WO2003055954A1 - A coating composition and method for preparing and applying the same - Google Patents

A coating composition and method for preparing and applying the same Download PDF

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Publication number
WO2003055954A1
WO2003055954A1 PCT/TR2002/000075 TR0200075W WO03055954A1 WO 2003055954 A1 WO2003055954 A1 WO 2003055954A1 TR 0200075 W TR0200075 W TR 0200075W WO 03055954 A1 WO03055954 A1 WO 03055954A1
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WO
WIPO (PCT)
Prior art keywords
mixture
coating
byk
total weight
butylate
Prior art date
Application number
PCT/TR2002/000075
Other languages
French (fr)
Inventor
Müge AKAY
Original Assignee
Arçelik A.S.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arçelik A.S. filed Critical Arçelik A.S.
Priority to TR2004/01372T priority Critical patent/TR200401372T1/en
Priority to AU2002367167A priority patent/AU2002367167A1/en
Publication of WO2003055954A1 publication Critical patent/WO2003055954A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32Epoxy compounds containing three or more epoxy groups
    • C08G59/3254Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating 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
    • C09D183/10Block or graft copolymers containing polysiloxane sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00Characterised by the use of 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; Derivatives of such polymers

Definitions

  • the present invention relates to a mixture that increases the resistance of polymeric materials, particularly of polycarbonate materials against scratching and against the effects of alkaline substances, and to a method for preparing and applying said mixture.
  • the polymeric material with such advantageous features as lightness, practical usage and low cost, are used instead of the glass based material, in the domestic appliances, for instance in washing machines, the physical strength of such material is not sufficient and they are scratched and influenced by the alkaline material.
  • the coating technologies are employed in order to produce material with more superior properties and with higher additional values by coating all kinds of surfaces with a material that will give different thickness and properties to said surfaces.
  • the sol-gel technology is one of the leading technologies, being preferred due to its various advantages and the superior physical, mechanical and chemical properties it provides to the material to be coated, as well as the extension of the service usage life of said material.
  • the sol-gel technique consists of applying the combination of organic polymeric materials and oxidized or not oxidized inorganic ceramic materials and/or a composite mixture formed of organic modified non- metallic compounds, to the surface. These techniques are designed by using different properties of the organic and inorganic material, according to the intended function of the desired coating and are applied in the suitable process with suitable combinations.
  • reaction is carried out in water or in an organic solvent.
  • a colloidal solution (SOL) comprising particles with nanometric (nm) dimensions, passes to a two-phased gel (GEL) (position) state as the result of the reaction and process while forming the inorg-tnic polymeric net structure of the hydrolyzable compounds, such as metal (position) state as the result of the reaction and process while forming the inorganic polymeric net structure of the hydrolyzable compounds, such as metal alkoxides, as the result of hydrolyzation-condensation reactions, the organic polymeric net layer is formed in the system by the addition of organic compounds.
  • the organic groups have two important functions:
  • the organic groups modify the inorganic net by carrying their properties to the inorganic net.
  • They form an organic polymeric net by being added in a polymerized form to the inorganic net.
  • the sol-gel technique is the technique for forming the organic polymeric net structure of the organic modified alkoxid compounds by using the hydrolyzation and condensation reactions.
  • the object of the present invention is to realize a mixture to be used for the coating of polymeric materials, particularly of polycarbonate materials in order to increase their resistance against scratching and against the effects of alkaline substances, and, a method for preparing and applying said mixture.
  • the mixture according to the invention comprises an epoxysilane compound to provide the inorganic polymerisation, an epoxy compound to provide the organic modification, a F-silan to provide the coated surface with hydrophobic properties and a metal alkoxide to harden the coating, which in turn provides resistance against alkali.
  • epoxy-containing silanes that provide the inorganic polymerization are listed below:
  • Aiternative 1 G YEO ⁇ -Gly ⁇ dox propyltrieth ⁇ xysilan
  • the mixture is composed of GLYEO (3- Glycidoxypropyltriethoxysilan), as the epoxy-silane that provides the inorganic polymerization, Araldite GZ 601 as an epoxy compound for organic modification, Tridecafluoro-l,l,2,2-tetrahydro-octyl-l-triethoxysilan
  • the surface of the substrate is cleaned to eliminate grease and dirt, surface activity is enhanced, for instance by the corona method, in order to increase the binding and adhering properties between the surface and the coating, and the surface is cleaned again.
  • the mixture is applied onto the surface, the coated plates are dried at a temperature between 25-250°C for 5-120 minutes, after they are allowed to stay at the room temperature for 10-60 minutes.
  • the surface is coated by immersing the material to be coated into the mixture and drawing it out at a certain speed.
  • the surface is coated by spraying the mixture onto said surface.

Abstract

The object of the present invention is to provide a mixture to be used for the coating of polymeric materials, particularly of polycarbonate materials in order to increase their resistance against scratching and against the effects of alkaline substances, and, a method for preparing and applying said mixture. The mixture according to the invention comprises an epoxysilane compound to provide the inorganic polymerisation, an epoxy compound to provide the organic modification, a F-silan to provide the coated surface with hydrophobic properties and a metal alkoxide to harden the coating, which in turn provides resistance against alkali.

Description

A COATING COMPOSITION AND METHOD FOR PREPARING AND APPLYING THE SAME
The present invention relates to a mixture that increases the resistance of polymeric materials, particularly of polycarbonate materials against scratching and against the effects of alkaline substances, and to a method for preparing and applying said mixture.
When the polymeric material with such advantageous features as lightness, practical usage and low cost, are used instead of the glass based material, in the domestic appliances, for instance in washing machines, the physical strength of such material is not sufficient and they are scratched and influenced by the alkaline material.
The coating technologies are employed in order to produce material with more superior properties and with higher additional values by coating all kinds of surfaces with a material that will give different thickness and properties to said surfaces. The sol-gel technology is one of the leading technologies, being preferred due to its various advantages and the superior physical, mechanical and chemical properties it provides to the material to be coated, as well as the extension of the service usage life of said material. The sol-gel technique consists of applying the combination of organic polymeric materials and oxidized or not oxidized inorganic ceramic materials and/or a composite mixture formed of organic modified non- metallic compounds, to the surface. These techniques are designed by using different properties of the organic and inorganic material, according to the intended function of the desired coating and are applied in the suitable process with suitable combinations. In this method, reaction is carried out in water or in an organic solvent. A colloidal solution (SOL) comprising particles with nanometric (nm) dimensions, passes to a two-phased gel (GEL) (position) state as the result of the reaction and process while forming the inorg-tnic polymeric net structure of the hydrolyzable compounds, such as metal (position) state as the result of the reaction and process while forming the inorganic polymeric net structure of the hydrolyzable compounds, such as metal alkoxides, as the result of hydrolyzation-condensation reactions, the organic polymeric net layer is formed in the system by the addition of organic compounds. Here, the organic groups have two important functions:
a) The organic groups modify the inorganic net by carrying their properties to the inorganic net. b) They form an organic polymeric net by being added in a polymerized form to the inorganic net.
As the result of the said method, a composite layer having the complementary properties of the organic and inorganic phases, such as flexibility, erosion, scratching and resistance to corrosion, is formed on the coated surface. In brief, the sol-gel technique is the technique for forming the organic polymeric net structure of the organic modified alkoxid compounds by using the hydrolyzation and condensation reactions.
In the International Patent Application No. WO 01-042373, a coating for plastic surfaces, which is resistant against scratches, is disclosed.
In the USA Patent No. US 4785067, a coating which is resistant against cleaning materials, is described.
In the European Patent Application No EP 0628610, a coating for plastic surfaces, which is resistant against scratches, is disclosed.
In the European Patent Application No. EP 1137729, a coating for surfaces on which powder paint has been applied, which is resistant against scratches, is disclosed. The object of the present invention is to realize a mixture to be used for the coating of polymeric materials, particularly of polycarbonate materials in order to increase their resistance against scratching and against the effects of alkaline substances, and, a method for preparing and applying said mixture.
The mixture according to the invention comprises an epoxysilane compound to provide the inorganic polymerisation, an epoxy compound to provide the organic modification, a F-silan to provide the coated surface with hydrophobic properties and a metal alkoxide to harden the coating, which in turn provides resistance against alkali.
The epoxy-containing silanes that provide the inorganic polymerization are listed below:
Aiternative 1: G YEO β-Glyάdox propyltriethøxysilan)
CH2 — CH — CH2 — OCtbCHaCHaS OCaHsb
\ / O
Alternative 2: GP S (S-Gfycidoxypropyliήmethoxysilane) CH2 — CH — CH2 — O — CH2CH2CH2St(OMe)3
\ /
0
In the preferred embodiment, the mixture is composed of GLYEO (3- Glycidoxypropyltriethoxysilan), as the epoxy-silane that provides the inorganic polymerization, Araldite GZ 601 as an epoxy compound for organic modification, Tridecafluoro-l,l,2,2-tetrahydro-octyl-l-triethoxysilan
(C6Fi3CH2Si(OC2H5)3) as the F-silane and Zirkonium butylate
(Zr(O(CH2)3CH3) ) as the metal alkoxide to provide resistance against alkali by hardening the coating. While preparing the mixture, GLYEO is mixed with Araldite at a ratio of 10- 50% of its weight. The mixture is hydrolysed by 0.1 N HC1; then the solution is diluted with 5-25% wt butoxyethanol or ethylalcohol or isopropoxyethanol ((CH3)2 CHOCH2CH2OH ) and F-silane (0.5-2.5% of its total weight) is added and stirred. 15-20% wt Zr-butylate is added to the mixture after each 1 mole Zr- butylate is modified by 0.2-1.0 mol acetylacetone. 0.1-0.5% of the total weight BYK 306 or BYK 341 (poly ether modified poly dimethyl polysiloxane) is added and the solution is stirred.
Before applying the mixture, the surface of the substrate is cleaned to eliminate grease and dirt, surface activity is enhanced, for instance by the corona method, in order to increase the binding and adhering properties between the surface and the coating, and the surface is cleaned again. Then the mixture is applied onto the surface, the coated plates are dried at a temperature between 25-250°C for 5-120 minutes, after they are allowed to stay at the room temperature for 10-60 minutes.
In a preferred embodiment of the invention, the surface is coated by immersing the material to be coated into the mixture and drawing it out at a certain speed.
In another embodiment of the invention, the surface is coated by spraying the mixture onto said surface.
In the domestic appliances, e.g. washing machines, by coating the surface of the windows made of polycarbonate material instead of glass, which are provided on the doors of said appliances, with the mixture according to the present invention, their resistance against scratches and alkali substances, is increased.

Claims

1. A mixture for coating the surfaces of polymeric material, particularly of polycarbonate material in order to increase their resistance against scratches and against the effects βf alkali substances, which comprises an epoxysilane compound to provide the inorganic polymerisation, an epoxy compound to provide the organic modification, a F-siϊan to provide the coated surface with hydrophobic properties and a metal alkoxide to harden the coating, which in turn provides resistance against alkali.
2. A mixture as defined in Claim 1, wherein the epoxysilane compound that provides inorganic polymerization is GLYEO (3- Glycidoxypropyltriethoxysilan).
3. A mixture as defined in Claim 1, wherein the epoxysilane compound that provides inorganic polymerization is GPTS (3- Glycidoxypropyltrimethoxysilane).
4. A mixture as defined in Claims 1 to 3, wherein F-silane is
Tridecafluoro- 1 , 1 ,2,2-tetrahydro-octyl- 1 -triethoxysilan (C6F13CH2Si(OC2H5)3).
5. A mixture as defined in Claims 1 to 4, wherein the epoxy compound that provides the organic modification is Araldite GZ 601.
6. A mixture as defined in Claims 1 to 5, wherein metal alkoxide is zirconium butylate.
7. Method for preparing a mixture as defined in Claims 1, 2 and 4-6, comprising the steps of; mixing GLYEO with Araldite at a ratio of 10-50% of its weight, hydrolyzing the mixture with 0.1N HC1, diluting the solution with 5-25% wt isopropoxyethanol ( (CH3)CHOCH2CH2OH ), adding F-silane (0.5-2.5 % of its total weight), adding 15-20% wt Zr-butylate to the mixture after each mole Zr-butylate is modified by 0.2-1.0 mol acetylacetone, and adding
0.1-0.5% of the total weight BYK 306 or BYK 341 (polyether modified polydimethyl polysiloxane).
8. Method for preparing a mixture as defined in Claims 1, 2 and 4-6, comprising the steps of; mixing GLYEO with Araldite at a ratio of 10-50% of its weight, hydrolyzing the mixture with 0. IN HC1, diluting the solution with 5- 25% wt butoxyethanol, adding F-silane (0.5-2.5 % of its total weight), adding 15-20% wt Zr-butylate to the mixture after each mole Zr-butylati is modified by 0.2-1.0 mol acetylacetone, and adding 0.1-0.5%of the total weight BYK 306 or BYK 341 (polyether modified polydimethyl polysiloxane).
9. Method for preparing a mixture as defined in Claims 1, 2 and 4-6, comprising the steps of; mixing GLYEO with Araldite at a ratio of 10-50% of its weight, hydrolyzing the mixture with 0. IN HC1, diluting the solution with 5-25% wt ethylalcohol, adding F-silane (0.5-2.5 % of its total weight), adding 15- 20% wt Zr-butylate to the mixture after each mole Zr-butylati is modified by 0.2-1.0 mol acetylacetone, and adding 0.1-0.5%of the total weight
BYK 306 or BYK 341 (polyether modified polydimethyl polysiloxane).
10. Method for applying a mixture as defined in Claims 1 to 9, onto the surface of a polymeric material based substrate, comprising the steps of; cleaning the surface to eliminate grease and dirt, enhancing the surface activity to increase the binding and adhering properties between the surface and the coating, cleaning the surface again, immersing the surface into the mixture, allowing the surface coated to stand at room temprature for 10-60 minutes, and drying it at 25-250°C for 5-120 minutes.
11. Method for applying a mixture as defined in Claims 1 to 9, onto the surface of a polymeric material based substrate, comprising the steps of; cleaning the surface to eliminate grease and dirt, enhancing the surface activity to increase the binding and adhering properties between the surface and the coating, cleaning the surface again, spraying the mixture onto the surface, allowing the surface coated to stand at room temprature for 10-60 minutes, and drying it at 25~250°C for 5-120 minutes.
12. A polymeric material based substrate which is coated with a mixture as defined in Claims 1 to 11.
PCT/TR2002/000075 2001-12-26 2002-12-26 A coating composition and method for preparing and applying the same WO2003055954A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
TR2004/01372T TR200401372T1 (en) 2001-12-26 2002-12-26 A coating mixture and method of preparing and applying the mixture
AU2002367167A AU2002367167A1 (en) 2001-12-26 2002-12-26 A coating composition and method for preparing and applying the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2001/03721 2001-12-26
TR200103721 2001-12-26

Publications (1)

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WO2003055954A1 true WO2003055954A1 (en) 2003-07-10

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TR (1) TR200401372T1 (en)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2928860A1 (en) * 2008-03-21 2009-09-25 Ereform Sarl Construction panel for fabricating a furniture, comprises a rigid support made of polycarbonate, a coating based on epoxy resin fixed on the support, and an intermediate layer of white color disposed between the support and the coating
US9051423B2 (en) 2009-09-16 2015-06-09 3M Innovative Properties Company Fluorinated coating and phototools made therewith
US9096712B2 (en) 2009-07-21 2015-08-04 3M Innovative Properties Company Curable compositions, method of coating a phototool, and coated phototool

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19857317A1 (en) * 1998-12-11 2000-06-15 Inst Neue Mat Gemein Gmbh domestic appliances
DE19915378A1 (en) * 1999-04-06 2000-10-12 Inst Neue Mat Gemein Gmbh Household appliances with a catalytic composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19857317A1 (en) * 1998-12-11 2000-06-15 Inst Neue Mat Gemein Gmbh domestic appliances
DE19915378A1 (en) * 1999-04-06 2000-10-12 Inst Neue Mat Gemein Gmbh Household appliances with a catalytic composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2928860A1 (en) * 2008-03-21 2009-09-25 Ereform Sarl Construction panel for fabricating a furniture, comprises a rigid support made of polycarbonate, a coating based on epoxy resin fixed on the support, and an intermediate layer of white color disposed between the support and the coating
US9096712B2 (en) 2009-07-21 2015-08-04 3M Innovative Properties Company Curable compositions, method of coating a phototool, and coated phototool
US9051423B2 (en) 2009-09-16 2015-06-09 3M Innovative Properties Company Fluorinated coating and phototools made therewith

Also Published As

Publication number Publication date
TR200401372T1 (en) 2005-01-24
AU2002367167A1 (en) 2003-07-15

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