CA2226633A1 - Metal substrate with enhanced corrosion resistance and improved paint adhesion - Google Patents
Metal substrate with enhanced corrosion resistance and improved paint adhesion Download PDFInfo
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- CA2226633A1 CA2226633A1 CA002226633A CA2226633A CA2226633A1 CA 2226633 A1 CA2226633 A1 CA 2226633A1 CA 002226633 A CA002226633 A CA 002226633A CA 2226633 A CA2226633 A CA 2226633A CA 2226633 A1 CA2226633 A1 CA 2226633A1
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- Prior art keywords
- organosilane
- resin
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- layer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
This invention is a blended powder mixture including a thermosetting resin and a solid, non-hydrolyzed, functional low molecular weight organosilane coupling agent. The powder mixture may be used to form a composite coating to protect a steel substrate from corrosion. The composite coating is formed by coating the substrate with an inorganic layer such as a silicate, depositing the powder mixture over the inorganic layer, heating the substrate to a temperature at least equal to the curing temperature of the resin and maintaining the substrate at the curing temperature for sufficient time to crosslink the resin and to diffuse the organosilane to the substrate whereby the crosslinked layer is coupled to the inorganic layer by the organosilane. The powder mixture include 0.01-10 wt.% organosilane having a melting point no greater than the curing temperature of the resin. Preferred thermosetting resins include epoxy, polyester, epoxy-polyester, acrylic, acrylic-urethane or fluorovinyl.
Description
PCT~US95/08718 METAL SUBSTRATE WITH ENHANCED CORROSION
RESISTANCE AND IMPROYED PAINT ADHESION
~ACKGROUND OF THE INVENTION
s This invention relates to an organic powder co--~rositisn and a method of using the powder composition tor forming a crosslinked paint coupled to a metal substrate for protecting the substrate from corrosion. More particularly, the powder composition inc4~des a homogeneous mixture of a thermosetting rasin 10 and a solid, non-hydrolyzed, functional organosilane coupling agent.
It is known to forrn a composite coating on steel sheet for providing corrosion protection. US patent 5,108,793; incorporated herein by reference, discloses rinsing a steel sheet with an alkaline solution containing a silicate,drying the sheet to form an insolubl~ inorganic silicate coating, rinsing the l 5 coated sheet in an aqueous solution containing an organosilane coupling agent and then drying the sheet forming a silane film on the outer sur~ace of the silicate coating. The silicate coating provides excellent corrosion protection of the steel sheet. If the sheet is painted, ihe silane film acts as a coupling agent forming a stn n~ oovalent bond between the silicate coating and the paint. An 20 embodiment of this patent includes coid-rolled and ~alvanized steel sheets initially treated with a phosphate conversion coating, then treated with the twostep silicate/silane rinse coating and lastly electrostatically coated with a powder paint or cathodically electrocoated with a paint for forming a composite coating. The silicate/silane layer improves corrosion protection and strengthens25 the bond between the inner phosphate layer and the outer paint layer. A
disadvantage with this process is that some of the sil c~t~ inevitably bscomes transferred to the silane rinse tank thereby contaminating the silane solution.
This contamination may reduce the effectiveness of the silane as a coupling agent. Another disadvantage is that hydrolyzed silane solutions have a 30 relatively short storage life. Organosilanol solutions tend to condense and polymerize thereby minimizing their chemical interaction with paints.
It is well known to provide corrosion protection to steel sheet by coating with a liquid resin containing an organosilane coupling agent. These liquid resins have the same disadvantage referred to above in that hydrolyzed silanes 3 5 have reduced effectiveness as coupling agents.
-CA 02226633 1998-01-li More recently, it has become known to provide c~rrosion protection to steel sheet by coating the sheet with a powder containing a silicon2 resin. US
patent 5,077,3~4 discloses an in-situ formed polymeric mixture comprising an acrylic graft copolymer of silicone resin used as a polymeric binder in powder paint. Silicone resin and ethylenic monomers are dissolved in a solvent heated to 50-1~0~C and mixed until polymerization is completed. The solvent then is stripped away leaving a non-~elled polymerized binder. A disadvantage of using this powder paint is believed to be that a ~ood bond is not ~ormed between the paint and steel substrate- Since the silicone resin has already l 0 been reacted when in-situ combined with the ethylenic monomers when forming the acrylic polymer, the silicone resin will not act as a coup6ng agent between the outer acrylic layer and the steel substr~ts.
Accordingly, there is a need to provide an organosilane having a long storage life that can be used as a coupling agent when forming a crosslinked 1 5 coating. There is a further need for developing a low cost, environmentally safe process for forming an adherent crosslinked coating coupled to a metal substrate such as cold-rolled steel or galvanized steel.
BRIEF SUMMARY OF THE INVENTION
The invention relates to an organic powder composition and a method of using the powder composition for forming a crosslinked paint coupled to a metal substrate for protecting the substrate from corrosion. The powder c~n-position of ths invention includes a homogeneous mixture of a thermosetting resin and ~
25 solid, non-hydrolyzed, functional low molecular weight organosilane coupling agsnt. The organosilane is a solid at ambient temperature, hss a me~ing point no greater than ths curing telmp~rature of the resin and is readily diss~lved into the resin during crosslinking on the su~s~t~te.
Another feature of the invention includes forming a corrosion rasistant 30 coating on a metal substrate using ths aforesaid powder mixture with the coating being coupled to the substrate by the organosilane. The coating is the reaction product ~ormed by in-situ curing of the powder mixture aRer being deposited onto the substrate. Preferably, the crosslinked layer has a thickness of at least 10 tlm.
_ Another feature of the invention is for the aforesaid corrosion resistant coating to be a composite coating including a non-toxic inor~anic inner layer scoupled to the outer crosslinked layer by the organosilane.
A furthsr feature of the invention is forming a corrosion resistant coating Son a metal substrate including the steps of providin~ a homogeneous powder mixture of a thermosetting resin and a solid, non-hydrolyzed, functional low mol~cu'~ weight organosilane coupling agent, depositin9 a layer of th~ powder mixture onto the substrate, heating the substrate to a temperature at least equal to the curing temperature of the resin and maintainin~ this temperature for 10sufficient time to melt the resin and the or~anosilane. The resin is cured andforms a crosslinked layer that becomes tightly bonded to the substrate by the organosilane.
Another feature of the invention is for the aforesaid powder mixtur2 to have an olganosilane concentration of 0.01-10 wt.%.
1 ~Another feature of the invention inclu~es the addRional step of depositing an inorganic îayer onto the substrate prior to depositing the powder layer.
Another feature of the invention is for the aforesaid crosslinked layer to have a thickness of at least 10 llm.
Another feature of the invention is for the aforesaid resin to have a curing 2 0temperature of 1 00-250~C.
Another feature of the invention is for the aforesaid inorganic layer to include a silicate.
Another feature of the invention is for the aforesaid resin beins from the group consisling of epoxy, polyester, epoxy-polyester, acrylic, acrylic-urethane2 Sor fluorovinyl.
An object of the invention is to form a corrQsion resistant adherent coating on a metal substrate using an organosilane coupling agent having a long storage life.
Another object is to form a corrosion resistant adherent composite 3 0coating on a metal substrate having an inorganic inner layer formed from a rinse solution having an extended storage life.
Another object is to provide a low cost, environmentally safe, process for forming a corrosion resistant adherent coating on cold-rolled or galvanized steel sheets using an organosilane coupling agent.
3 SAdvantages of the invention include a long storage life Sor an organosilane coupling agent, forming a corrosion resistant coating having good -adhsrencQ to a variety of metal surfaces without using an environmentally hazardous waste subst~nce, e.Q. chromate rinsss, and no contamination of a rinse solution containing an inorganic coating material.
S DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention includes providing a homogeneously blended powder composition, i.e., a paint, including a thermosetting resin and a solid, non-hydrolyzed, functional low molecular weight organosilane coupling agent that is 10 soluble in the thermoseffing resin. Th~ organic resin may be any thermosetting polymer such as epoxy, polyester, epoxy-polyester, acrylic, acrylic-urethane or fluorovinyl. The sitane rnay be any organic compound so long it is solid at ambient temperature, has a melting temperature no higher than the curing temperature of the resin, capable of being dissolved into the resin and docs notl ~i include OH groups. By a low molecular weight silane is meant monomeric, dimer'ic or oligomeric mol~cules, i.s., RSi(OX)3.
Hydrolyzed organosilanes, such as NH2-(CH2)3Si(OH)3, are undesirable because they are liquid at ambient temperature and tend to polymerize quickly.
Although solid, non-hydrolyzed organosilanes react more slowly than 20 hydrolyzed organosilanes, the non-hydrolyzed forms do not polymerize as rapidly. For epoxy, polyester and acrylic resins, the following commercially available alkoxy silanes and chlorosilanes could be used:
triphenylethoxysilane, triphenylfluorosilane, phenylallyldichlorosilane, N-phenylaminopropyltrimethoxysilane, neophylmethyldiethoxysilane (or the 2~i dimethoxy version), n-octadecyldimethylmethoxysilane, n-octadecyldimethyl[3- trimethoxysilyl-propyl] ammoniumchloride, 2-(3,4-epoxyclyclohexyl)ethyltrimethoxysilane, t-butyldiphenylmethoxysilane, phenethyltrimethoxysilane and styrylethyltrimethoxysilan~. For fluorovinyl resins such as PVDF or PTFE, the following commercially available silanes 3 0 could be used: [2-(perfluorohexyl)ethylltrichlorosilane, t2-(perfluorooctyl)ethyl~trichlorosilane, 1 H, 1 H, 2H, 2H
perfluoralkyltriethoxysilane, 3,3,3-trifluoropropyltriethoxysilane or (heptafluoroisopropoxy)propyltriethoxysilane. A preferred silane is 3-(N-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilanehydrochloride having 3 ~ the following structure: ' W O 97/04034 PCT/U~5S1~718 CH2~H
~NHcH2cH2NH2+
\CH2CH2Si(OCH3)3 The blended resinlorganosilane mixture preferably is used as paint with the mixture includin~ one or more ~ditional powder additives such as a pi~ment and a filler. For example, one or more-of titanium-oxide, lead oxide, 15 zinc oxide, silica, calcium oxide, calcium carbonata, chromium oxide, carbon black and mixtures thereof may be used 85 a pigment. One or more of clay, silica, talc, mica, woolastomite and wood flower may be used as a filler. The powders of the mixture preferably have a particle size less than 32~ mesh. The curing temperature of the resin preferably is within the range of about 100-20 250~C. The composition of the mixture, including any additives, preferablyshould be 0.01-10 wt.% organosilane, mors preferably at least about 0.2 wt.%
organosilane. The concentration of the organosilane should be a2 least 0.01 wt.% be~se this amount is needed so that the silane diffvses to the interface of the metal substrate. The concentration of the organosilane should not 2 S exoeed 10 wt% bec?vse it may adversely affect the paint properties, may cause the paint to become pl~stic~ and may weaken the covalent bond be~e~n the paint layer and the metal sul,~tr~e by weak boundary byer effects.
