIS K-5400, 6.14), and -the 180 bending test.
As shown in Table 1, the hardness and the stain resistance are remarkably improved by the plasma treatment without lowering the workability.
Example 5:
A galvanic Zn-Wi alloy coated steel sheet (0.8 mm in thickness, 100 mm in width, 100 mm in length; alloy coat of 2,0 g/m2) was coated with a primer coat of epoxy alkid resin paint of 5~ in thickness and baked, then further applied with a top coat of urethane resin paint of 20~
in thickness and again baked. The surface of the resultant paint coated sheet was fluorinated by using a gas plasma of 6~ fluorine-94% helium under the following conditions:
Gas flow rate 40 cm ~STP)/min.
Gas pressure 2 ~orr Dis-charge power 50 W
Discharge time one-minute The paint film qualities of the resultant paint coated galvanic Zn-Ni alloy coated steel sheet were determined by the pencil hardness test (JIS K-5400, 6.14) and the sta1n test.
As shown ln Table 1, the hardness and the resistance to stain are remarkably improved by the plasma treatment.
::
:
' Exarnple 6: ~ 2~5~
A pre-coated steel sheet was prepared by applying 2 primer coat of ~poxy paint of 5~ in tilickness and a top coat of polyester paint of 20~ in thickness onto a galvanized steel sheet (zinc coat of 20 g/m ) and baking the pain coating. The surface of the paint coated steel sheet thus prepared was fluorinated by using a gas plasma of ethane hexafluoride under the following conditions:
Gas flow rate 3 to 10 cm (STP)/min.
Gas pressure: 0.035 Torr Discharge power 300 W
Discharge time 5 seconds The paint film qualities of the resultant pai.nt coated steel sheet were determined by the pencil hardness test (JIS K-5400, 6.14) and the 180 bending test and the ; stain test. The results are shown in Table 1.
The above embodiments are described limitedly to the steel materials, but similar results can be obtained when metal materials mentioned hereinbefore other than steel are used.
The paint coated metal materials according to the present invention has remarkable advantages that the surface hardness of the paint film, resistance to damages, as well as stain resistance are markedly improved without lowering the excellent properties inherent to the paint film by introduction of fluorine or a perfluoroalkyl group such as methyl fluoride, and ethyl fluoride into the surface ~ ~ layer of the palnt film. Therefore, the paint coated ; ~ ~ metal materials according to the present invention lS very ~;
~ ~ - 12 -:: :
' ~z~
useful as a pre-coa~ed metal sheet for roofings, walls, automobiles and electric appliances, and also can be advan-tageously used as a paint coated metal material fo~ general purposes such as buildings, bridges, and tanks and can greatly contribute to elongate the service life of these constructions and articles.
~' , i, : - 13 -, ~r ~: ~8 m (~ 3 o a) ~ ra I ~ \ ~I s~
~ ~ ~ ~ ~ Q) ~ ~ ~: U~ ~
td ~n a o ~ a: ~ X
~ a) ~ <I d x .~q~
3 ~ ~ ~ ~
S~ 3 o I ~ o O ~ ~ O
.~ '11 ~E ~ X
~:: R ~ _ ,q P~ ~h d I El ~ ~
4~ ,_m E~ ~ o ~ ~ o 3 ~o ~ ~ ~
~ ~ t~l h ~ ~ ~ 3 5 ~ ~ x ~n ~ ~1 0 ~ ~ ~ ~ ~ ~
~ ~ ~ X~ ~ ~ ~ ~ X ~ ~ ~, 4~ h 1.1 ~ ~ u~ u~ ~ " ~ ~
0 ~ m 4~ .c .~ So~ ~ .Y ~ ~ m E~ ~ ~ a) ~ s~ ~ ~ ~ ~ ~ ~:
~ m E~ ¦ m u~ ~ x ~ _ ,~ ~ ~
Q) ~ a D ~ O
c) I c~ '~ ~
d~ d~ o\O R h ~ D
f) ~D
a E~ ~ -x X X X X X X
.
. .
Claims (3)
1. A paint coated material comprising a metal substrate and a paint film applied on the substrate, said paint film having a surface layer containing fluorine atoms introduced thereinto as perfluoroalkyl groups including methyl fluoride and ethyl fluoride by a plasma treatment.
2. A paint coated metal material according to claim 1, in which the metal substrate is metal-coated.
3. A paint coated metal material according to claim 1, in which the metal substrate is a galvanized steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/349,934 US4898775A (en) | 1985-04-27 | 1989-05-08 | Paint coated metal sheets |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-89933 | 1985-04-27 | ||
| JP8993385A JPS61248734A (en) | 1985-04-27 | 1985-04-27 | Coated metallic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1295888C true CA1295888C (en) | 1992-02-18 |
Family
ID=13984494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000507657A Expired - Lifetime CA1295888C (en) | 1985-04-27 | 1986-04-25 | Paint coated metal materials |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS61248734A (en) |
| AU (1) | AU567414B2 (en) |
| CA (1) | CA1295888C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03169372A (en) * | 1989-11-29 | 1991-07-23 | Nippon Steel Corp | Manufacture of precoated metal molded item and molded item thereby |
| JPH049732U (en) * | 1990-05-11 | 1992-01-28 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5838701A (en) * | 1981-08-31 | 1983-03-07 | Japan Synthetic Rubber Co Ltd | Surface treatment by plasma chemical reaction |
| JPS59169851A (en) * | 1983-03-15 | 1984-09-25 | 日本ペイント株式会社 | Polyvinyl chloride dispersion paint precoated steel plate |
-
1985
- 1985-04-27 JP JP8993385A patent/JPS61248734A/en active Pending
-
1986
- 1986-04-22 AU AU56486/86A patent/AU567414B2/en not_active Ceased
- 1986-04-25 CA CA000507657A patent/CA1295888C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU567414B2 (en) | 1987-11-19 |
| AU5648686A (en) | 1986-10-30 |
| JPS61248734A (en) | 1986-11-06 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |