WO2014120607A1 - Composition pour traitement de surface, procédés de préparation d'un article à surface traitée et article à surface traitée - Google Patents

Composition pour traitement de surface, procédés de préparation d'un article à surface traitée et article à surface traitée Download PDF

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Publication number
WO2014120607A1
WO2014120607A1 PCT/US2014/013191 US2014013191W WO2014120607A1 WO 2014120607 A1 WO2014120607 A1 WO 2014120607A1 US 2014013191 W US2014013191 W US 2014013191W WO 2014120607 A1 WO2014120607 A1 WO 2014120607A1
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composition
siloxane polymer
subscript
article
layer
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PCT/US2014/013191
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English (en)
Inventor
Brian R. Harkness
Daesup Hyun
Lei Fang
William J. Schulz
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Dow Corning Corporation
Dow Corning (China) Holding Co., Ltd.
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Publication of WO2014120607A1 publication Critical patent/WO2014120607A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention generally relates to a composition and, more specifically, to a composition for surface treatment and to methods of preparing surface-treated articles with the composition.
  • conventional surface treatment compositions have been applied on the surfaces of various devices/components to form conventional layers.
  • Such conventional surface treatment compositions typically consist of a fluorinated polymer and a solvent.
  • fluorinated polymers are typically expensive to manufacture or obtain.
  • conventional layers formed from such conventional surface treatment compositions have an undesirably high sliding coefficient of friction.
  • the present invention provides a composition for surface treatment of a substrate.
  • the composition comprises a siloxane polymer comprising repeating R2S1O2/2 units, where R is an independently selected substituted or unsubstituted hydrocarbyl group.
  • the composition further comprises a vehicle different from the siloxane polymer.
  • the siloxane polymer is present in the composition in an amount of from 0.01 to 0.5 percent by weight and the vehicle is present in the composition in an amount of from 90.0 to 99.99 percent by weight, each based on the total weight of the composition.
  • the present invention additionally provides methods of preparing a surface-treated article.
  • the composition is applied to a surface of an article to form a wet layer thereof on the surface of the article.
  • the first embodiment further comprises removing the vehicle from the wet layer to form a layer on the surface of the article and give the surface- treated article.
  • the composition and a pellet are combined to form an impregnated pellet.
  • the second embodiment further comprises the step of removing the vehicle from the impregnated pellet to form a neat pellet.
  • the second embodiment also comprises the step of forming a layer on a surface of an article with the neat pellet via a deposition apparatus.
  • the present invention provides surface-treated articles formed in accordance with the methods.
  • the composition forms layers that are easy to clean and which have excellent physical properties, including stain and smudge resistance. Further, the layers formed from the composition may have a selectively controlled coefficient of friction contingent on the type of siloxane polymer utilized in the composition. Further, the layers and composition may be prepared as a significantly lower cost than conventional layers formed from conventional compositions while still maintaining such excellent physical properties and while providing additional benefits.
  • the present invention provides a composition for surface treatment, methods of preparing surface-treated articles with the composition, and surface-treated articles formed in accordance with the methods.
  • the composition forms layers that are easy to clean and which have excellent physical properties, including smudge and stain resistance. Further, the layers formed from the composition have a desirable coefficient of friction and a significantly reduced cost relative to conventional layers formed from conventional compositions including fluorinated polymers.
  • the composition comprises a siloxane polymer.
  • the siloxane polymer comprises repeating R2S1O2/2 units, where R is an independently selected substituted or unsubstituted hydrocarbyl group.
  • R may be aliphatic, aromatic, cyclic, alicyclic, etc.
  • R may include ethylenic unsaturation.
  • substituted it is meant that one or more hydrogen atoms of the hydrocarbon may be replaced with atoms other than hydrogen (e.g.
  • a halogen atom such as chlorine, fluorine, bromine, etc.
  • a carbon atom within the chain of R may be replaced with an atom other than carbon, i.e., R may include one or more heteroatoms within the chain, such as oxygen, sulfur, nitrogen, etc.
  • R typically has from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms.
  • Substituted or unsubstituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
  • hydrocarbyl groups represented by R include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; alkenyl, such as vinyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenethyl.
  • alkyl such as methyl
  • halogen-substituted hydrocarbyl groups represented by R include, but are not limited to, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, and 2,2,3,3,4,4,5,5- octafluoropentyl .
  • the siloxane polymer may include additional substituents or functional groups at any terminal or pendent position.
  • the siloxane polymer may include silicon-bonded hydroxyl groups, hydrogen atoms, amine groups, silazane groups, (meth)acrylate groups, epoxy groups, etc.
  • Such groups or atoms may be present in the repeating D units (described below) or in terminal M units (which generally have the formula R3S1O1 /3, unless one or more of R is replaced by one of these additional substituents or functional groups). Most typically, if present, such groups are terminal in the siloxane polymer.
  • the siloxane polymer comprises repeating R2S1O2/2 units
  • the siloxane polymer has a linear portion.
  • the siloxane polymer may optionally be branched, partially branched, and/or may include a resinous portion having a three-dimensional networked structure.
  • the siloxane polymer further comprises includes RS1O3/2 units and/or S1O4/2 units.
  • R2S1O2/2 units are generally referred to as D units
  • RS1O3/2 units are generally referred to as T units
  • S1O4/2 units are generally referred to as Q units. Branching of the siloxane polymer itself, or the resinous portion of the siloxane polymer, if present, is attributable to the presence of T and/or Q units.
  • the siloxane polymer may consist of siloxane bonds (Si-O-Si) within the backbone of the siloxane polymer.
  • the siloxane polymer may include siloxane bonds separated by one or more bivalent groups, e.g. a CH2 linking group, where CH2 may be repeated up to, for example, 10 times.
  • the presence of absence of such bivalent groups is generally attributable to the reaction mechanism by which the siloxane polymer is formed, with siloxane polymers consisting of siloxane bonds being formed from condensation and siloxane polymers including one or more bivalent groups being formed from hydro silylation.
  • the siloxane polymer may optionally have functional groups, such as silicon-bonded alkenyl groups, silicon-bonded hydroxyl groups, silicon-bonded alkoxy groups, etc.
  • the functional groups may be terminal, pendent, or both.
  • the functional groups are terminal.
  • the siloxane polymer may be dimethylvinyl endblocked, divinylmethyl endblocked, dimethylhydroxyl endblocked, dihydroxylmethyl endblocked, etc.
  • the siloxane polymer includes a terminal group selected from a hydrolysable group, an alkenyl group, of combinations thereof. Generally, physical properties of the layers formed from the compositions are improved when the siloxane polymer includes such a terminal group.
  • the siloxane polymer has the following general formula (A):
  • X is an independently selected hydrolysable group; R is defined above; a and p are each integers independently selected from 0 to 3; b, f, i, and n are each integers independently selected from 0 to 10; c and m are each independently 0 or 1; d, g, and k are each integers independently selected from 0 or from 1 to 200 with the proviso that d, g, and k are not simultaneously 0; e, h, and 1 are each integers independently selected from 0 and 1 with the proviso that e, h, and 1 are not simultaneously 0; and j is an integer selected from 0 to 5; provided that when subscript d is 0, subscript e is also 0; when subscript d is greater than 0, subscript e is 1; when subscript g is 0, subscripts h, i, and j are also 0; when subscript g is greater than 1, subscript h is 1 and subscript j is at least 1; when subscript
  • subscripts d, g, and k represent the repeating R2S1O2/2 units of the siloxane polymer.
  • subscripts c and m are 0 and subscripts b, d, e, f, g, h, i, j, k, 1, and n are each integers of 1 or more.
  • subscript j is 1
  • the resulting siloxane polymer includes three segments of repeating siloxane bonds each separated by a bivalent linking group, which such bivalent linking groups being represented by subscripts b, f, i, and n, respectively.
  • the siloxane polymer is typically formed from hydro silylation and may be represented by the following general formula:
  • the siloxane polymer has the following general formula: (X)3-a(R)a-Si-(CH 2 )b-(SiR2-0)d-SiR 2 -(CH2)f-(SiR2-0) g -SiR2-(CH 2 )i-(SiR2-0) k -SiR2- (CH 2 )n-Si-(X) 3 -p(R)p.
  • subscripts d and k are each 1 and subscript g is an integer greater than 1 such that the block represented by subscript g provides the repeating R2S1O2/2 units in the siloxane polymer.
  • the siloxane polymer has the following general formula:
  • subscripts a and p are each 0 such that the siloxane polymer is endblocked with three silicon-bonded hydrolysable groups (represented by X) at each end.
  • the siloxane polymer need not have any silicon-bonded hydrolysable groups as subscripts a and p may each be 3.
  • the siloxane polymer has the following general formula:
  • R is independently selected such that even within the repeating block represented by subscript g there may be different substituents represented by R in different blocks.
  • R may independently vary between methyl and CH 2 CH 2 CF 3
  • siloxane polymer is typically formed from condensation and may be represented by the following general formula:
  • R is independently selected and may vary in different R2S1O2/2 units
  • the general formula above may be rewritten to exclude any of the blocks represented by subscripts e, h, j, and 1, so long as not all of these subscripts are simultaneously 0.
  • the general formula above may be rewritten while only including the R2S1O2/2 units within the block represented by subscript d, subscript h, subscript j, and/or subscript 1, as each of these formulas would be duplicative with one another, save for potential differences in molecular weight in embodiments in which the siloxane polymer includes greater than 200 repeating R2S1O2/2 units.
  • Subscripts a and p may each independently be from 0 to 3 such that the siloxane polymer of these embodiments need not have any silicon-bonded hydrolysable groups.
  • Specific species of the siloxane polymer within the general formula immediately above are set forth below for illustrative purposes only:
  • subscript g represents the repeating R2S1O2/2 units, and g is selected based on the desired molecular weight and viscosity of the siloxane polymer.
  • siloxane polymer when the siloxane polymer includes hydrolysable groups (in this case, methoxy groups) are set forth below for illustrative purposes only:
  • subscript g represents the repeating R2S1O2/2 units, and g is selected based on the desired molecular weight and viscosity of the siloxane polymer.
  • Subscript b represents an optionally repeating CH2 group and is defined above.
  • a single species of the siloxane polymer may be utilized or various combinations of different species of the siloxane polymer may be utilized in concert with one another in the composition.
  • two different types of siloxane polymers may be utilized in combination with one another, or a siloxane polymer may be utilized in combination with a silicone resin, e.g. an MQ resin.
  • the molecular weight or viscosity of the siloxane polymer is generally not limited when the composition is utilized in wet coating methods. In these embodiments, the viscosity of the siloxane polymer is typically such that the composition including the siloxane polymer is flowable. However, when the composition is utilized in other methods, e.g. physical vapor deposition, the molecular weight or viscosity of the siloxane polymer is typically selected such that the siloxane polymer volatilizes. In these embodiments, the siloxane polymer typically has a viscosity of from 50 to 500,000, alternatively from 100 to 300,000, alternatively from 300 to 100,000, cSt at 25 °C.
  • the relative amount of the siloxane polymer utilized in the composition may vary dependent upon the desired physical properties of the layer formed from the composition as well as the method by which the layer is formed. For example, when the composition is utilized in wet coating applications, the siloxane polymer is present in the composition in an amount of from 0.01 to 0.5, alternatively from 0.05 to 0.35, alternatively from 0.10 to 0.30, percent by weight based on the total weight of the composition.
  • the composition further comprises a vehicle different from the siloxane polymer.
  • the vehicle of the composition may, in certain embodiments, be referred to as a solvent when capable of solubilizing the siloxane polymer.
  • the vehicle is generally referred to as a vehicle as opposed to a solvent because the vehicle need only disperse the siloxane polymer, but not solubilize the siloxane polymer, although solubilization is typical.
  • the vehicle is typically selected such that the vehicle is non-reactive relative to or with the siloxane polymer.
  • the vehicle generally has a lesser molecular weight and viscosity than the siloxane polymer.
  • the vehicle comprises a siloxane fluid.
  • the siloxane fluid comprises a volatile methylsiloxane fluid.
  • volatile methylsiloxane fluid suitable for the purposes of the vehicle of the composition include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and combinations thereof.
  • Volatile methylsiloxane fluids are commercially available, such as OS-10, OS-20, or OS-30, from Dow Corning® Corporation of Midland, ML
  • the vehicle of the composition is a non-polar hydrocarbon vehicle, which may be aromatic, aliphatic, cyclic, alicyclic, etc.
  • aliphatic hydrocarbon vehicles suitable for solubilizing the siloxane polymer include hexane, heptane, octane, etc.
  • aromatic hydrocarbon vehicles suitable for solubilizing the siloxane polymer include toluene, xylene, trimethylbenzene, etc.
  • the vehicle is typically present in the composition in an amount of from 90 to 99.99, alternatively from 95 to 99.99 alternatively from 97 to 99.99, alternatively from 99 to 99.9, percent by weight based on the total weight of the composition, independent of the particular vehicle utilized.
  • the amount of the vehicle may vary from the ranges set forth immediately above contingent on the absence or presence of various optional components employed in the composition, as described in greater detail below.
  • the composition may additionally include any other suitable component(s), such as a coupling agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a leveling agent, a pigment, a catalyst, and so on.
  • a coupling agent such as a coupling agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a leveling agent, a pigment, a catalyst, and so on.
  • the composition consists essentially of, or consists of, the siloxane polymer and the vehicle.
  • Catalysts may optionally be utilized to promote surface modification by the composition. These catalysts can be used individually or as a combination of two or more in the composition. Examples of suitable catalytic compounds include acids, such as carboxylic acid, e.g.
  • the catalysts are typically utilized in an amount of from greater than 0 to 5, alternatively 0.01 to 2, percent by weight, based on 100 parts by weight of the composition.
  • the composition may further comprise various additive compounds for improving adhesion and/or durability of the layer formed from the composition.
  • additive compounds are silanes, such as tetrakis(dimethylamine)silane, methyltrimethoxysilane, tetraethylorthosilicate, glycidoxypropyltrimethoxysilane, triethylsilane, isobutyltrimethoxysilane; and siloxanes, such as heptamethyltrisiloxane, tetramethyldisloxane etc.
  • the present invention further provides surface-treated articles and methods of preparing surface-treated articles, which are described collectively in greater detail below.
  • the surface-treated article comprises an article presenting a surface.
  • a layer is deposited on the surface of the article.
  • the layer is formed from the composition, which is applied on the surface of the article to prepare the surface-treated article.
  • the method of preparing the surface-treated article comprises applying the composition on the surface of the article to form a wet layer thereof on the surface of the article.
  • the method further comprises removing the vehicle from the wet layer to form a layer on the surface of the article and give the surface-treated article.
  • the article may be any article, because of the excellent physical properties obtained from the composition of the present invention, the article is typically an electronic article, an optical article, consumer appliances and components, automotive bodies and components, etc. Most typically, the article is an article for which it is desirable to reduce stains and/or smudges resulting from fingerprints or skin oils.
  • Examples of electronic articles typically include those having electronic displays, such as LCD displays, LED displays, OLED displays, plasma displays, etc. These electronic displays are often utilized in various electronic devices, such as computer monitors, televisions, smart phones, GPS units, music players, remote controls, portable readers, etc. Exemplary electronic articles include those having interactive touch-screen displays or other components which are often in contact with the skin and which oftentimes display stains and/or smudges.
  • the article may also be a metal article, such as consumer appliances and components.
  • exemplary articles include a dishwasher, a stove, a microwave, a refrigerator, a freezer, etc, typically having a glossy metal appearance, such as stainless steel, brushed nickel, etc.
  • the article may be an automotive body or component.
  • the composition may be applied directly on a top coat of an automobile body to form the layer, which imparts the automobile body with a glossy appearance, which is aesthetically pleasing and resists stains, such as dirt, etc., as well as smudges from fingerprints.
  • suitable optical articles include inorganic materials, such as glass plates, glass plates comprising an inorganic layer, ceramics, and the like. Additional examples of suitable optical articles include organic materials, such as transparent plastic materials and transparent plastic materials comprising an inorganic layer, etc. Specific examples of optical articles include antireflective films, optical filters, optical lenses, eyeglass lenses, beam splitters, prisms, mirrors, etc.
  • examples of transparent plastic materials include materials comprising various organic polymers. From the view point of transparency, refractive index, dispersibility and like optical properties, and various other properties such as shock resistance, heat resistance and durability, materials used as optical members usually comprise polyolefins (polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamides (nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyimides, polyvinyl alcohol, ethylene vinyl alcohol, acrylics, celluloses (triacetylcellulose, diacetylcellulose, cellophane, etc.), or copolymers of such organic polymers.
  • polyolefins polyethylene, polypropylene, etc.
  • polyesters polyethylene terephthalate, polyethylene naphthalate, etc.
  • polyamides nylon 6, nylon 66, etc.
  • polystyrene polyvinyl chloride
  • polyimides polyvin
  • ophthalmic elements include corrective and non-corrective lenses, including single vision or multi-vision lenses like bifocal, trifocal and progressive lenses, which may be either segmented or non-segmented, as well as other elements used to correct, protect, or enhance vision, including without limitation contact lenses, intra-ocular lenses, magnifying lenses and protective lenses or visors.
  • Preferred material for ophthalmic elements comprises one or more polymers selected from polycarbonates, polyamides, polyimides, polysulfones, polyethylene terephthalate and polycarbonate copolymers, polyolefins, especially polynorbornenes, diethylene glycol-bis(allyl carbonate) polymers - known as CR39 - and copolymers, (meth)acrylic polymers and copolymers, especially (meth)acrylic polymers and copolymers derived from bisphenol A, thio(meth) acrylic polymers and copolymers, urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, and episulfide polymers and copolymers.
  • composition of the invention can be applied to form the layer on other articles, such as window members for automobiles or airplanes, thus providing advanced functionality.
  • sol-gel process using a combination of the composition and TEOS (tetraethoxysilane).
  • One particular substrate of interest on which the composition may be applied to form the layer is any generation of Gorilla ® Glass, commercially available from Corning Incorporated of Corning, New York.
  • Another particular substrate of interest is Dragontrail ® glass, commercially available from Asahi Glass Company of Tokyo, Japan.
  • the step of applying the composition on the surface of the article to form the layer comprises a wet coating method.
  • wet coating application methods suitable for the method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, inkjet printing, and combinations thereof.
  • the vehicle may be removed from the wet layer via heating or other known methods.
  • the step of applying the composition on the surface of the article may comprise forming the layer on the surface of the article with a deposition apparatus.
  • the deposition apparatus typically comprises a physical vapor deposition apparatus.
  • the deposition apparatus is typically selected from a sputtering apparatus, an atomic layer deposition apparatus, a vacuum apparatus, and a DC magnetron sputtering apparatus. The optimum operating parameters of each of these physical deposition vapor apparatuses are based upon the composition utilized, the article on which the layer is to be formed, etc., as readily understood in the art.
  • the deposition apparatus comprises a vacuum apparatus.
  • the method comprises combining the composition and a pellet to form an impregnated pellet.
  • the pellet typically comprises a metal, alloy, or other robust material, such as iron, stainless steel, aluminum, carbon, copper, ceramic, etc.
  • the pellet has a very high surface area to volume ratio for contacting the siloxane polymer of the composition.
  • the surface area to volume ratio of the pellet may be attributable to porosity of the pellet, i.e., the pellet may be porous.
  • pellet may comprise woven, unwoven, and/or randomized fibers, such as nanofibers, so as to provide the desired surface area to volume ratio.
  • the pellet may comprise a material selected from, for example, S1O2, T1O2, ZrC"2, MgO, AI2O3, CaSC”4, Cu, Fe, Al, stainless steel, carbon, or combinations thereof.
  • the material may be a plug within a casing, which comprises the metal, alloy, or other robust material.
  • the composition may be introduced in or to the pellet in any manner so long as the material of the pellet and the siloxane polymer are combined or otherwise contacted.
  • the pellet may be submerged in the composition, or the composition may be disposed within the casing such that the porous material is impregnated with the composition.
  • the pellet may be submerged in the vehicle, or the vehicle may be disposed within the casing such that the material of the pellet is impregnated with the vehicle, and then the siloxane polymer is disposed in the vehicle within the casing such that the material of the pellet is impregnated with the composition, which is formed in situ in or on the pellet.
  • the method further comprises removing the vehicle from the impregnated pellet to form a neat pellet prior to deposition.
  • the vehicle may be flashed from the pellet via the application of heat.
  • the vehicle may be removed from the pellet by drying at room temperature or a slightly elevated temperature, optionally in the presence of a vacuum or purging air.
  • the neat pellet may be stored until utilized in the deposition apparatus.
  • the neat pellet is stored in a vacuum-sealed aluminum bag.
  • One specific example of a vacuum apparatus suitable for forming the layer from the composition is an HVC-900DA vacuum apparatus, commercially available from Hanil Vacuum Machine Co., Ltd. of Incheon, South Korea.
  • Another example of a deposition apparatus is an Edwards AUTO 306, commercially available from Edwards of Sanborn, NY.
  • the neat pellet is generally placed on a substrate in a chamber of the deposition apparatus along with the article to be coated and the siloxane polymer is volatilized via resistive heat evaporation, thereby forming the layer on the surface of the article.
  • the layer may further undergo heating, humidification, catalytic post treatment, photoirradiation, electron beam irradiation, etc.
  • the layer formed therefrom is generally heated at an elevated temperature, e.g. 80-150 °C, for a period of time, e.g. 45-75 minutes.
  • the layer formed from the composition may be allowed to stand at room temperature and ambient conditions for a period of time, e.g. 24 hours.
  • the thickness of the layer formed from the composition is from 1-1,000, alternatively 1-200, alternatively 1-100, alternatively 5-75, alternatively 10-50, nm.
  • sliding (kinetic) coefficient of friction may be measured by disposing an object having a determined surface area and mass onto a surface-treated article including a layer formed from the composition with a select material (e.g. a standard piece of legal paper) between the object and the layer. A force is then applied perpendicular to gravitational force to slide the object across the layer for a predetermined distance, which allows for a calculation of the sliding coefficient of friction of the layer.
  • the sliding coefficient of friction and durability may vary depending on the particular siloxane polymer utilized in the composition.
  • molecular weight (and corresponding viscosity) and any terminal functionalities in the siloxane polymer generally influence physical properties of the resulting layer.
  • Durability of the layers formed from the composition is generally measured via the water contact angles of the layers after subjecting the layers to an abrasion test. For example, for layers having a lesser durability, the water contact angle decreases after abrasion, which generally indicates that the layer has at least partially deteriorated. Accordingly, the composition can be custom tailored to achieve certain physical properties desirable in specific applications based on the selection of the siloxane polymer.
  • the layers formed from the composition have a water contact angle of from 75 to 125, alternatively from 80-120, alternatively from 90-110, before and after subjecting the layers to the abrasion test.
  • the layers also typically have a sliding (kinetic) coefficient of friction of less than 0.1 ⁇ .
  • any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range such as "at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
  • compositions for surface treatment are prepared in accordance with the subject disclosure.
  • each of the compositions described below comprises a siloxane polymer and a vehicle.
  • the vehicles utilized in the Examples solubilize the siloxane polymers, the vehicles are referred to herein as solvents. Unless otherwise indicated, any percentages set forth below relate to weight percentages.
  • Table 1 below illustrates 6 different compositions (corresponding to Practical Examples 1-6).
  • each of the compositions below comprises a siloxane polymer and a solvent. All values in Table 1 below relate to parts by weight based on the total weight of each respective composition.
  • Siloxane Polymer 1 has a viscosity of 50 centistokes at 25 °C.
  • Siloxane Polymer 2 has a viscosity of 100 centistokes at 25 °C.
  • Siloxane Polymer 3 has a viscosity of 350 centistokes at 25 °C.
  • Siloxane Polymer 4 has a viscosity of 1,000 centistokes at 25 °C.
  • Siloxane Polymer 5 has a viscosity of 5,000 centistokes at 25 °C.
  • Siloxane Polymer 6 has a viscosity of 10,000 centistokes at 25 °C.
  • Solvent 1 comprises octamethyltrisiloxane.
  • compositions of Practical Examples 1-6 are each applied to a surface of a substrate via flow coating.
  • these compositions are applied to a glass substrate via flow coating with a pipette.
  • the compositions are cured at room temperature for about 24 hours to form layers on the substrates.
  • Physical properties of the layers formed from the compositions are measured. In particular, physical properties of the respective layers are measured before and after subjecting the layers to an abrasion resistance test, as described below.
  • the water contact angle (WCA) of each of the layers is measured via a VCA Optima XE goniometer, which is commercially available from AST Products, Inc., Billerica, MA.
  • the water contact angle measured is a static contact angle based on a 2 droplet on each of the layers. This WCA is referred to in Table 2 below as the WCA (initial).
  • the sliding coefficient of friction is also measured for each of the layers.
  • the sliding coefficient of friction is measured by placing a sled having a load of about 156 grams onto each of the layers with a piece of standard paper disposed between each of the layers and the sled.
  • the sled has an area of about 25 x 25 millimeters.
  • a force is applied in a direction perpendicular to gravity to move the sled along each of the layers at a speed of about 2.5 millimeters/sec for a distance of about 42 millimeters to measure the sliding coefficient of friction.
  • the abrasion resistance test utilizes a reciprocating abraser - Model 5900, which is commercially available from Taber Industries.
  • the abrading material utilized is a WypAll microfiber cloth (83630) commercially available from Kimberly-Clark Corporation of Dallas, TX.
  • the reciprocating abraser is operated for 1,500 cycles at a speed of 40 cycles per minute with a stroke length of 1 inch and a load of 5 N.
  • the water contact angle (WCA) is measured again after the abrasion resistance test in accordance with the procedure described above.
  • WCA water contact angle
  • the greater the WCA the greater the durability of the layer. Said differently, the greater the deterioration of the layer via the abrasion test, the lesser the WCA after abrasion.
  • Table 2 sets forth the WCA (initial), sliding (kinetic) coefficient of friction, and WCA after abrasion for the layers of Practical Examples 1-6.
  • Table 3 below illustrates 6 different compositions (corresponding to Practical Examples 7-12).
  • each of the compositions below comprises a siloxane polymer and a solvent. All values in Table 3 below relate to parts by weight based on the total weight of each respective composition.
  • Siloxane Polymer 7 has a viscosity of 65 centistokes at 25 °C.
  • Siloxane Polymer 8 has a viscosity of 190 centistokes at 25 °C.
  • Siloxane Polymer 9 has a viscosity of 450 centistokes at 25 °C.
  • Siloxane Polymer 10 has a viscosity of 2,000 centistokes at 25 °C.
  • Siloxane Polymer 11 has a viscosity of 9,500 centistokes at 25 °C.
  • Siloxane Polymer 12 has a viscosity of 55,000 centistokes at 25 °C.
  • compositions of Practical Examples 7-12 are each applied to a surface of a substrate via flow coating.
  • these compositions are applied to a glass substrate via flow coating with a pipette.
  • the compositions are cured at room temperature for about 24 hours to form layers on the substrates.
  • Table 4 below illustrates the physical properties of each of the layers formed from the compositions of Practical Examples 7-12.
  • the sliding coefficient of friction generally decreases as the viscosity of the siloxane polymer increases.
  • the WCA (initial) and WCA (after abrasion) was generally improved for the layers formed from Practical Examples 7- 12 as compared to those formed from Practical Examples 1-6, which is likely attributable to the vinyl functionality of Siloxane Polymers 7-12.
  • Table 5 below illustrates 4 different compositions (corresponding to Practical Examples 13-16).
  • each of the compositions below comprises a siloxane polymer and a solvent. All values in Table 5 below relate to parts by weight based on the total weight of each respective composition.
  • Siioxane Polymer 13 has a viscosity of 42 centistokes at 25 °C.
  • Siioxane Polymer 14 has a viscosity of 72 centistokes at 25 °C.
  • Siioxane Polymer 15 has a viscosity of 2,000 centistokes at 25 °C.
  • Siioxane Polymer 16 has a viscosity of 13,500 centistokes at 25 °C.
  • compositions of Practical Examples 13-16 are each applied to a surface of a substrate via flow coating.
  • these compositions are applied to a glass substrate via flow coating with a pipette.
  • the compositions are cured at room temperature for about 24 hours to form layers on the substrates.
  • Table 6 below illustrates the physical properties of each of the layers formed from the compositions of Practical Examples 13-16.
  • Siloxane Polymer 17 has the general formula:
  • c" and d" are selected such that the Siloxane Polymer 1 has a viscosity of about 38,000 centistokes at 25 °C.
  • Siloxane Polymer 18 has the general formula:
  • e is selected such that the Siloxane Polymer 18 has a viscosity of about 650 centistokes at 25 °C.
  • Solvent 2 is hexamethyldisiloxane.
  • compositions of Practical Examples 17-18 are each applied to a surface of a substrate via spray coating.
  • these compositions are applied to a glass substrate via a PVA-1000 dispensing machine (commercially available from PVA of Cohoes, NY) having an atomization pressure of 8 psi, a liquid pressure of 5 psi, a stroke of from 2 to 2.5 mil, a nozzle height of 5.3 cm, and a speed of about 100 mm/sec.
  • PVA-1000 dispensing machine commercially available from PVA of Cohoes, NY
  • the compositions are cured at room temperature for about 24 hours to form layers on the substrates.
  • the abrasion test utilizes a reciprocating abraser - Model 5900, which is commercially available from Taber Industries of North Tonawanda, NY.
  • the abrading material utilized is a rubbing eraser having dimensions of 6.0 x 12.2 mm.
  • the reciprocating abraser is operated for 1,500 cycles at a speed of 40 cycles per minute with a stroke length of 1 inch and a load of 5 N.
  • the WCA after abrasion is measured in accordance with the procedure described above with respect to Practical Examples 1-6.
  • Table 8 illustrates the physical properties of each of the layers formed from the compositions of Practical Examples 17-18.
  • Table 9 below illustrates 3 different compositions (corresponding to Practical Examples 19-21).
  • each of the compositions below comprises a siloxane polymer and a solvent. All values in Table 9 below relate to parts by weight based on the total weight of each respective composition.
  • Siloxane Polymers 19-21 include branching and/or a resinous networked structure.
  • Siloxane Polymer 19 is a branched polymer including a silicon-bonded alkenyl group. Siloxane Polymer 19 is similar to the general structure of Siloxane Polymers 7-12 but for the branching of Siloxane Polymer 19. Siloxane Polymer 19 has a viscosity of 750 centistokes at 25 °C.
  • Siloxane Polymer 20 is a blend of a vinylated MQ resin and a siloxane polymer having the general formula of Siloxane Polymers 7-12 and a viscosity of 2,000 centistokes at 25 °C.
  • the blend of Siloxane Polymer 20 has an overall viscosity of 5,000 centistokes at 25 °C.
  • Siloxane Polymer 21 is a blend of a vinylated MQ resin and a siloxane polymer having the general formula of Siloxane Polymers 7-12 and a viscosity of 55,000 centistokes at 25 °C.
  • the blend of Siloxane Polymer 21 has an overall viscosity of 45,000 centistokes at 25 °C.
  • compositions of Practical Examples 19-21 are each applied to a surface of a substrate via flow coating.
  • these compositions are applied to a glass substrate via flow coating with a pipette.
  • the compositions are cured at room temperature for about 24 hours to form layers on the substrates.
  • Table 10 illustrates the physical properties of each of the layers formed from the compositions of Practical Examples 19-21.
  • Siloxane Polymer 22 and a volatile methylsiloxane solvent are impregnated into a pellet comprising steel wool and a copper casing.
  • Siloxane Polymer 22 has the following general formula:
  • g' is selected such that the Siloxane Polymer 22 has a viscosity of about 380 centistokes at 25 °C.
  • the solvent is driven from the pellet at room temperature under vacuum purge.
  • Siloxane Polymer 22 is deposited via a resistive heat evaporation apparatus (Edwards AUTO 306, commercially available from Edwards of Sanborn, NY).
  • the resistive heat evaporation apparatus operates at a vacuum of 2.0E-5 torr to deposit the Siloxane Polymer 22 on a surface of glass.
  • the Siloxane Polymer 22 is heated at 125 °C for about 1 hour to form a layer on the glass.
  • the layer has a thickness of about 45-55 nm.
  • Siloxane Polymer 23 and a volatile methylsiloxane solvent are impregnated into a pellet comprising steel wool and a copper casing.
  • Siloxane Polymer 23 has the following general formula:
  • g' is selected such that the Siloxane Polymer 23 has a viscosity of about 650 centistokes at 25 °C.
  • the solvent is driven from the pellet at room temperature under vacuum purge.
  • Siloxane Polymer 23 is deposited via a resistive heat evaporation apparatus (Edwards AUTO 306, commercially available from Edwards of Sanborn, NY).
  • the resistive heat evaporation apparatus operates at a vacuum of 2.0E-5 torr to deposit the Siloxane Polymer 23 on a surface of glass.
  • the Siloxane Polymer 23 is heated at 125 °C for about 1 hour to form a layer on the glass.
  • the layer has a thickness of about 45-55 nm.
  • a deposition apparatus e.g. a PVD apparatus
  • a PVD apparatus may be utilized to form layers which have similar excellent physical properties (such as the sliding coefficient of friction and durability) to layers formed from wet coating methods.
  • the thickness of the layers formed in Practical Examples 22 and 23 also influences the physical properties thereof.
  • Table 12 below illustrates the physical properties of the layers formed in Practical Examples 22 and 23 at thicknesses of 25 nm, 50 nm, and 75 nm, respectively.
  • the thicknesses listed below were measured via a crystal monitor included in the resistive heat evaporation apparatus, and thus the thicknesses below in Table 12 may not represent absolute thicknesses, but nonetheless illustrate physical properties as a function of thickness.

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

Abstract

L'invention concerne une composition qui permet de traiter une surface et qui comporte un polymère siloxane et un milieu de suspension. La composition forme des couches qui sont faciles à nettoyer et qui ont d'excellentes propriétés physiques, comprenant une résistance aux salissures et aux taches. De plus, la durabilité et le coefficient de frottement des couches peuvent être régulés de façon sélective en fonction de la composition. Un article à surface traitée et des procédés de préparation de l'article à surface traitée avec la composition sont également décrits.
PCT/US2014/013191 2013-01-30 2014-01-27 Composition pour traitement de surface, procédés de préparation d'un article à surface traitée et article à surface traitée WO2014120607A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104448999A (zh) * 2014-11-18 2015-03-25 厦门建霖工业有限公司 一种耐指纹表面处理剂及其使用方法
WO2016036750A1 (fr) * 2014-09-02 2016-03-10 Sung Wung Yeom Application d'un revêtement à un substrat, structures composites formées par l'application d'un revêtement
US11963868B2 (en) 2020-06-01 2024-04-23 Ast Products, Inc. Double-sided aspheric diffractive multifocal lens, manufacture, and uses thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023204276A1 (fr) * 2022-04-20 2023-10-26 ダイキン工業株式会社 Agent de traitement de surface

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671484A (en) * 1969-07-23 1972-06-20 Kenneth G Cooper Silicone release coatings
EP0330234A2 (fr) * 1988-02-25 1989-08-30 Dow Corning Corporation Composition pour couche d'accrochage
EP0987317A1 (fr) * 1997-06-04 2000-03-22 Toto Ltd. Procede de traitement prealable de surface avant formation d'une pellicule hydrophile photocatalytique, detergent et composition de sous-couche mis en application dans ce procede
US6652599B1 (en) * 1997-03-13 2003-11-25 Takemoto Oil & Fat Co., Ltd. Treatment agent for elastic polyurethane fibers and elastic polyurethane fibers treated therewith
US20040202872A1 (en) * 2002-07-23 2004-10-14 Pennzoil-Quaker State Company Hydrophobic surface treatment composition and method of making and using same
US20040235683A1 (en) * 2003-05-23 2004-11-25 Moffett Robert Harvey Mold release composition and process therewith
JP2011212568A (ja) * 2010-03-31 2011-10-27 Kansai Paint Co Ltd 塗膜形成方法及び親水化処理剤溶液

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3671484A (en) * 1969-07-23 1972-06-20 Kenneth G Cooper Silicone release coatings
EP0330234A2 (fr) * 1988-02-25 1989-08-30 Dow Corning Corporation Composition pour couche d'accrochage
US6652599B1 (en) * 1997-03-13 2003-11-25 Takemoto Oil & Fat Co., Ltd. Treatment agent for elastic polyurethane fibers and elastic polyurethane fibers treated therewith
EP0987317A1 (fr) * 1997-06-04 2000-03-22 Toto Ltd. Procede de traitement prealable de surface avant formation d'une pellicule hydrophile photocatalytique, detergent et composition de sous-couche mis en application dans ce procede
US20040202872A1 (en) * 2002-07-23 2004-10-14 Pennzoil-Quaker State Company Hydrophobic surface treatment composition and method of making and using same
US20040235683A1 (en) * 2003-05-23 2004-11-25 Moffett Robert Harvey Mold release composition and process therewith
JP2011212568A (ja) * 2010-03-31 2011-10-27 Kansai Paint Co Ltd 塗膜形成方法及び親水化処理剤溶液

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 201171, Derwent World Patents Index; AN 2011-N30761, XP002721217 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016036750A1 (fr) * 2014-09-02 2016-03-10 Sung Wung Yeom Application d'un revêtement à un substrat, structures composites formées par l'application d'un revêtement
CN104448999A (zh) * 2014-11-18 2015-03-25 厦门建霖工业有限公司 一种耐指纹表面处理剂及其使用方法
US11963868B2 (en) 2020-06-01 2024-04-23 Ast Products, Inc. Double-sided aspheric diffractive multifocal lens, manufacture, and uses thereof

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JP2014148657A (ja) 2014-08-21
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