WO2016055157A1 - Substrats transparents et résistants à l'abrasion, pourvus d'un revêtement anti-adhésif en composite céramique, procédé de fabrication et utilisation - Google Patents

Substrats transparents et résistants à l'abrasion, pourvus d'un revêtement anti-adhésif en composite céramique, procédé de fabrication et utilisation Download PDF

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Publication number
WO2016055157A1
WO2016055157A1 PCT/EP2015/001964 EP2015001964W WO2016055157A1 WO 2016055157 A1 WO2016055157 A1 WO 2016055157A1 EP 2015001964 W EP2015001964 W EP 2015001964W WO 2016055157 A1 WO2016055157 A1 WO 2016055157A1
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WO
WIPO (PCT)
Prior art keywords
transparent
abrasion
resistant
ceramic composite
coated substrates
Prior art date
Application number
PCT/EP2015/001964
Other languages
German (de)
English (en)
Other versions
WO2016055157A8 (fr
Inventor
Ertugrul Arpac
Murat Akarsu
Ömer KESMWZ
Helmut Schmidt
Esin AKARSU
Original Assignee
Hsm Techconsult Gmbh
Nanoen Ar-Ge Danismanlik Mühendislik Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hsm Techconsult Gmbh, Nanoen Ar-Ge Danismanlik Mühendislik Ltd. filed Critical Hsm Techconsult Gmbh
Publication of WO2016055157A1 publication Critical patent/WO2016055157A1/fr
Publication of WO2016055157A8 publication Critical patent/WO2016055157A8/fr

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Classifications

    • 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
    • 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

Definitions

  • PTFE has a low surface energy, both for the polar and for the dispersive fraction. Therefore, coatings of PTFE are very often used for non-stick purposes, for example as release coatings, liners of chemical reactors or cookware. Disadvantages of such coatings are, for example, that they require a sintering process at a temperature between 350 and in some cases above 400 ° C. at which parts of the coating can decompose to form toxic compounds (eg fluorophosgene, tetrafluoroethylene or trifluoroacetic acid) (David A. Ellis, Scott A. Mabury, Jonathan W. Martin and Derek CG Muir, Nature 412, 2).
  • toxic compounds eg fluorophosgene, tetrafluoroethylene or trifluoroacetic acid
  • Another disadvantage is that due to the low adhesion of the Teflon layer to a substrate, adhesion-enhancing measures are required, such as stainless steel and aluminum, an intermediate layer of roughening oxides such as alumina or titania.
  • adhesion-enhancing measures such as stainless steel and aluminum, an intermediate layer of roughening oxides such as alumina or titania.
  • Other disadvantages are the low scratch resistance of PTFE and problematic disposal due to the high chemical resistance of the material. Transparent layers on metals can not be produced by these methods.
  • FR 2739392 describes a sol-gel layer which does not contain fluorinated hydrocarbons, but instead uses PDMS and condensates of ortho-silicic acid esters and alkoxysilanes. To achieve sufficient scratch resistance, oxidic components such as aluminum oxide or titanium dioxide are then added to the system. Even with this, no transparent coating systems can be produced.
  • the object of the present invention is to provide coating systems for transparent non-stick coated glass ceramic or metal substrates with high thermal resistance and high abrasion resistance, in which the optical character of the substrate is practically unchanged, and for example the so-called "metal look" of a
  • the layer system should be able to be used in the sense of a one-component system.
  • inorganic particles are materials such as feldspar, quartz, boehmite or crown glass, but also all other colorless inorganic components whose refractive index is in the required range, For this purpose, 20-40%, preferably 25-35%, of the compounds of general formula (I)
  • SiY 4 (Sol-gel starting component II), where Y may be silicon-bonded hydrolyzable groups, for example alkoxy groups, -NH 2 groups, halides or OH groups, alkoxy groups and halides being preferred and alkoxy groups being particularly preferred, and optionally with 5-30%, preferably 10-20%, of the compounds of general formula (III)
  • Me “" 'v Z 2 -4 (sol gel -Ausgangskomponente III), wherein Me represents the elements Mg, Sc, Y, Ti, Zr, Nb, B, Al, Ge, Fe, Co, Ni, Cu, Cr, And wherein Ti, Zr, Nb, B, Al and Sn are preferred and Al, Sn, Ti, and Zr are particularly preferred, and Z is a hydrolyzable group directly bonded to Me and which is, for example, a halide, an OH May be a group or an alkoxy group, and wherein alkoxy groups are particularly preferred, in a hydrolysis and condensation process (see also Brinker and Scherer book), are reacted to aqueous or non-aqueous sols, and with 0.1-5%, preferably 0, 3-3%, of the compounds of general formula (IV)
  • Such materials are for example feldspar, quartz, boehmite or crown glass, but also all other colorless inorganic components in which the refractive index is in the required range.
  • the reaction takes place for example in a solvent mixture of water and aliphatic alcohols, the chain lengths of the aliphatic alcohols 1-6, preferably 1-5 and particularly preferably 2-3 and the mixing ratio of water: alcohol 0.3: 3.0 and preferably 0, 7: 1.3.
  • both mineral and organic acids can be used in amounts of 0.05-2%, with 0.1 to 0.5% being preferred.
  • the coatings can also be prepared colorless transparent, if temperature-resistant, ionic or colloid color support according to the general formula (II) are used.
  • Fe, Co, Ni, Cu, and Cr yield transparent ionically colored layers, while Au results in colloidal transparent dyeings (gold ruby red).
  • the object of the invention can be solved by several embodiments.
  • the component (V) is added and stirred for 5-30, preferably 10-20 minutes, wherein the temperature is between room temperature and 50 ° C and wherein room temperature is preferred.
  • mineral components or molten silicate glasses which are in the questionable refractive index range.
  • the suspension is dispersed by stirring for 30 minutes to 2 hours, preferably at 1 hour, and then in a rotary ball mill at high speed, preferably 2000-4000, more preferably 3000 revolutions per minute using inorganic grinding media, especially glass beads and more preferably glass beads with diameters of 2-3 mm.
  • Embodiment 2 Embodiment 2
  • the object according to the invention is also achieved by preparing a mixture of the acidic catalyst with compounds of the general formula (IV), where (IV) has a molecular weight of 300-1000, preferably 400-700, to this mixture the component (V ) and stirred for 5-30, preferably for 10-20 minutes, wherein the temperature is between room temperature and 50 ° C and room temperature is preferred.
  • the reaction is continued until the free amount of water, e.g. determined via the Karl Fischer titration, reaching a constant value.
  • a sol of compounds of the general formula (III) is added dropwise to the reaction mixture with stirring.
  • Embodiment can be performed with the two alternatives a) and b) according to the first embodiment.
  • the suspension is dispersed by stirring for 30 minutes to 2 hours, preferably at 1 hour, and then in a rotary ball mill at high speed, preferably 2000-4000, more preferably 3000 revolutions per minute using inorganic grinding media, especially glass beads and more preferably glass beads with diameters of 2-3 mm.
  • This embodiment can also be carried out with the two alternatives a) and b) according to embodiment 1.
  • the object according to the invention is also achieved by preparing a mixture of the acid catalyst with compounds of the general formula (IV), where (IV) has a molecular weight of 300-1000, preferably 400-700, to this mixture the compounds of the general Formula (II) and 20-40% water, preferably 30% added and stirred for 5-30, preferably 10-20 minutes, wherein the temperature is between room temperature and 50 ° C and room temperature is preferred.
  • the reaction is continued until the free amount of water, determined for example via the Karl Fischer titration, reaches a constant value.
  • a sol of compounds of general formula (III) is added dropwise to the reaction mixture with stirring.
  • reaction mixture a compound of general formula (III) are added dropwise and added by adding a quantity of water of 5-20%, preferably 10% with stirring.
  • a quantity of water of 5-20%, preferably 10% with stirring is added to the reaction mixture.
  • all mineral components or molten silicate glasses which are in the questionable refractive index range.
  • the suspension is dispersed by stirring for 30 minutes to 2 hours, preferably at 1 hour, and then in a rotary ball mill at high speed, preferably 2000-4000, more preferably 3000 revolutions per minute using inorganic grinding media, especially glass beads and more preferably glass beads with diameters of 2-3 mm.
  • This embodiment can also be carried out with the two alternatives a) and b) according to embodiment 1.
  • Embodiments 1-4 may be applied to the substrates by any conventional wet coating method, such as dipping, spraying, flooding, spin coating, roll coating or printing. Dipping and spraying are preferred, spraying is particularly preferred. Before spraying, the substrates are cleaned and freed from dust and adhering contaminants, especially greasy and oily substances. For this purpose industrie busye cleaning methods are used according to the prior art.
  • the spraying is carried out with a commercially available spray gun, for example a cup gun and the layer is applied in thicknesses of 10-60 ⁇ wet film thickness, allowed to dry at room temperature to dry dust and then heated continuously in an oven, the heating rate 5-20 ° C, preferably 10-11 ° C / min. After heating to temperatures between 300-400 ° C, preferably 320-350 ° C, 30 min to 2 h, preferably 1 h, held at this temperature.
  • the layer thicknesses of the baked layer are 5-30 m, preferably 25 m.
  • Various metals can be used as substrates for metals, preferred are stainless steel and aluminum, but also glass or ceramic.
  • the surface hardness of the layers is between 2 and 4 Newton, the pencil hardness is 8-9.
  • a coated stainless steel substrate was heated to 150 ° C and an egg was added. After 10 minutes, the underside of the egg is browned and can be removed from the substrate without any effort. On the substrate surface no traces of adhesion can be observed.
  • the layers can be easily cleaned after use, e.g. Wet wiping, spraying or even in the dishwasher, with very mild conditions and short times are sufficient.
  • 0.01 g of formic acid and 0.09 g of polydimethylsiloxane are weighed into a round bottom flask and stirred for 5 min at room temperature.
  • 8.74 g of Levasil 200 S / 30 become the reaction mixture added and stirred for a further 15 min at room temperature.
  • 5.84 g of trimethoxymethylsilane are then added dropwise to the solution and stirred for an additional hour.
  • 8.52 g of 10% boehmite suspension are added dropwise and stirred for an additional hour.
  • 0.30 g of quartz powder (Sikron SF 800) and 30.99 g of i-propanol are added and stirred for 1 h.
  • the suspension is placed in a rotary ball mill with 2-3 mm diameter glass beads and milled for 1 hour at 3000 rpm.
  • 0.57 g of formic acid and 2.49 g of polydimethylsiloxane are weighed into a round bottom flask and stirred for 5 min at room temperature.
  • 41.57 g of trimethoxymethylsilane and 15.9 g of tetraethyl orthosilicate are added to the reaction mixture and it is stirred for 15 minutes at room temperature.
  • 21.98 g of water are slowly added dropwise, the solution is stirred for 1 h at room temperature, and then 49.63 g of boehmite suspension are added dropwise and stirred for an additional hour.
  • the suspension is placed in a rotary ball mill with 2-3 mm diameter glass beads and milled for 1 hour at 3000 rpm.
  • the coating materials according to embodiments 1-4 were sprayed with a cup spray gun with a nozzle diameter of 0.8 mm at 2 bar on the cleaned, planar stainless steel substrates with a wet film thickness of 45 ⁇ and dried at 50 ° C to dry dust. Subsequently, the substrates were heated in an oven at a failure rate of 11 ° C per minute to 320 ° C and held at this temperature for 1 h, and then cooled in air.
  • Example 5 the coating of a brushed stainless steel substrate is carried out according to Example 5. After cooling, a transparent coated stainless steel substrate is obtained in which the optical effect of the brush structure is maintained.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

Selon l'invention, on a recours à une technique sol-gel avec des silanes hydrolisables et condensables pour la synthèse d'une suspension hétéropolycondensée destinée à pourvoir des composants et articles de couches de revêtement résistantes à de hautes températures, transparentes, résistantes à l'abrasion et ayant des propriétés anti-adhésives. Afin d'obtenir une grande résistance à l'abrasion, des particules minérales transparentes abrasives, d'un indice de réfraction adapté à la matrice durcie, sont broyées avec l'hétéropolycondensé dans un broyeur à haute énergie et mélangées à un polysiloxane thermiquement stable pour obtenir une flexibilité suffisante permettant d'éviter toute formation de craquelures. Ce revêtement convient aux substrats en métal, verre et céramique et s'applique par un procédé de revêtement par voie humide en une seule étape puis est durci. Les couches sont de incolores à transparentes, et ont un grand effet anti-adhésif. L'aspect visuel de la surface du substrat demeure intacte. Des structures brossées en acier inoxydable sont facilement reconnaissables après application et durcissement.
PCT/EP2015/001964 2014-10-09 2015-10-07 Substrats transparents et résistants à l'abrasion, pourvus d'un revêtement anti-adhésif en composite céramique, procédé de fabrication et utilisation WO2016055157A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014014735.5A DE102014014735A1 (de) 2014-10-09 2014-10-09 Transparente, abriebfeste, mit einem Keramikkomposit antihaftbeschichtete Substrate, Verfahren zu ihrer Herstellung und ihre Anwendung
DE102014014735.5 2014-10-09

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WO2016055157A1 true WO2016055157A1 (fr) 2016-04-14
WO2016055157A8 WO2016055157A8 (fr) 2016-06-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109704730A (zh) * 2019-03-07 2019-05-03 昆山卡德姆新材料科技有限公司 一种具双色玉石质感的陶瓷饰品及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6342097B1 (en) * 1999-04-23 2002-01-29 Sdc Coatings, Inc. Composition for providing an abrasion resistant coating on a substrate with a matched refractive index and controlled tintability
US6538092B1 (en) * 1999-04-23 2003-03-25 Sdc Coatings, Inc. Composition for providing an abrasion resistant coating on a substrate with a matched refractive index:2
EP1175466B1 (fr) * 1999-04-23 2007-08-01 Sdc Coatings, Inc. Composition produisant un revetement resistant a l'abrasion

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2739392B1 (fr) 1995-09-28 1997-12-26 Corning Inc Systemes pour conferer a des surfaces des proprietes d'antiadherence et de non mouillabilite
KR101104680B1 (ko) 2009-07-23 2012-01-13 (주) 더몰론코리아 난스틱 세라믹 코팅층을 구비한 법랑재 가열조리기구

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6342097B1 (en) * 1999-04-23 2002-01-29 Sdc Coatings, Inc. Composition for providing an abrasion resistant coating on a substrate with a matched refractive index and controlled tintability
US6538092B1 (en) * 1999-04-23 2003-03-25 Sdc Coatings, Inc. Composition for providing an abrasion resistant coating on a substrate with a matched refractive index:2
EP1175466B1 (fr) * 1999-04-23 2007-08-01 Sdc Coatings, Inc. Composition produisant un revetement resistant a l'abrasion

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109704730A (zh) * 2019-03-07 2019-05-03 昆山卡德姆新材料科技有限公司 一种具双色玉石质感的陶瓷饰品及其制备方法
CN109704730B (zh) * 2019-03-07 2024-01-02 昆山卡德姆新材料科技有限公司 一种具双色玉石质感的陶瓷饰品及其制备方法

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WO2016055157A8 (fr) 2016-06-09
DE102014014735A1 (de) 2016-04-14

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