The ~le.-~e~l resin/organosilane mixture will form a very adherent, corrosion res;sla~t, cro~s-inked coating or paint coupled to a metal substrate by 3 0 the silane. The coating can be formed on a variety of metai sur~acas including, but not limited to, hot rolled and pickled steel sheets, cold-rolled steel sheets, stainless steei sheets, hot dip metallic coated steel sheets, electroplated mstallic coated steel sheets, aluminum sheets and aluminum alloy sheets. The metallic coating may include one or more layers of lead, Isad alloy, nickel, 3 5 nickel alloy, nickel terne, zinc, zinc alloy, aluminum, aluminum alloy, and the like. A phosphate conversion coating also may be applied to these steel sheets W O 97io4034 PCTnUS95/08718 prior to being coated with the resin/organosilan~ powder mixture. The metal substrate may include continuous stnp and 10il, sheets cut to length as well as bars, anglas, tubes and b~ams.
After the resin/or~anosilane powder mixture is applied to a metal 5 subsl-ale. the substrate is heated to at l~ast the curin3 t~mp~rature of the resin.
The resin and organosilane melt with the silane bein dissolved into the liquid resin. Prior to the rssin being crosslinked and l~ecG--,ing solid, the silane will have interacted with the resin and hav~ migrated to the surface of the substrate.
The silane reacts with OH groups on the surface of the substrate forming a 10 strong ccvalent bond of the type:
X~H + CH30-~i- ~ X O-~ + CH30H t or X~H + C:l-$i- _ X~$i. + HCI t where X is a metal oxide on the surface of ~he substrate or an inor~anic lay3r.
15 The oxides of some metals include OH groups. In ths cas8 where the me!al substrate is aluminum, an aluminum alloy or a steel sh~et coa~ed with aluminum or an aluminum alloy, th~ silane may react with the OH groups present in the aluminum oxide surface of the substrate forming a covalent bond of the type Me-O-Si-. In the case where the metal sul,slra~e is steel or a st~el2 O substrate coated with a metallic coating other than aluminum or an aluminum alloy, the substrate first should be preferably coated with an inner inorganic silicon containing layer having OH groups prior to deposition of the resin/organosilans powder mixture. The inorganic layer may be a silicats or a silica. In tha latter oase, the silans r~acts with ths OH groups present in the 2 5 inor~anic silicon containin~ layer ~Gr.ni,-~ a stron~ coYal~nt bond of the type Si-O-Si- which is preferr~d to the Me~Si- bond descri~e~ above.
While the silane is reactin~ with the OH groups on the surface of the metaJ substrate during curin~ of the r~sin, the fur,c~ion~l ~roup of the silane also will have interacte~ with a ~unctional group in the resin or the cr~sslinl~r in tha 3 O r~sin, e.g., R-NH2 ~ H2C--CH-R' ~ R-NH-CH2-CH-R' ~ OH
35 where R may be -(CH2)3Si(OCH3)3 and R' is the thermosetting resin, ~.9., epoxy.
W O 97/04034 PCT/U~5S~5718 In a preferred embodiment, ~he corrosion resistant coating is a composite of the previously described inner inorganic layer and the outer crosslinked paint layer. Preferably, the inner layer is a silicate formed in a manner as describedin US patent 5,108,793; incorporated herein by r~ference. Waterglass is J S dissolvad in~v8ter, e.g., an alkaline solution containing Ba(N03)3 ~ n. The solution preferably is maintained at an elevated temperatur~, e.g., 55-60~C, to reduc~ the rinse time. A steel strip is rinsed with the silicats solL~ion preferably by dipping the strip into the solution for at least 20 seconds. After dipping, the strip is rinsed and dried. The silicate coating provides excellent corrosion 1 0 protection for the steel strip.
The silicate coated strip then is coated with a layer having a uniform thickness of the blended powder mixture of the thermosetting powder and organosilane powdsr. The organic powder may be applied to the strip by olsoll(,slalic spray guns such as ~isclose~ in US patent 5,0~9,446; incorporatedl 5 herein by reference, or by passing the strip through an ele~l,osl~l;c~ charged fluidized bed. If the fluidi7ed bed is not electrost~ti~lly c~arged, the strip must be preheated. The strip is heated to at least the curing temperature of the thermosetting resin by n-st passing the powder coated strip preferably through an induction coil. The heated strip then passes through another heater such as 2 0 infrared for maintaining the molten resin for sufficient time so that the organosilane becomes dissolved into and diffuses to a sur~ace of the steel strip.
An important feature of the invention is that the organosilane be soluble with the thermosetting resin. That is, the organosilane must be ~r~bl~ of being melted as well as go into solution with the molten resin. During this time period, the organosilane also migrates toward the inorganic inner layer, e.g., silicate, thoreby establishing a ti~ht covalent bond b~tween th~ inorganic tayer and the crosslinked outer paint layer.
Details of a blended resin/organosilane mixturs of the invention will be better understood from the following example. A powder containing a 3 0 th~rmosettinq resin and optionally one or more fillers or pigments is prepared in a conventional manner. Thereafter, a solid, non-hydrolyzed low molecular weight organosilane is blended with the powder mixture by cryogenic grinding until a homogeneous powder resin/organosilane paint containing at least 0.01 wt.% silane is forrned.
3 5 A preferred embodiment of a metal substrate coated with an adherent corrosion resistant composite coating of the invention formed from the above CA 02226633 l998-0l-l2 W O 97/04034 PCT~US9~/08718 described blended resin/organosilane powder mixture now will be described.
A steel strip is solvent cleaned of di~, oil and other surface contaminants. Thestrip then is rinsed for 20-30 seconds with a solution having a pH of about 12, a temp~rature of about ~5-60~C and containing 0.005 M of one ot waterglass, 5 sodium silicate or sodium met~si';c~te and 0.00~ M of one of Ba(NO3)2 or Ca(N03)2. After being dried, the silica or s ' cale coated strip then is coated with the above d3scribed blend2d r~sin~organosilane mixture of the invention such as with electrosPtic spray ~uns or by being passed through a nuidized bed.
Whon being coated usin9 el~ctro-~latic guns, the strip preferably is at ambient l O temperature. When being coated using a fluidized bed, the strip pre~erably is preheated to an elevated temperature. The powder coaled strip then would be heated in a conventional manner such as by indvction, infrared and the like, to at least the cufins temperature of the thermosstting r~sin. The stnp would be .~...i.ltained at this temparature for suJ-.~ s.n time to- melt the ~asin and silane, 1 5 ~iS501VEI the silane into the resin and diffuse the silane to the surface of the inorganic silicon coating. Tha strip now would be coated with an adherent, durable, corrosion resistant composite coating having an outer crosslinked paint layer bonded to an inner inorganic layer by an organosilane. This coated steel would have particular advantages over ordinary painted steels because 20 the interface between the steel and the paint, i.~., th~ silicon containing inorganic layer, is very resistant to moisture. Thus, the composite coated strip of the invention can advantageously be used in wet environments.
It will be understood various modifications can be made to the invention without departing from the spirit and scope of it. Therefore, the limits of the 2 ~ inv~ntion should be determined ~rom the appended claims.
RESISTANCE AND IMPROYED PAINT ADHESION
~ACKGROUND OF THE INVENTION
s This invention relates to an organic powder co--~rositisn and a method of using the powder composition tor forming a crosslinked paint coupled to a metal substrate for protecting the substrate from corrosion. More particularly, the powder composition inc4~des a homogeneous mixture of a thermosetting rasin 10 and a solid, non-hydrolyzed, functional organosilane coupling agent.
It is known to forrn a composite coating on steel sheet for providing corrosion protection. US patent 5,108,793; incorporated herein by reference, discloses rinsing a steel sheet with an alkaline solution containing a silicate,drying the sheet to form an insolubl~ inorganic silicate coating, rinsing the l 5 coated sheet in an aqueous solution containing an organosilane coupling agent and then drying the sheet forming a silane film on the outer sur~ace of the silicate coating. The silicate coating provides excellent corrosion protection of the steel sheet. If the sheet is painted, ihe silane film acts as a coupling agent forming a stn n~ oovalent bond between the silicate coating and the paint. An 20 embodiment of this patent includes coid-rolled and ~alvanized steel sheets initially treated with a phosphate conversion coating, then treated with the twostep silicate/silane rinse coating and lastly electrostatically coated with a powder paint or cathodically electrocoated with a paint for forming a composite coating. The silicate/silane layer improves corrosion protection and strengthens25 the bond between the inner phosphate layer and the outer paint layer. A
disadvantage with this process is that some of the sil c~t~ inevitably bscomes transferred to the silane rinse tank thereby contaminating the silane solution.
This contamination may reduce the effectiveness of the silane as a coupling agent. Another disadvantage is that hydrolyzed silane solutions have a 30 relatively short storage life. Organosilanol solutions tend to condense and polymerize thereby minimizing their chemical interaction with paints.
It is well known to provide corrosion protection to steel sheet by coating with a liquid resin containing an organosilane coupling agent. These liquid resins have the same disadvantage referred to above in that hydrolyzed silanes 3 5 have reduced effectiveness as coupling agents.
-CA 02226633 1998-01-li More recently, it has become known to provide c~rrosion protection to steel sheet by coating the sheet with a powder containing a silicon2 resin. US
patent 5,077,3~4 discloses an in-situ formed polymeric mixture comprising an acrylic graft copolymer of silicone resin used as a polymeric binder in powder paint. Silicone resin and ethylenic monomers are dissolved in a solvent heated to 50-1~0~C and mixed until polymerization is completed. The solvent then is stripped away leaving a non-~elled polymerized binder. A disadvantage of using this powder paint is believed to be that a ~ood bond is not ~ormed between the paint and steel substrate- Since the silicone resin has already l 0 been reacted when in-situ combined with the ethylenic monomers when forming the acrylic polymer, the silicone resin will not act as a coup6ng agent between the outer acrylic layer and the steel substr~ts.
