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WO2010060006A1 - Article avec surface en acier inoxydable facile à nettoyer et son procédé de fabrication - Google Patents

Article avec surface en acier inoxydable facile à nettoyer et son procédé de fabrication Download PDF

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Publication number
WO2010060006A1
WO2010060006A1 PCT/US2009/065443 US2009065443W WO2010060006A1 WO 2010060006 A1 WO2010060006 A1 WO 2010060006A1 US 2009065443 W US2009065443 W US 2009065443W WO 2010060006 A1 WO2010060006 A1 WO 2010060006A1
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group
stainless steel
easy
carbon atoms
formula
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Inventor
Lifei Hao
Wenbin Liu
Xiaodong Zhai
Yan Wang
Wayne W. Fan
Rudolf J. Dams
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3M Innovative Properties Co
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3M Innovative Properties Co
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • silane compounds or compositions having one or more fluorinated groups have been successfully used for rendering substrates such as glass and ceramics oil- and water-repellent.
  • Such silane compounds or compositions have typically included one or more hydrolysable groups and at least one fluorinated alkyl group or fluorinated polyether group.
  • Substrates that have been treated for oil and water repellency include glass, ceramics such as bathroom tile, enamel, metals, natural and man-made stone, polymers, and wood.
  • the methods for treating these substrates typically have not been demonstrated to be successful for treating stainless steel. There continues to be a need for methods for imparting repellent properties to stainless steel surfaces and for stainless steel substrates having durable oil and water repellency.
  • stainless steel surfaces are found on a variety of commonly used articles in the home and outdoors.
  • stainless steel is a popular material in kitchens and bathrooms and is used for faucets, shower heads, hand rails, range hoods, and other appliances.
  • stainless steel is used for exterior parts such as wheel rims.
  • Such stainless steel surfaces come in contact with a variety of oily and aqueous deposits such as cooking or automotive oil or grease, food, soap, dirt, sand, and minerals (e.g., lime). These deposits, which may be in the form of fingerprints, stains, or smudges, tend to show up easily on the surface and can be difficult to remove.
  • the present disclosure provides a method of making an easy-to-clean article having a stainless steel surface, the method comprising treating the stainless steel surface with a treatment composition comprising: water; acid; organic solvent; a fluorinated composition represented by formula: Rf ⁇ X 1 -[Si(Y) 3 . ⁇ (R 1 ) ⁇ ] y ⁇ z ; and a first compound represented by formula:
  • Rf is a polyfluoropolyether group
  • each X 1 is independently a divalent or trivalent organic linking group
  • each Y is independently halogen, alkoxy, acyloxy, polyalkyleneoxy, or aryloxy;
  • R 1 is an alkyl group having up to 8 carbon atoms or a phenyl group
  • L is an amino group, a mercapto group, or an epoxy group
  • R 2 is alkylene optionally interrupted by at least one ether linkage; x is 0 or 1 or 2; y is 1 or 2; z is 1 or 2; and k is 1 , with the proviso that when L is an amino group, k is 1 or 2.
  • the treatment composition further comprises at least one of (i.e., one or the other or both): a second compound represented by formula: a third compound represented by formula:
  • each R 3 is independently an alkyl group having up to 8 carbon atoms or a phenyl group, each of which may be substituted by halogen; each Y 1 is independently halogen, alkoxy, acyloxy, polyalkyleneoxy, or aryloxy; M is Si, Ti, or Zr, and b is 1 or 2.
  • the present disclosure provides an easy-to-clean article comprising a stainless steel surface, wherein the surface is treated according to any one of the above embodiments of the method disclosed herein.
  • the present disclosure provides an easy-to-clean article comprising a stainless steel surface, wherein at least a portion of the stainless steel surface is treated with a siloxane, the siloxane comprising a condensation product of at least a first compound and a fluorinated composition, the first compound represented by formula: L-[R 2 Si(Y) 3 ] k ; and the fluorinated composition represented by formula:
  • Rf is a polyfluoropolyether group
  • each X 1 is independently a divalent or trivalent organic linking group
  • each Y is independently halogen, alkoxy, acyloxy, polyalkyleneoxy, or aryloxy;
  • R 1 is an alkyl group having up to 8 carbon atoms or a phenyl group
  • L is an amino group, a mercapto group, or an epoxy group
  • R 2 is alkylene optionally interrupted by at least one ether linkage; x is 0 or 1 or 2; y is 1 or 2; z is 1 or 2; and k is 1 , with the proviso that when L is an amino group, k is 1 or 2.
  • the siloxane comprises a condensation product of the fluorinated composition, the first compound, and at least one of: a second compound represented by formula: (R 3 ) b Si(Y 1 ) 4 . b ; or a third compound represented by formula:
  • alkyl and the prefix “alk” are inclusive of both straight chain and branched chain groups and of cyclic groups, e.g., cycloalkyl. Unless otherwise specified, these groups contain from 1 to 20 carbon atoms.
  • these groups have a total of up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms.
  • Cyclic groups can be monocyclic or polycyclic and preferably have from 3 to 10 ring carbon atoms.
  • alkylene is the divalent or trivalent form of the "alkyl” groups defined above.
  • halogen refers to a halogen atom or one or more halogen atoms, including chlorine, bromine, iodine, and fluorine atoms.
  • aryl as used herein includes carbocyclic aromatic rings or ring systems optionally containing at least one heteroatom (i.e., O, N, or S). Examples of aryl groups include phenyl, naphthyl, biphenyl, and pyridinyl.
  • arylene is the divalent form of the "aryl” groups defined above.
  • Arylalkylene refers to an “alkylene” moiety to which an aryl group is attached.
  • carbamate refers to the group -0-C(O)-N(R')- wherein R is as defined below.
  • urea refers to the group -N(R')-C(0)-N(R')- wherein each R' is independently as defined below.
  • the present disclosure can overcome several challenges typically associated with coating stainless steel and provides easy-to-clean stainless steel articles and a method of making them using a chemical coating treatment. Due to its inert nature, coatings typically do not adhere well to stainless steel, which can result in poor durability of the coating. Stainless steel can be resistant to some types of surface treatments that are typically used to improve adhesion. While adhesion (e.g., of a coating) to some metals is improved by surface abrasion of the metal, stainless steel tends to work-harden under abrasive treatments.
  • Chemical conversion coatings can be used to improve the corrosion resistance and adhesion capabilities of some metals (e.g., galvanized steel, zinc, and aluminum) but are typically not used with stainless steel.
  • Chromating solutions which are acidic and function by dissolving some of the surface metal of the substrate to be chromated, are specifically designed for the metal to be treated.
  • a chromated steel surface which may contain various levels of hexavalent chromium depending on the type of chromating solution
  • stainless steel In contrast to a chromated steel surface, which may contain various levels of hexavalent chromium depending on the type of chromating solution, stainless steel generally forms a passivation layer of chromium(III) oxide on its surface. Therefore, the surfaces of stainless steel and treated metals such as chromated steel are quite different.
  • Stainless steel useful for practicing the present disclosure includes a variety of grades.
  • the article can have a surface of austenitic, ferritic, or martensitic stainless steel containing at least about 10 (in some embodiments, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) percent by weight of chromium.
  • the chromium content in the stainless steel at least about 10 percent by weight, the steel can generally readily be formed into a desired shape.
  • suitable stainless steels include 430, 304, and 316.
  • Examples of articles having a stainless steel surface include kitchen and bathroom faucets, taps, handles, spouts, sinks, drains, hand rails, towel holders, curtain rods, dish washer panels, refrigerator panels, stove tops, stove, oven, and microwave panels, exhaust hoods, grills, automotive wheels or rims, and chemical reactors.
  • Stainless steel articles that are treated according to the present disclosure include those having stainless steel surfaces in a wide range of thicknesses, depending on the application.
  • Treatment compositions useful for practicing the methods disclosed herein include a fluorinated composition comprising a polyfluoropolyether group and a hydrolysable silane group and a first compound comprising an amino group, an epoxy group, or a mercapto group and a hydrolysable silane group.
  • Easy-to-clean articles according to the present disclosure include those having a stainless steel surface treated with the fluorinated composition and first compound themselves, those treated with a siloxane comprising a condensation product of at least the fluorinated composition and the first compound, and combinations thereof (e.g., partial condensates).
  • hydrolysis of the hydrolysable groups (e.g., alkoxy, acyloxy, or halogen) of the fluorinated compositions and first compounds typically generates silanol groups, which participate in condensation reactions to form fluorinated siloxanes, for example, according to the following reaction sequence:
  • fluorinated compositions useful in practicing the present disclosure are represented by formula 1-1 :
  • fluorinated compositions useful in practicing the present disclosure are represented by formula I:
  • Rf is a polyfluoropolyether group, containing two or more in-chain oxygen atoms, which may be monovalent or divalent.
  • Rf may be linear, branched, cyclic, or a combination thereof, and may be saturated or unsaturated.
  • Rf is typically a perfluorinated group (i.e., all C-H bonds are replaced by C-F bonds).
  • hydrogen or chlorine atoms may be present instead of fluorine atoms.
  • Rf includes at least one trifluoromethyl group.
  • Compositions of formula 1-1 and I, being oligomeric or polymeric in nature typically exist as mixtures and are suitable for use as such.
  • each X 1 is independently a divalent or trivalent organic linking group, which includes linear, branched, and cyclic structures.
  • X 1 may be saturated or unsaturated and can contain 1 to 20 (1 to 15, or 1 to 10) carbon atoms and optionally one or more heteroatoms (e.g., O, N, or S).
  • X 1 contains up to four heteroatoms.
  • the one or more heteroatoms can be combined into functional groups containing more than one heteroatom (e.g., amides, esters, and carbamates).
  • X 1 contains at least one functional group (e.g., up to 4 functional groups).
  • Q is a bond, -C(O)-N(R')-, -C(O)-O-, -SO 2 N(R)-, or -0-C(O)-N(R)-.
  • Q is a bond, -C(O)-N(R')-, or -C(O)-O-.
  • Q is -C(O)-N(R')-.
  • R is hydrogen or alkyl having up to 4 carbon atoms (i.e., methyl, ethyl, propyl, or butyl).
  • R is hydrogen, methyl, or ethyl.
  • R' is hydrogen or methyl.
  • X is alkylene or arylalkylene. In some embodiments, X is alkylene. In some embodiments, X has up to 10, 8, 6, or 4 carbon atoms. X can be divalent or trivalent and is optionally at least one of interrupted or terminated by at least one functional group that is independently ether, thioether, sulfone, amine, ester, amide, carbamate, or urea. In some embodiments, X is optionally at least one of interrupted or terminated by at least one functional group that is independently ether, ester, carbamate, or amino. The phrase "interrupted by at least one functional group” refers to having alkylene or arylalkylene on either side of the functional group.
  • Representative X groups that are interrupted by at least one functional group include -(CH 2 )I-IoOC(O)N(R)-(CH 2 )I-Io-, -(CH 2 )I-IOO(CH 2 )I-IOS(CH 2 )I-IO-, and -(CH 2 )I-IoOC(O)-(CH 2 )I-Io-.
  • the term "terminated by a functional group" refers to the functional group being connected to the R group in formula I.
  • Q is -C(O)-N(R)-, wherein X is alkylene having up to 8 carbon atoms, and wherein X is optionally at least one of interrupted or terminated by at least one functional group that is independently ether, ester, carbamate, or amino.
  • each Y is independently halogen (i.e., fluoride, chloride, bromide, or iodide), alkoxy (i.e., -O-alkyl), acyloxy (i.e., -OC(O)alkyl), polyalkyleneoxy, or aryloxy (i.e., -O-aryl).
  • the Y groups are generally capable of hydro lyzing, for example, in the presence of water under acidic conditions to produce groups capable of undergoing a condensation reaction, for example silanol groups.
  • alkyl e.g., in alkoxy and acyloxy
  • alkoxy and acyloxy have up to 8, 6, 4, 3, or 2 carbon atoms.
  • aryloxy has 6 to 12 (or 6 to 10) carbon atoms which may be unsubstituted or substituted by halogen, alkyl (e.g., having up to 4 carbon atoms), and haloalkyl.
  • Polyalkyleneoxy is, for example, -O-(CH(CH 3 )-CH 2 O) q -C 1 _ 4 alkyl, -O-(CH 2 -CH 2 O)q " -Ci_4 alkyl, or a combination thereof (e.g., -O-(CH(CH 3 )-CH2 ⁇ ) q .-(CH2-CH 2 O) q" -C 1 -4 alkyl with a ratio of q' to q" of 1 :1 to 1 :10), and q', q", or q' + q" is 1 to 40 (in some embodiments, 2 to 10).
  • each Y is independently selected from the group consisting of halide, hydroxyl, alkoxy, aryloxy, and acyloxy. In some embodiments, each Y is independently selected from the group consisting of halide (e.g., chloride) and alkoxy having up to ten carbon atoms. In some embodiments, each Y is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms. In some embodiments, each Y is independently methoxy or ethoxy.
  • Rf comprises perfluorinated repeating units comprising at least one of -(C n F 2n O)-, -(CF(Z)O)-, -(CF(Z)C n F 2n O)-, or -(C n F 2n CF(Z)O)-; wherein Z is a perfluoroalkyl group or a perfluoroalkoxy group, each of which is optionally interrupted by at least one ether linkage, and n is an integer from 1 to 12 (in some embodiments, 1 to 6, 1 to 4, or 1 to 3).
  • Z can be linear, branched, or cyclic, and have 1 to 9 carbon atoms and 0 to 4 oxygen atoms.
  • the perfluorinated repeating units may be arranged randomly, in blocks, or in an alternating sequence.
  • Rf is monovalent, and z is 1.
  • Rf is terminated with a group selected from the group consisting Of C n F 2n+1 -, C n F 2n+1 O-, and X'C n F 2n O- wherein X' is a hydrogen or chlorine atom.
  • the terminal group is C n F 2n+1 - or C n F 2n+1 O-, wherein n is an integer from 1 to 6 or 1 to 3.
  • the approximate average structure of Rf is C3FvO(CF(CF3)CF 2 O) q CF(CF3)-, C 3 F 7 O(CF 2 CF 2 CF 2 O) q CF 2 CF 2 -, or CF 3 O(C 2 F 4 O) q CF 2 -, wherein q has an average value of
  • Rf is C 3 F 7 O(CF(CF 3 )CF 2 O) q CF(CF 3 )-, wherein q has an average value of 4 to 7.
  • Rf is -CF 2 O(CF 2 O) m (C 2 F 4 O) p CF 2 -, -CF 2 O(C 2 F 4 O) P CF 2 -, -(CF 2 ) 3 O(C 4 F 8 O) P (CF 2 ) 3 -, or -CF(CF 3 )-(OCF 2 CF(CF 3 )) P O-Rf -0(CF(CF 3 )CF 2 O) P CF(CF 3 )-, wherein Rf is a perfluoroalkylene group optionally interrupted by at least one ether or amine linkage, m is 1 to 50, and p is 3 to 40.
  • Rf is (C n F 2n ), wherein n is 2 to 4.
  • Rf is -CF 2 O(CF 2 O) m (C 2 F 4 O) p CF 2 -, -CF 2 O(C 2 F 4 O) P CF 2 -, or -CF(CF 3 )-(OCF 2 CF(CF 3 )) p O-(C n F 2n )-O(CF(CF 3 )CF 2 O) p CF(CF 3 )-, and wherein n is 2 to 4, and the average value of m+p or p+p or p is from about 4 to about 24.
  • the above described fluorinated compositions represented by formulas 1-1 and I typically include a distribution of oligomers and/or polymers, so p and m may be non- integral.
  • the above structures are approximate average structures where the approximate average is over this distribution.
  • These distributions may also contain perfluoropolyethers with no silane groups or more than two silane groups. Typically, distributions containing less than about 10% by weight of compounds without silane groups can be used.
  • R is a bond or alkylene having up to 4 carbon atoms (i.e., methylene, ethylene, propylene, or butylene). In some embodiments, R is a bond. In some embodiments, R is alkylene having up to 4 carbon atoms.
  • R 1 is an alkyl group having up to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, or n-octyl) or a phenyl group.
  • R 1 is an alkyl group having up to 4 carbon atoms.
  • R 1 is methyl or ethyl.
  • x is 0, 1, or 2. In some embodiments, including any one of the above embodiments, x is 0 or 1 (in some embodiments, 0).
  • y is 1 or 2.
  • X is terminated by an amine or amide group, and y is 2.
  • y is 1.
  • the number average molecular weight of the fluorinated composition is about 750 to about 6000, or about 800 to about 4000.
  • Rf is -CF 2 O(CF 2 O) m (C 2 F 4 O) p CF 2 -, z is 2, y is 1, and X 1 -Si(Y) 3 .
  • ⁇ (R 1 ) x is C(O)NH(CH 2 )3Si(OCH 3 )3 or C(O)NH(CH 2 ) 3 Si(OCH 2 CHs) 3 .
  • m and p are each about 9 to 12.
  • the fluorinated compositions represented by formulas 1-1 and I can be synthesized, for example, from a fluorinated carboxylic acid or salt thereof, an acid fluoride thereof, or a fluorinated carboxylic acid ester (e.g., Rf-[C(O)-OCH 3 ] Z ) using a variety of conventional techniques.
  • a fluorinated methyl ester can be treated with an amine having formula NH 2 -X-Si(Y) 3 _ x (R 1 ) x according to the following reaction sequence.
  • Rf, X, Y, R 1 , x, and z are as defined in any of the above embodiments.
  • Some amines having formula NH 2 -X-Si(Y) 3 _ x (R 1 ) x are commercially available (e.g., (3- aminopropyl)trimethoxysilane and (3-aminopropyl)triethoxysilane).
  • the reaction may be carried out, for example, at an elevated temperature (e.g., up to 80 0 C, 70 0 C, 60 0 C, or 50 0 C), and may be carried out neat or in a suitable solvent.
  • Conditions for carrying out these transformations are known in the art; see, e.g., U.S. Pat. Nos. 3,810,874 (Mitsch et al.) and 3,646,085 (Bartlett), the disclosures of which, relating to the preparation of fluorinated silanes, are incorporated herein by reference.
  • fluorinated methyl esters are commercially available (e.g., CH 3 OC(0)CF 2 (OCF 2 CF 2 ) 9 -io(OCF 2 ) 9 -ioCF 2 C(0)OCH 3 , a perfiuoropolyether diester available from Solvay Solexis, Houston, TX, available under the trade designation
  • FABLIN ZDEAL Fluorinated methyl ester
  • Others can be prepared, for example, through direct fluorination of a hydrocarbon polyether diester using techniques known in the art; see, e.g., methods disclosed in U.S. Patent Nos. 5,578,278 (Fall et al.) and 5,658,962 (Moore et al).
  • a fluorinated methyl ester is prepared by oligomerization of hexafluoropropylene oxide (HFPO) and functionalization of the resulting perfiuoropolyether carbonyl fluoride according to the methods described in U. S. Pat. No. 4,647,413 (Savu), the disclosure of which is incorporated herein by reference.
  • HFPO hexafluoropropylene oxide
  • Fluorinated compositions represented by formulas 1-1 and I can also be prepared, for example, by reaction of a carboxylic acid ester (e.g., Rf-[C(O)-OCHs] 2 ) with an amino alcohol having formula NH2-X"-0H (e.g., ethanolamine) to prepare fluorinated hydroxyl compound Rf-[(CO)NHX"OH] Z as shown in the following reaction sequence, wherein Rf is as defined in any of the above embodiments, and X" is a precursor to X, wherein X is interrupted by at least one ether, ester, or carbamate group.
  • a carboxylic acid ester e.g., Rf-[C(O)-OCHs] 2
  • an amino alcohol having formula NH2-X"-0H e.g., ethanolamine
  • the conditions for the reaction with NH 2 -X-Si(Y) 3 _ x (R 1 ) x , described above, can be used for the reaction with NH2-X"-0H.
  • the fluorinated hydroxyl compound can then be treated with, for example, a haloalkyl silane (e.g., chloropropyltrimethoxysilane) or an isocyanatoalkyl silane (e.g., 3-isocyanatopropyltriethoxysilane).
  • the reaction with a haloalkyl silane can be carried out, for example, by first treating the fluorinated hydroxyl compound with a base (e.g., sodium methoxide or sodium tert-butoxide) in a suitable solvent (e.g., methanol), optionally at an elevated temperature (e.g., up to the reflux temperature of the solvent), followed by heating (e.g., at up to 100 0 C, 80 0 C, or 70 0 C) the resulting alkoxide with the haloalkyl silane.
  • a base e.g., sodium methoxide or sodium tert-butoxide
  • a suitable solvent e.g., methanol
  • reaction of a fluorinated hydroxyl compound represented by formula Rf-[C(O)-NH-X"-OH] Z with an isocyanatoalkyl silane can be carried out, for example, in a suitable solvent (e.g., methyl ethyl ketone), optionally at an elevated temperature (e.g., the reflux temperature of the solvent), and optionally in the presence of a catalyst (e.g., stannous octanoate).
  • a suitable solvent e.g., methyl ethyl ketone
  • an elevated temperature e.g., the reflux temperature of the solvent
  • a catalyst e.g., stannous octanoate
  • Fluorinated compositions represented by formulas 1-1 and I can also be prepared, for example, by reducing an ester of formula Rf-[C(O)-OCHs] 2 or a carboxylic acid of formula Rf-[C(O)-OH] 2 using conventional methods (e.g., hydride, such as sodium borohydride, reduction) to a fluorinated hydroxyl compound of formula Rf-[CH 2 OH] 2 as shown in the following reaction sequence, wherein Rf, X, Y, R 1 , x, and z are as defined in any of the above embodiments, and X is interrupted by at least one ether, ester, or carbamate group.
  • Rf-[C(O)-OCHs] 2 ⁇ Rf-[CH 2 OH] 2 ⁇
  • the fluorinated hydroxyl compound of formula Rf-[CH 2 OH] 2 can then be converted, for example, to a silane by reaction with a haloalkyl silane or isocyanatoalkyl silane using the techniques described above.
  • Some useful fluorinated hydroxyl compounds are commercially available (e.g., HOCH 2 CF 2 (OCF 2 CF 2 ) 9 .io(OCF 2 ) 9 .ioCF 2 CH 2 OH, a perfluoropolyether diol available from Solvay Solexis available under the trade designation "FOMBLIN ZDOL").
  • Fluorinated hydroxyl compounds can also be treated, for example, with allyl halides (e.g., allyl chloride, allyl bromide, or allyl iodide) under the conditions described above for the reaction of fluorinated hydroxyl compounds with haloalkyl silanes.
  • allyl halides e.g., allyl chloride, allyl bromide, or allyl iodide
  • the resulting allyl-substituted compounds can be treated with, for example, a commercially available, or readily synthesized, mercaptosilane of the formula HS-X-Si(Y) 3 _ x (R 1 ) x , wherein X, Y, R 1 , and x can be defined as in any of the above embodiments, under free radical conditions.
  • Useful free radical initiators include hydrogen peroxide, potassium persulfate, t-butyl hydroperoxide, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, 2,2'-azobis(2-methylbutyronitrile), azobis(isobutyronitrile) (AIBN), and free radical photoinitiators such as those described by K.K. Dietliker in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Volume 3, pages 276- 298, SITA Technology Ltd., London (1991). Conditions for carrying out this transformation are known in the art; see, e.g., U.S. Pat. No.
  • Fluorinated hydroxyl compounds can also be treated, for example, with acryloyl halides, esters, anhydrides or acrylic acid to produce fluorinated acrylate esters, which can then be treated, for example, with amines having formula NH(3_ y )-[R-Si(Y)3- ⁇ (R 1 ) ⁇ ] y , wherein R, Y, R 1 , x, and y can be defined as in any of the above embodiments, according to the methods described in U. S. Pat. Appl. No.
  • fluorinated acrylate esters and amines are optionally carried out in dry solvent and optionally in the presence of 0.05 percent to 2 percent by weight catalyst (e.g., a base such as 1 ,4-dihydropyridines, methyl diphenylphosphane, methyl di-p-tolylphosphane, 2-allyl-N-alkyl imidazolines, tetra-t-butylammonium hydroxide, DBU (l,8-diazabicyclo[5.4.0]undec-7-ene), tetramethylguanidine, DBN (1,5- diazabicyclo[4.3.0]non-5-ene), potassium methoxide, sodium methoxide, or sodium hydroxide).
  • a base such as 1 ,4-dihydropyridines, methyl diphenylphosphane, methyl di-p-tolylphosphane, 2-allyl-N-alkyl imidazolines, te
  • Fluorinated acrylate esters can also be treated with mercaptosilanes represented by formula HS-X-Si(Y)3_ x (R 1 ) x , under similar conditions.
  • Treatment compositions useful for practicing the present disclosure include a first compound represented by formula II:
  • L is an amino group (e.g., primary or secondary amino group), a o mercapto group (i.e., HS-), or an epoxy group (i.e., ⁇ — ⁇ ). In some embodiments, L is an epoxy group.
  • k is typically 1, but when L is an amino group, k is 1 or 2.
  • R is alkylene (e.g., having up to 8, 6, or 4 carbon atoms) optionally interrupted by at least one ether linkage. In some embodiments, R is interrupted by one ether linkage.
  • each Y is independently as defined in any of the embodiments for formula I above.
  • Useful first compounds represented by formula II include 3- glycidoxypropyltrimethoxysilane, available, for example, from Dow Corning Corporation, Midland, Michigan, under the trade designation "DOW CORNING Z-6040 SILANE"; bis(trimethoxysilylpropyl)amine available, for example, from Gelest, Morrisville, PA; (3- aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane), (3- mercaptopropyl)trimethoxysilane, and (3-mercaptopropyl)triethoxysilane available, for example, from Sigma-Aldrich, St. Louis, MO.
  • the first compound is 3-glycidoxypropyltrimethoxysilane.
  • treatment compositions useful for practicing the present disclosure include a second compound represented by formula III:
  • Easy-to-clean articles include those having a stainless steel surface treated with the fluorinated composition and the first and second compounds themselves, those treated with a siloxane comprising a condensation product of at least the fluorinated composition, the first compound, and the second compound represented by formula III, and combinations thereof (e.g., partial condensates).
  • each R 3 is independently an alkyl group having up to 8 (in some embodiments, up to 6 or 4) carbon atoms or a phenyl group, each of which may be substituted by halogen (i.e., fluoride, chloride, bromide, or iodide).
  • each R is independently an alkyl group having up to 8 (in some embodiments, up to 6 or 4) carbon atoms and optionally substituted by halogen.
  • b is 1 or 2. In some embodiments, b is 1.
  • each Y 1 is independently halogen, alkoxy, acyloxy, polyalkyleneoxy, or aryloxy.
  • alkyl e.g., in alkoxy and acyloxy
  • alkoxy and acyloxy have up to 8, 6, 4, 3, or 2 carbon atoms.
  • aryloxy has 6 to 12 (or 6 to 10) carbon atoms which may be unsubstituted or substituted by halogen, alkyl (e.g., having up to 4 carbon atoms), and haloalkyl.
  • Polyalkyleneoxy is, for example, -0-(CH(CHs)-CH 2 O) ⁇ -C 1-4 alkyl, -0-(CH 2 -CH 2 O) ⁇ -C 1-4 alkyl, or a combination thereof
  • each Y 1 is independently selected from the group consisting of halide, hydroxyl, alkoxy, aryloxy, and acyloxy. In some embodiments, each Y 1 is independently selected from the group consisting of halide (e.g., chloride) and alkoxy having up to ten carbon atoms. In some embodiments, each Y 1 is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms. In some embodiments, each Y 1 is independently methoxy or ethoxy.
  • Useful second compounds represented by formula III include methyltriethoxysilane, dimethyldiethoxysilane, methyltrichlorosilane, and 3- chloropropyltriethoxysilane.
  • treatment compositions useful for practicing the present disclosure use a third compound represented by formula IV:
  • Easy-to-clean articles include those having a stainless steel surface treated with the fluorinated compositions, the first and third compound themselves, those treated with a siloxane comprising a condensation product of at least the fluorinated composition, the first compound, and the third compound represented by formula IV, and combinations thereof (e.g., partial condensates).
  • M is Si, Ti, or Zr. In some embodiments, M is Si.
  • Y 1 is as defined above in any of the embodiments described for formula III.
  • Useful third compounds of formula IV include tetramethoxysilane (i.e., tetramethyl orthosilicate), tetraethoxysilane (i.e., tetraethyl orthosilicate), tetramethyl orthotitanate, tetraethyl orthotitanate, tetraisopropyl orthotitanate, tetraethylzirconate, tetraisopropylzirconate, and tetrapropylzirconate.
  • M(Y ⁇ 4 is Si(O-alkyl) 4 .
  • a treatment composition useful for practicing the present disclosure typically includes from at least 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, 0.1, 0.15, 0.2, 0.25, or 0.5 percent by weight, up to 1, 1.5, or 2 percent by weight of at least one fluorinated composition represented by formula I or 1-1, based on the total weight of the treatment composition.
  • the amount of a fluorinated composition represented by formula I or 1-1 in a treatment composition may be in a range of from 0.01 to 2, 0.01 to 1, 0.05 to 2, 0.05 to 1, or from 0.1 to 1 percent by weight, based on the total weight of the treatment composition. Lower or higher amounts of the fluorinated composition may also be used, and may be desirable for some applications.
  • a treatment composition useful for practicing the present disclosure typically includes from at least 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, 0.1, 0.15, 0.2, 0.25, 0.5, or 1 percent by weight, up to 2, 3, 4, or 5 percent by weight of at least one first compound represented by formula II, based on the total weight of the treatment composition.
  • the amount of a first compound represented by formula II in a treatment composition may be in a range of from 0.025 to 5, 0.1 to 5, 0.05 to 3, 0.1 to 3, or from 0.1 to 2 percent by weight, based on the total weight of the treatment composition.
  • the weight ratio of the first compound to the fluorinated composition in the treatment composition is at least 2 to 1 (in some embodiments, at least 2.2:1, 2.5:1, 2.8:1, 3:1, 3.5:1, or 4:1).
  • treatment compositions wherein the ratio of the first compound to the fluorinated composition is at least 2:1 have at least one of better easy-to-clean performance or more durable easy-to- clean performance than treatment compositions wherein this ratio is less than 2:1.
  • treatment compositions useful for practicing the present disclosure contain a second compound represented by formula III.
  • the fluorinated composition is present in the treatment composition in a range from 0.01 percent to 2 percent by weight, based on the total weight of the treatment composition
  • the second compound is present in the treatment composition in a range from 0.05 percent to 10 percent by weight, based on the total weight of the treatment composition
  • the first compound is present in the treatment composition in a range from 0.1 percent to 5 percent by weight, based on the total weight of the treatment composition.
  • the siloxane treating the surface of the easy-to-article comprises a condensation product of the fluorinated composition relative to the first and second compounds combined in a weight ratio ranging from 1 :5 to 1 :120.
  • treatment compositions useful for practicing the present disclosure contain a third compound represented by formula IV. In some embodiments, treatment compositions useful for practicing the present disclosure contain less than 0.1 percent by weight of the third compound, based on the total weight of the composition. In some embodiments, the third compound is present relative to the first and second compounds combined in a weight ratio not greater than 1 :1. In some of these embodiments, the third compound is present relative to the first and second compounds combined in a weight ratio ranging from 1 :1 to 1 :5. When this ratio is about 1 : 1.8 to 1 :3.5, typically, improved durability is observed. In some embodiments of treatment compositions comprising a third compound of formula IV, the ratio of the third compound to the fluorinated composition may be, for example, in a range from 3:1 to 12:1, or in a range from 6:1 to 9: 1.
  • treatment compositions useful for practicing the present disclosure comprise compounds (e.g., the first compound and at least one of the second compound or the third compound) and the fluorinated composition in a ratio of at least 10:1, 15:1, or at least 20:1.
  • Treatment compositions useful for practicing the present disclosure comprise acid.
  • the acid comprises at least one of (i.e., comprises one or more of) acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid, sulfuric acid, or hydrochloric acid.
  • the acid is hydrochloric acid. Stronger acids typically effect the hydrolysis of silane groups at a lower temperature than weaker acids and are therefore sometimes desirable.
  • the acid may be present in the treatment composition in a range, for example, from about 0.004, 0.007, 0.01, or 0.015 percent by weight to about 1, 1.5, 2, 2.5, or 3 percent by weight, based on the total weight of the treatment composition.
  • the acid is present in an amount up to 0.5, 0.4, 0.3, 0.2, or 0.1 percent by weight based on the total weight of the treatment composition. In some embodiments, when the amount of acid exceeds about 0.05 percent by weight, the substrate has a spotty appearance. In some embodiments, the acid is hydrochloric acid and is present in the treatment composition in a range from 0.004 to 0.05 percent by weight, based on the total weight of the treatment composition.
  • Treatment compositions useful for practicing the present disclosure comprise water.
  • Water may be useful in the treatment composition, for example, to alter the distribution the fluorinated composition in the treatment composition after it is introduced to the surface of the stainless steel article.
  • the water is present in the treatment composition in a range from 0.01 percent to 10 percent (in some embodiments, 0.05 to 10, 0.1 to 10, 0.15 to 10, 1 to 10, or 1 to 8 percent) by weight, based on the total weight of the treatment composition.
  • Water may be added to the treatment compositions separately or may be added as part of an aqueous acidic solution (e.g., concentrated hydrochloric acid is 37% by weight of the acid in water).
  • treatment compositions useful in practicing the present disclosure include organic solvent.
  • organic solvent includes a single organic solvent and a mixture of two or more organic solvents.
  • Useful organic solvents are typically capable of dissolving at least about 0.01 percent by weight of a fluorinated composition represented by formula I or 1-1 in the presence of at least 0.01 (e.g., 0.1) percent by weight water and at least 0.004 (e.g., 0.01) percent by weight acid.
  • Suitable organic solvents include aliphatic alcohols (e.g., methanol, ethanol, and isopropanol); ketones (e.g., acetone and methyl ethyl ketone); esters (e.g., ethyl acetate and methyl formate); ethers (e.g., diethyl ether, diisopropyl ether, methyl t-butyl ether and dipropyleneglycol monomethylether (DPM)); hydrocarbons such as alkanes (e.g., heptane, decane, and paraffinic solvents); and fluorinated solvents such as partially or fully fluorinated hydrocarbons (e.g., perfluorohexane, perfluorooctane, and pentafluorobutane) and hydrofluoroethers (e.g,.
  • aliphatic alcohols e.g., methanol, ethanol, and isoprop
  • the organic solvent is methanol, ethanol, isopropanol, or a mixture thereof. In some embodiments, the organic solvent is ethanol.
  • the ratio of the solvents, water, acid, fluorinated compositions, first compounds, and other components may be chosen to provide a homogeneous mixture.
  • Treatment compositions useful in practicing the present disclosure may be applied to stainless steel articles either shortly after their preparation (e.g., up to one hour), or after standing at room temperature for a period of time (e.g., more than 1 hour, 3 to 8 hours, several days, or several weeks). Hydrolysis and condensation of the fluorinated compositions and the first, second, and third compounds may be more likely to occur after compositions are exposed to time and temperature. Typically treatment compositions disclosed herein are applied within several (e.g., up to 8, 6, 5, 3, 2, or 1) hours after they are prepared and are not heated prior to their application.
  • Treatment compositions useful for practicing the present disclosure may be prepared from a concentrate (e.g., a concentrated solution of a fluorinated composition represented by formula I or 1-1 and/or a first compound in organic solvent).
  • the concentrate may be stable for several weeks (e.g., at least one, two, or three months) and may comprise the fluorinated composition in an amount of at least 10, 20, 25, 30, or at least 40 percent by weight, based on the total weight of the concentrate.
  • Concentrates may be diluted shortly before use, for example, with water, organic solvent, acid, and optionally additional fluorinated composition or first, second, or third compounds.
  • the concentrate comprises the fluorinated composition and the first compound in the same weight ratio desired in the final, diluted treatment composition.
  • the concentrate comprises the fluorinated composition and the first, second, and optionally third compound in the same weight ratio desired in the final, diluted treatment composition.
  • the surface of the stainless steel article to be treated may be cleaned before treatment. It is typically desirable to remove foreign materials such as dust, oil, grease, and other contamination. Cleaning may be carried out, for example, with a solution of sodium hydroxide (e.g., 2, 5, or 10 percent by weight aqueous sodium hydroxide), with water, with an organic solvent (e.g., a ketone such as acetone or an alcohol such as ethanol), or with a combination thereof. The cleaning may be carried out at room temperature or at an elevated temperature (e.g., in a range from about 50 0 C to about 100 0 C). Techniques for cleaning the surface of the stainless steel article include wiping, rinsing, and sonicating. After cleaning, the surface of the stainless steel article may be dried, for example, under a stream of air or nitrogen or at an elevated temperature.
  • a solution of sodium hydroxide e.g., 2, 5, or 10 percent by weight aqueous sodium hydroxide
  • water with an organic solvent (e.g.,
  • a wide variety methods can be used to treat a stainless steel surface with a treatment composition disclosed herein (e.g., brushing, spraying, dipping, rolling, spreading, or chemical vapor deposition).
  • a stainless steel surface can typically be treated with a treatment composition at room temperature (typically, about 15 0 C to about 30 0 C or about 20 0 C to about 25 0 C).
  • the treatment composition can be applied to surfaces that are preheated (e.g., at a temperature of 60 0 C to 150 0 C).
  • the treated article can be dried and cured at ambient or elevated temperature (e.g., at 40 ° C to 300 0 C, 50 0 C to 150 0 C, or 60 0 C to 120 0 C) and for a time sufficient to dry.
  • repellent and durable surface treatments according to the present disclosure can be obtained upon treating an article and drying at ambient temperature.
  • methods disclosed herein further comprise a polishing step to remove excess material.
  • Easy-to-clean articles prepared according to the present disclosure wherein the treatment composition is dried typically no longer have organic solvent or water present on the surface.
  • the method of making an easy-to-clean article having a stainless steel surface further comprises subjecting at least the surface to an elevated temperature after treating the stainless steel surface with the treatment composition.
  • the thickness of the treatment is at least about 10, 20, 30, or 50 nanometers, up to about 100, 150, or 200 nanometers.
  • Thin coatings made according to the methods disclosed herein typically and advantageously are transparent and do not change the luster of the stainless steel surface.
  • the easy-to-clean performance of the articles and methods disclosed herein is typically measured by evaluating contact angles of at least one of water or hydrocarbon (e.g., hexadecane) on the treated surface. Receding contact angle and contact angle hysteresis (i.e., the difference between the advancing and receding contact angle values) are believed to be indicative of easy-to-clean performance.
  • contact angles are measured at room temperature (e.g., about 25 0 C to 30 0 C) using equipment obtained from Kruss GmbH, Hamburg, Germany, and are usually measured three times to obtain an average measurement.
  • the treated stainless steel surface has an initial receding contact angle versus water of at least 80 (in some embodiments, at least 82, 84, 86, 88, or 90) degrees. In some embodiments of the methods and articles disclosed herein, the treated stainless steel surface has an initial contact angle hysteresis versus water of up to 30 (in some embodiments, up to 28, 26, 24, 22, or 20) degrees. In some embodiments of the methods and articles disclosed herein, the treated stainless steel surface has an initial receding contact angle versus hexadecane of at least 50 (in some embodiments, at least 52, 54, 56, 58, or 60) degrees.
  • the treated stainless steel surface has an initial contact angle hysteresis versus hexadecane of up to 30 (in some embodiments, up to 28, 26, 24, 22, or 20) degrees.
  • "initial” refers to contact angles measured for the treated surface about 24 hours after treating the surface and before any abrading or wiping of the treated surface.
  • Stainless steel surfaces treated according to the present disclosure typically have at least one of a higher receding contact angle or a lower contact angle hysteresis versus at least one of water or hexadecane than an equivalent surface treated with an acidic solution of a 6:1 ratio of tetraethyl orthosilicate to (CH3 ⁇ )3Si(CH 2 )3NHCOCF 2 (OCF 2 CF 2 ) 9 .io(OCF 2 ) 9 .ioOCF 2 CONH(CH 2 )3Si(OCH 3 )3, described in U. S. Pat. No. 6,716,534 (Moore et al.).
  • equivalent surface refers to a stainless steel surface that is similar to or the same (e.g., in grade, surface preparation, and surface composition) as a stainless steel surface disclosed herein before it is treated according to the present disclosure.
  • contact angles are determined after cleaning stainless steel plates of grade 304 having dimensions of 8 cm by 5 cm by 0.05 cm (obtained from Shanghai Yongfeng International Trading Co., Ltd., China) with neutral cleaner (obtained from 3M China, Limited, Shanghai, China) followed by placing the plates in acetone in a sonicating bath for 20 minutes and drying with compressed air.
  • the treatment composition is allowed stand for 1 hour at room temperature and then sprayed onto cleaned and dried stainless steel plates under compressed air (2 kg/cm ). The plate is then dried in an oven at 120 0 C for 30 minutes and allowed to stand for 24 hours before evaluation by contact angle.
  • Stainless steel surfaces treated according to the present disclosure typically provide durable easy-to-clean performance (i.e., the easy-to-clean performance is maintained after cleaning the surface several times). In this application, durability is measured by measuring contact angles versus water of a treated stainless steel plate before and after being subjected to abrasion.
  • Abrasion is carried out by fixing the stainless steel plate on an abrasion tester (obtained from BYK-Gardener GmbH, Geretsried, Germany, under the trade designation "BYK-GARDENER ABRASION TESTER") and scrubbing for 5000 cycles with a microf ⁇ ber cloth obtained from 3M Company, St. Paul, MN under the trade designation "3M HIGH PERFORMANCE CLOTH", which is water- wet.
  • the scrubbing cycles are carried out with 1 kg force.
  • the treated stainless steel surface has a receding contact angle versus water of at least 65 (in some embodiments, at least 68, 70, 72, or 75) degrees after 5000 scrub cycles under 1 kilogram force with a water- wet cloth. In some embodiments of the methods and articles disclosed herein, the treated stainless steel surface has a contact angle hysteresis versus water of up to 35 (in some embodiments, up to 33, 31, 28, or 25) degrees after 5000 scrub cycles under 1 kilogram force with a water-wet cloth.
  • the treated stainless steel surface has a receding contact angle versus hexadecane of at least 20 (in some embodiments, at least 22, 25, 28, 30, 32, or 35) degrees after 5000 scrub cycles under 1 kilogram force with a water- wet cloth. In some embodiments of the methods and articles disclosed herein, the treated stainless steel surface has a contact angle hysteresis versus hexadecane of up to 30 (in some embodiments, up to 28, 26, 24, 22, or 20) degrees after 5000 scrub cycles under 1 kilogram force with a water-wet cloth. In some embodiments, including any of the above embodiments in which scrub cycles are carried out with a water- wet cloth, the cloth is a micro fiber cloth.
  • the cloth is a polyester-polyamide microf ⁇ ber cloth.
  • Stainless steel surfaces treated according to the present disclosure typically have, after abrasion, at least one of a higher receding contact angle or a lower contact angle hysteresis versus at least one of water or hexadecane than an equivalent surface treated with an acidic solution of a 6:1 ratio of tetraethyl orthosilicate to (CHsO ⁇ SiCC ⁇ NHCOCFjCOCFjCFjVioCOCFjV described in U. S. Pat. No. 6,716,534 (Moore et al). Unexpectedly durable performance is typically observed when the weight ratio of the first compound to the fluorinated composition in the treatment composition is at least 2 to 1.
  • 3-Aminopropyltrimethoxysilane (9.1 g) (obtained from Momentive Performance Materials, Albany, NY, available under the trade designation "SILQUEST A-1110") was added to the flask in one portion. Initially the mixture was two-phase, and as the reagents mixed the mixture became cloudy. A reaction exotherm to a temperature of 30 0 C was observed, and then the reaction gradually cooled to room temperature and became a slightly hazy light yellow liquid.
  • the reaction was monitored by gas chromatography (GC) to observe excess 3-aminopropyltrimethoxysilane and fourier transform infrared spectroscopy (FTIR) to observe unreacted ester functional groups and was found to be complete within 30 minutes after the addition of 3- aminopropy ltrimethoxy silane .
  • GC gas chromatography
  • FTIR Fourier transform infrared spectroscopy
  • HFPO-AEA was prepared as described in paragraphs 100 to 103 of U.S. 2005/0249942 (Coggio et al), the disclosure of which paragraphs are incorporated herein by reference.
  • Bis(trimethoxysilylpropyl)amine (2.43 grams, 0.00714 mole, obtained from Gelest, Morrisville, PA) was added dropwise to the flask over a period of 15 minutes.
  • reaction was exothermic, and was stirred for 30 minutes at room temperature and subsequently heated at 55 0 C for 12 hours to provide F(CF(CF 3 )CF 2 O) n CF(CF 3 )-CONHCH 2 CH 2 OCOCH 2 -CH 2 -N-[(CH 2 ) 3 -Si(OCH 3 ) 3 ] 2 .
  • Preparations 22 to 26 were made according to the method of Preparations 1 to 13 except Compounds 1, 2, and 2a, shown in Table 2, below, instead of GPTS and MTS were combined with 1 wt. % Mixture 1. For each of Preparations 22 to 26, 0.0125 wt. % of concentrated HCl was used. 3-Chloropropyltriethoxysilane (CPTS) was obtained from TCI (Shanghai) Development Co. Ltd., under the trade designation "JH- 130".
  • CPTS 3-Chloropropyltriethoxysilane
  • DMDS Dimethyldiethoxysilane
  • MPTS 3-Mercaptopropyl)triethoxysilane
  • Example 1 For Examples 1 to 15 and Comparative Example A, the plate was then placed in an oven and dried at 120 0 C for 30 minutes.
  • Comparative Example B the plate was placed in an oven and dried at 60 0 C for 30 minutes. The samples were allowed to stand for 24 hours before evaluation by contact angle.
  • Examples 1 to 15, Comparative Examples A and B, and control example I were evaluated for contact angle versus water and hexadecane, and oil repellency before and after abrasion.
  • a stainless steel plate was fixed on an abrasion tester (obtained from BYK- Gardener GmbH, Geretsried, Germany, under the trade designation "BYK-GARDENER ABRASION TESTER") and scrubbed for 5000 cycles with a microfiber cloth obtained from 3M Company, St. Paul, MN under the trade designation "3M HIGH
  • Stainless steel plates were also treated with Preparations 11 and 12 according to the method of Examples 1 to 15 to prepare Examples 16 and 17, respectively.
  • Example 16 had a course surface with some spots, and Example 17 had many spots on the surface.
  • Examples 5 to 16, Comparative Examples A and B, and Control Example I were tested for Oil Repellency.
  • a stainless steel plate was immersed in soy oil (obtained from COFCO Limited, China under the trade designation "FULINMEN"). The plate was then removed from the oil and the time was observed. The flow of oil from the plate was observed from the time the plate was pulled from the oil until the time when the final drop of oil dropped from the plate, and the total time was recorded. The results are given in Table 5, below.
  • Examples 18 to 22 Comparative Examples C to E, and control example II were evaluated for contact angle versus water and hexadecane and cleanability before and after being subjected to abrasion.
  • Abrasion test was carried out by fixing a stainless steel plate on an Erichsen cleaning machine (obtained from DCI , Belgium) applying cleaner (obtained from Procter and Gamble, Cincinnati, OH, under the trade designation "MR PROPER”) and wiping with a microf ⁇ ber cloth (available from 3M Company, St. Paul, MN under the trade designation "3M HIGH PERFORMANCE CLOTH”) for 4000 cycles.
  • Preparation 29 was made according to the method of Preparation 28 except F(CF(CF 3 )CF2 ⁇ ) n CF(CF3)-CONHCH2CH2CH 2 Si(OCH3)3 silane was used instead of F(CF(CF3)CF2 ⁇ ) n CF(CF3)-CONHCH2CH 2 OCOCH2-CH2-N-[(CH2)3-Si(OCH3)3]2 disilane to provide a solution of 0.2 wt. % silane, 0.4% wt. % MTS, 0.4% wt. % GPTS, 1 wt. % HCl, and 98 wt. % ethanol.
  • Preparation 30 was made according to the method of Preparation 28 except no MTS or GPTS was used. A solution of 0.2 wt. % disilane, 1 wt. % HCl, and 98.8 wt. % ethanol was provided. Preparation 31
  • Preparation 31 was made according to the method of Preparation 28 except F(CF(CF 3 )CF2 ⁇ ) n CF(CF3)-CONHCH2CH2CH2Si(OCH3) 3 silane was used instead of F(CF(CF3)CF2 ⁇ ) n CF(CF3)-CONHCH2CH 2 OCOCH2-CH2-N-[(CH2)3-Si(OCH3)3]2 disilane, and no MTS or GPTS was used.
  • Examples 23 and 24 and Comparative Examples F and G For Examples 23 and 24 and Comparative Examples F and G, the procedure of preparing and treating stainless steel plates in Examples 1 to 15 and Comparative
  • Examples 23 and 24 and Comparative Examples F and G were evaluated for contact angle versus water and hexadecane (static, advancing, and receding) before and after being subjected to abrasion.
  • Abrasion A stainless steel plate was fixed on an abrasion tester (obtained from Paul

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Abstract

L’invention concerne un article avec une surface en acier inoxydable facile à nettoyer, lequel article est traité avec un mélange d’une composition fluorée et d’un premier composé. La composition fluorée comprend un groupe polyfluoropolyéther et un groupe silane hydrolysable.  Le premier composé comprend un groupe amino, un groupe époxy ou un groupe mercapto et un groupe silane hydrolysable. L’invention concerne également un procédé de traitement d’une surface en acier inoxydable avec le mélange.
PCT/US2009/065443 2008-11-24 2009-11-23 Article avec surface en acier inoxydable facile à nettoyer et son procédé de fabrication Ceased WO2010060006A1 (fr)

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CN200810181093.7 2008-11-24
CN200810181093A CN101736346A (zh) 2008-11-24 2008-11-24 在不锈钢表面形成易清洁层的制品及其制备方法

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WO2010060006A1 true WO2010060006A1 (fr) 2010-05-27

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US (1) US20100129672A1 (fr)
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US11634525B2 (en) 2018-12-19 2023-04-25 3M Innovative Properties Company Zwitterionic copolymers, coating compositions, articles, and coating methods

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