Accordingly, there is a need to provide an organosilane having a long storage life that can be used as a coupling agent when forming a crosslinked 1 5 coating. There is a further need for developing a low cost, environmentally safe process for forming an adherent crosslinked coating coupled to a metal substrate such as cold-rolled steel or galvanized steel.
BRIEF SUMMARY OF THE INVENTION
The invention relates to an organic powder composition and a method of using the powder composition for forming a crosslinked paint coupled to a metal substrate for protecting the substrate from corrosion. The powder c~n-position of ths invention includes a homogeneous mixture of a thermosetting resin and ~
25 solid, non-hydrolyzed, functional low molecular weight organosilane coupling agsnt. The organosilane is a solid at ambient temperature, hss a me~ing point no greater than ths curing telmp~rature of the resin and is readily diss~lved into the resin during crosslinking on the su~s~t~te.
Another feature of the invention includes forming a corrosion rasistant 30 coating on a metal substrate using ths aforesaid powder mixture with the coating being coupled to the substrate by the organosilane. The coating is the reaction product ~ormed by in-situ curing of the powder mixture aRer being deposited onto the substrate. Preferably, the crosslinked layer has a thickness of at least 10 tlm.
_ Another feature of the invention is for the aforesaid corrosion resistant coating to be a composite coating including a non-toxic inor~anic inner layer scoupled to the outer crosslinked layer by the organosilane.
A furthsr feature of the invention is forming a corrosion resistant coating Son a metal substrate including the steps of providin~ a homogeneous powder mixture of a thermosetting resin and a solid, non-hydrolyzed, functional low mol~cu'~ weight organosilane coupling agent, depositin9 a layer of th~ powder mixture onto the substrate, heating the substrate to a temperature at least equal to the curing temperature of the resin and maintainin~ this temperature for 10sufficient time to melt the resin and the or~anosilane. The resin is cured andforms a crosslinked layer that becomes tightly bonded to the substrate by the organosilane.
Another feature of the invention is for the aforesaid powder mixtur2 to have an olganosilane concentration of 0.01-10 wt.%.
1 ~Another feature of the invention inclu~es the addRional step of depositing an inorganic îayer onto the substrate prior to depositing the powder layer.
Another feature of the invention is for the aforesaid crosslinked layer to have a thickness of at least 10 llm.
Another feature of the invention is for the aforesaid resin to have a curing 2 0temperature of 1 00-250~C.
Another feature of the invention is for the aforesaid inorganic layer to include a silicate.
Another feature of the invention is for the aforesaid resin beins from the group consisling of epoxy, polyester, epoxy-polyester, acrylic, acrylic-urethane2 Sor fluorovinyl.
An object of the invention is to form a corrQsion resistant adherent coating on a metal substrate using an organosilane coupling agent having a long storage life.
Another object is to form a corrosion resistant adherent composite 3 0coating on a metal substrate having an inorganic inner layer formed from a rinse solution having an extended storage life.
Another object is to provide a low cost, environmentally safe, process for forming a corrosion resistant adherent coating on cold-rolled or galvanized steel sheets using an organosilane coupling agent.
3 SAdvantages of the invention include a long storage life Sor an organosilane coupling agent, forming a corrosion resistant coating having good -adhsrencQ to a variety of metal surfaces without using an environmentally hazardous waste subst~nce, e.Q. chromate rinsss, and no contamination of a rinse solution containing an inorganic coating material.
S DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention includes providing a homogeneously blended powder composition, i.e., a paint, including a thermosetting resin and a solid, non-hydrolyzed, functional low molecular weight organosilane coupling agent that is 10 soluble in the thermoseffing resin. Th~ organic resin may be any thermosetting polymer such as epoxy, polyester, epoxy-polyester, acrylic, acrylic-urethane or fluorovinyl. The sitane rnay be any organic compound so long it is solid at ambient temperature, has a melting temperature no higher than the curing temperature of the resin, capable of being dissolved into the resin and docs notl ~i include OH groups. By a low molecular weight silane is meant monomeric, dimer'ic or oligomeric mol~cules, i.s., RSi(OX)3.
Hydrolyzed organosilanes, such as NH2-(CH2)3Si(OH)3, are undesirable because they are liquid at ambient temperature and tend to polymerize quickly.
Although solid, non-hydrolyzed organosilanes react more slowly than 20 hydrolyzed organosilanes, the non-hydrolyzed forms do not polymerize as rapidly. For epoxy, polyester and acrylic resins, the following commercially available alkoxy silanes and chlorosilanes could be used:
triphenylethoxysilane, triphenylfluorosilane, phenylallyldichlorosilane, N-phenylaminopropyltrimethoxysilane, neophylmethyldiethoxysilane (or the 2~i dimethoxy version), n-octadecyldimethylmethoxysilane, n-octadecyldimethyl[3- trimethoxysilyl-propyl] ammoniumchloride, 2-(3,4-epoxyclyclohexyl)ethyltrimethoxysilane, t-butyldiphenylmethoxysilane, phenethyltrimethoxysilane and styrylethyltrimethoxysilan~. For fluorovinyl resins such as PVDF or PTFE, the following commercially available silanes 3 0 could be used: [2-(perfluorohexyl)ethylltrichlorosilane, t2-(perfluorooctyl)ethyl~trichlorosilane, 1 H, 1 H, 2H, 2H
perfluoralkyltriethoxysilane, 3,3,3-trifluoropropyltriethoxysilane or (heptafluoroisopropoxy)propyltriethoxysilane. A preferred silane is 3-(N-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilanehydrochloride having 3 ~ the following structure: ' W O 97/04034 PCT/U~5S1~718 CH2~H
~NHcH2cH2NH2+
\CH2CH2Si(OCH3)3 The blended resinlorganosilane mixture preferably is used as paint with the mixture includin~ one or more ~ditional powder additives such as a pi~ment and a filler. For example, one or more-of titanium-oxide, lead oxide, 15 zinc oxide, silica, calcium oxide, calcium carbonata, chromium oxide, carbon black and mixtures thereof may be used 85 a pigment. One or more of clay, silica, talc, mica, woolastomite and wood flower may be used as a filler. The powders of the mixture preferably have a particle size less than 32~ mesh. The curing temperature of the resin preferably is within the range of about 100-20 250~C. The composition of the mixture, including any additives, preferablyshould be 0.01-10 wt.% organosilane, mors preferably at least about 0.2 wt.%
organosilane. The concentration of the organosilane should be a2 least 0.01 wt.% be~se this amount is needed so that the silane diffvses to the interface of the metal substrate. The concentration of the organosilane should not 2 S exoeed 10 wt% bec?vse it may adversely affect the paint properties, may cause the paint to become pl~stic~ and may weaken the covalent bond be~e~n the paint layer and the metal sul,~tr~e by weak boundary byer effects.
The ~le.-~e~l resin/organosilane mixture will form a very adherent, corrosion res;sla~t, cro~s-inked coating or paint coupled to a metal substrate by 3 0 the silane. The coating can be formed on a variety of metai sur~acas including, but not limited to, hot rolled and pickled steel sheets, cold-rolled steel sheets, stainless steei sheets, hot dip metallic coated steel sheets, electroplated mstallic coated steel sheets, aluminum sheets and aluminum alloy sheets. The metallic coating may include one or more layers of lead, Isad alloy, nickel, 3 5 nickel alloy, nickel terne, zinc, zinc alloy, aluminum, aluminum alloy, and the like. A phosphate conversion coating also may be applied to these steel sheets W O 97io4034 PCTnUS95/08718 prior to being coated with the resin/organosilan~ powder mixture. The metal substrate may include continuous stnp and 10il, sheets cut to length as well as bars, anglas, tubes and b~ams.
After the resin/or~anosilane powder mixture is applied to a metal 5 subsl-ale. the substrate is heated to at l~ast the curin3 t~mp~rature of the resin.
The resin and organosilane melt with the silane bein dissolved into the liquid resin. Prior to the rssin being crosslinked and l~ecG--,ing solid, the silane will have interacted with the resin and hav~ migrated to the surface of the substrate.
The silane reacts with OH groups on the surface of the substrate forming a 10 strong ccvalent bond of the type:
X~H + CH30-~i- ~ X O-~ + CH30H t or X~H + C:l-$i- _ X~$i. + HCI t where X is a metal oxide on the surface of ~he substrate or an inor~anic lay3r.
15 The oxides of some metals include OH groups. In ths cas8 where the me!al substrate is aluminum, an aluminum alloy or a steel sh~et coa~ed with aluminum or an aluminum alloy, th~ silane may react with the OH groups present in the aluminum oxide surface of the substrate forming a covalent bond of the type Me-O-Si-. In the case where the metal sul,slra~e is steel or a st~el2 O substrate coated with a metallic coating other than aluminum or an aluminum alloy, the substrate first should be preferably coated with an inner inorganic silicon containing layer having OH groups prior to deposition of the resin/organosilans powder mixture. The inorganic layer may be a silicats or a silica. In tha latter oase, the silans r~acts with ths OH groups present in the 2 5 inor~anic silicon containin~ layer ~Gr.ni,-~ a stron~ coYal~nt bond of the type Si-O-Si- which is preferr~d to the Me~Si- bond descri~e~ above.
While the silane is reactin~ with the OH groups on the surface of the metaJ substrate during curin~ of the r~sin, the fur,c~ion~l ~roup of the silane also will have interacte~ with a ~unctional group in the resin or the cr~sslinl~r in tha 3 O r~sin, e.g., R-NH2 ~ H2C--CH-R' ~ R-NH-CH2-CH-R' ~ OH
35 where R may be -(CH2)3Si(OCH3)3 and R' is the thermosetting resin, ~.9., epoxy.
W O 97/04034 PCT/U~5S~5718 In a preferred embodiment, ~he corrosion resistant coating is a composite of the previously described inner inorganic layer and the outer crosslinked paint layer. Preferably, the inner layer is a silicate formed in a manner as describedin US patent 5,108,793; incorporated herein by r~ference. Waterglass is J S dissolvad in~v8ter, e.g., an alkaline solution containing Ba(N03)3 ~ n. The solution preferably is maintained at an elevated temperatur~, e.g., 55-60~C, to reduc~ the rinse time. A steel strip is rinsed with the silicats solL~ion preferably by dipping the strip into the solution for at least 20 seconds. After dipping, the strip is rinsed and dried. The silicate coating provides excellent corrosion 1 0 protection for the steel strip.
The silicate coated strip then is coated with a layer having a uniform thickness of the blended powder mixture of the thermosetting powder and organosilane powdsr. The organic powder may be applied to the strip by olsoll(,slalic spray guns such as ~isclose~ in US patent 5,0~9,446; incorporatedl 5 herein by reference, or by passing the strip through an ele~l,osl~l;c~ charged fluidized bed. If the fluidi7ed bed is not electrost~ti~lly c~arged, the strip must be preheated. The strip is heated to at least the curing temperature of the thermosetting resin by n-st passing the powder coated strip preferably through an induction coil. The heated strip then passes through another heater such as 2 0 infrared for maintaining the molten resin for sufficient time so that the organosilane becomes dissolved into and diffuses to a sur~ace of the steel strip.
An important feature of the invention is that the organosilane be soluble with the thermosetting resin. That is, the organosilane must be ~r~bl~ of being melted as well as go into solution with the molten resin. During this time period, the organosilane also migrates toward the inorganic inner layer, e.g., silicate, thoreby establishing a ti~ht covalent bond b~tween th~ inorganic tayer and the crosslinked outer paint layer.
Details of a blended resin/organosilane mixturs of the invention will be better understood from the following example. A powder containing a 3 0 th~rmosettinq resin and optionally one or more fillers or pigments is prepared in a conventional manner. Thereafter, a solid, non-hydrolyzed low molecular weight organosilane is blended with the powder mixture by cryogenic grinding until a homogeneous powder resin/organosilane paint containing at least 0.01 wt.% silane is forrned.
3 5 A preferred embodiment of a metal substrate coated with an adherent corrosion resistant composite coating of the invention formed from the above CA 02226633 l998-0l-l2 W O 97/04034 PCT~US9~/08718 described blended resin/organosilane powder mixture now will be described.
A steel strip is solvent cleaned of di~, oil and other surface contaminants. Thestrip then is rinsed for 20-30 seconds with a solution having a pH of about 12, a temp~rature of about ~5-60~C and containing 0.005 M of one ot waterglass, 5 sodium silicate or sodium met~si';c~te and 0.00~ M of one of Ba(NO3)2 or Ca(N03)2. After being dried, the silica or s ' cale coated strip then is coated with the above d3scribed blend2d r~sin~organosilane mixture of the invention such as with electrosPtic spray ~uns or by being passed through a nuidized bed.
Whon being coated usin9 el~ctro-~latic guns, the strip preferably is at ambient l O temperature. When being coated using a fluidized bed, the strip pre~erably is preheated to an elevated temperature. The powder coaled strip then would be heated in a conventional manner such as by indvction, infrared and the like, to at least the cufins temperature of the thermosstting r~sin. The stnp would be .~...i.ltained at this temparature for suJ-.~ s.n time to- melt the ~asin and silane, 1 5 ~iS501VEI the silane into the resin and diffuse the silane to the surface of the inorganic silicon coating. Tha strip now would be coated with an adherent, durable, corrosion resistant composite coating having an outer crosslinked paint layer bonded to an inner inorganic layer by an organosilane. This coated steel would have particular advantages over ordinary painted steels because 20 the interface between the steel and the paint, i.~., th~ silicon containing inorganic layer, is very resistant to moisture. Thus, the composite coated strip of the invention can advantageously be used in wet environments.
It will be understood various modifications can be made to the invention without departing from the spirit and scope of it. Therefore, the limits of the 2 ~ inv~ntion should be determined ~rom the appended claims.
Claims (17)
1. An organic powder composition for protecting metal from corrosion, comprising:
a homogeneous powder mixture of a thermosetting resin and a solid, non-hydrolyzed low molecular weight organosilane coupling agent wherein said organosilane is soluble with said resin when molten, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, and wherein the concentration of said organosilane in said Powder mixture is 0.2-10 wt.% and said mixture has a particle size less than 325 mesh.
a homogeneous powder mixture of a thermosetting resin and a solid, non-hydrolyzed low molecular weight organosilane coupling agent wherein said organosilane is soluble with said resin when molten, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, and wherein the concentration of said organosilane in said Powder mixture is 0.2-10 wt.% and said mixture has a particle size less than 325 mesh.
2. The mixture of claim 1 wherein said organosilane is of the form of 3-(N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilanehydrochloride.
3. The mixture of claim 1 wherein said resin has a curing temperature of 100-250°C.
4. The mixture of claim 1 wherein said resin is from the group consisting of epoxy, polyester, epoxy-polyester, acrylic, acrylic-urethane or fluorovinyl.
5. The mixture of claim 1 including one or more of a pigment and a filler.
6. A metal having a corrosion resistant coating, comprising:
a crosslinked layer coupled to a metal substrate, said crosslinked layer being the reaction product formed by curing a powder, said powder having a particle size less than 325 mesh and being a blended mixture of a thermosetting resin and 0.2-10 wt. % of a solid, non-hydrolyzed low molecular weight organosilane, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, said crosslinked layer being coupled to said substrate by said organosilane.
a crosslinked layer coupled to a metal substrate, said crosslinked layer being the reaction product formed by curing a powder, said powder having a particle size less than 325 mesh and being a blended mixture of a thermosetting resin and 0.2-10 wt. % of a solid, non-hydrolyzed low molecular weight organosilane, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, said crosslinked layer being coupled to said substrate by said organosilane.
7. The metal of claim 6 wherein the coating includes a non-toxic, inorganic inner layer, said crosslinked layer being coupled to said inner layer by said organosilane.
8. The metal of claim 7 wherein said inner layer is a silicate.
9. The metal of claim 8 wherein said crosslinked layer has a thickness of at least 10 µm.
10. The metal of claim 9 wherein said resin has a curing temperature of 100-250°C.
11. A method of forming a corrosion resistant coating on metal, comprising the steps of:
providing a homogeneous powder mixture including a thermosetting resin and an non-hydrolyzed low molecular weight organosilane coupling agent wherein said organosilane is soluble with said resin, when molten, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, depositing a layer of said mixture onto a metal substrate, heating said substrate to a temperature at least equal to the curing temperature of said resin, and maintaining said substrate at said temperature for sufficient time to melt said resin and said organosilane whereby said organosilane is dissolved into said resin, said resin being crosslinked and said organosilane being diffused to the surface of said substrate whereby said crosslinked coating is coupled to said substrate by said organosilane.
providing a homogeneous powder mixture including a thermosetting resin and an non-hydrolyzed low molecular weight organosilane coupling agent wherein said organosilane is soluble with said resin, when molten, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, depositing a layer of said mixture onto a metal substrate, heating said substrate to a temperature at least equal to the curing temperature of said resin, and maintaining said substrate at said temperature for sufficient time to melt said resin and said organosilane whereby said organosilane is dissolved into said resin, said resin being crosslinked and said organosilane being diffused to the surface of said substrate whereby said crosslinked coating is coupled to said substrate by said organosilane.
12. The method of claim 11 including the additional step of depositing an inorganic layer on said substrate prior to deposition of said mixture.
13. The method of claim 12 wherein said inorganic layer is a silicate having a thickness of at least 2 nm.
14. The method of claim 11 wherein said powder mixture is deposited electrostatically.
15. The method of claim 11 wherein said resin has a curing temperature of 100-250°C.
16. The method of claim 11 wherein the concentration of said organosilane in said mixture is 0.2-10 wt. %.
17. A method of forming a corrosion resistant composite coating on a steel strip, comprising the steps of:
providing a rinsing solution and a homogeneous powder mixture, said rinsing solution including an alkaline inorganic silicate and a metal salt, said mixture including a thermosetting resin having a curing temperature of 100-250°C and a solid, non-hydrolyzed low molecular weight organosilane coupling agent wherein said organosilane is soluble with said resin when molten, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, the concentration of said organosilane in said mixture being 0.2-10 wt. %.
rinsing the steel strip with said solution, drying the steel strip thereby forming a relatively insoluble silicate layer, electrostatically depositing a layer of said mixture onto said silicate layer, heating the steel strip to a temperature at least equal to the curing temperature of said resin, and maintaining the steel strip at said temperature for sufficient time to melt said resin and said organosilane whereby said resin forms a crosslinked layer, said crosslinking layer being coupled to said silicate layer by said organosilane.
providing a rinsing solution and a homogeneous powder mixture, said rinsing solution including an alkaline inorganic silicate and a metal salt, said mixture including a thermosetting resin having a curing temperature of 100-250°C and a solid, non-hydrolyzed low molecular weight organosilane coupling agent wherein said organosilane is soluble with said resin when molten, said organosilane being a solid at ambient temperature and having a melting point no greater than the curing temperature of said resin, the concentration of said organosilane in said mixture being 0.2-10 wt. %.
rinsing the steel strip with said solution, drying the steel strip thereby forming a relatively insoluble silicate layer, electrostatically depositing a layer of said mixture onto said silicate layer, heating the steel strip to a temperature at least equal to the curing temperature of said resin, and maintaining the steel strip at said temperature for sufficient time to melt said resin and said organosilane whereby said resin forms a crosslinked layer, said crosslinking layer being coupled to said silicate layer by said organosilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002226633A CA2226633A1 (en) | 1995-07-14 | 1995-07-14 | Metal substrate with enhanced corrosion resistance and improved paint adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002226633A CA2226633A1 (en) | 1995-07-14 | 1995-07-14 | Metal substrate with enhanced corrosion resistance and improved paint adhesion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2226633A1 true CA2226633A1 (en) | 1997-02-06 |
Family
ID=4161980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002226633A Abandoned CA2226633A1 (en) | 1995-07-14 | 1995-07-14 | Metal substrate with enhanced corrosion resistance and improved paint adhesion |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2226633A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694775A (en) * | 2020-12-19 | 2021-04-23 | 天津西敦粉漆科技有限公司 | Method for improving corrosion resistance of powder coating |
| CN115120028A (en) * | 2022-07-13 | 2022-09-30 | 东莞市凤仪堂化妆用具有限公司 | Copper pipe cosmetic brush and preparation method thereof |
-
1995
- 1995-07-14 CA CA002226633A patent/CA2226633A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694775A (en) * | 2020-12-19 | 2021-04-23 | 天津西敦粉漆科技有限公司 | Method for improving corrosion resistance of powder coating |
| CN115120028A (en) * | 2022-07-13 | 2022-09-30 | 东莞市凤仪堂化妆用具有限公司 | Copper pipe cosmetic brush and preparation method thereof |
| CN115120028B (en) * | 2022-07-13 | 2024-01-30 | 东莞市凤仪堂化妆用具有限公司 | Copper pipe cosmetic brush and preparation method thereof |
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