Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups

Definitions

• compositions useful as surface protectants for automotive applications and related methods are compositions useful as surface protectants for automotive applications and related methods.
• surfaces of motor vehicles for example, are regularly exposed to weather effects such as rain, snow, sleet, ice formation, and other precipitation, as well as environmental contaminants (e.g., dirt, grime, dust, air-borne pollutants, road surface residue, insect debris, and bird droppings). It is desirable to maintain the physical condition of these vehicles by cleaning or washing them and, in some cases, subsequently waxing and polishing or buffing them.
• Many products that are intended to improve or restore a vehicle’s finish are commercially available.
• a coating composition said to be useful for imparting water repellency, gloss, and durability to a surface, particularly on an automobile or other vehicle is described in U.S. Pat. Appl. Pub. No.2017/0349783 (Kirino).
• a highly abrasion-resistant vehicle paint is described in U.S. Pat. Appl. Pub. No.2011/0082254 (Sepeur et al.).
• Certain compositions including polyorganosiloxanes having hydrolyzable groups have been reported to be useful for automotive coatings and are described in U.S. Pat. No. 9,334,408 (Onai), U.S. Pat. Appl. Pub. No.2008/0026163 (Hamaguchi et al.), Int. Pat. Appl.
• a first tier uses carnauba-based or natural wax-based products. While easy to use, these products tend to have unremarkable hydrophobic properties and poor longevity on a vehicle.
• the next tier uses synthetic materials such as specialty organo-functional silicones, which offer higher durability due to increased affinity between the vehicle surface and the active ingredients, and generally, greater hydrophobicity. These materials have higher temperature stability compared to natural waxes and can display improved water and soap resistance.
• the highest tier is typically limited to the professional market, and uses reactive chemistries such as blends of silane, polyorganosiloxane, and/or silazane that react with moisture and cure over time in ambient conditions.
• reactive chemistries such as blends of silane, polyorganosiloxane, and/or silazane that react with moisture and cure over time in ambient conditions.
• these products can display even higher chemical and wash resistance, with even further improved durability compared to the lower tier products.
• One downside of the highest tier products relates to their reactivity. Because these products can cure very quickly, there are special formulation, packaging, shelf-life and application considerations and specialized training for users/installers of these types of products. This in turn, can significantly reduce access and increase cost of obtaining such protection for consumers. Additionally, mistakes in application using these products can lead to streaks and high spots.
• the provided composition which contains a multifunctional polyorganosiloxane, optionally at least one silane, and at least one non- ionic surfactant.
• the multifunctional polyorganosilane is an oligomeric or polymeric material comprising silicon atoms covalently bonded to both oxygen and carbon atoms, and an alkoxysilane group.
• This emulsion can be activated by use of a water-soluble catalyst in which breaking the emulsion (e.g., through evaporation or wiping onto a vehicle) causes the oil droplets to coalesce and crosslink into a protective film that is resistant to both solvents and car washing.
• breaking the emulsion e.g., through evaporation or wiping onto a vehicle
• breaking the emulsion causes the oil droplets to coalesce and crosslink into a protective film that is resistant to both solvents and car washing.
• the surface protectant composition comprises: an oil component comprised of a multifunctional polyorganosiloxane; and optionally at least one silane; an aqueous component comprised of a phosphorus-based acid catalyst, optionally with a neutral acid Log P greater than -2.0; a base acting as a blocking agent to the acid catalyst; and water; and at least one non-ionic surfactant present in either the oil component or aqueous component, wherein the oil component and aqueous component form a water-based emulsion.
• a method of making a coated article comprising: applying the composition on at least a portion of a surface of a substrate; and allowing the water and base in the composition to evaporate, thereby inducing a curing of the oil component through the acid catalyst to obtain a coating on at least a portion of the surface of the substrate.
• a coated article is provided, as made by the method.
• aliphatic group means a saturated or unsaturated linear, branched, or cyclic hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.
• alkyl refers to a monovalent group that is a radical of an alkane and includes straight-chain, branched, cyclic, and bicyclic alkyl groups, and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise indicated, the alkyl groups typically contain from 1 to 30 carbon atoms. In some embodiments, the alkyl groups contain 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Cyclic groups can be monocyclic or polycyclic and typically have from 3 to 10 ring carbon atoms.
• alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and norbornyl.
• alkylene refers to the divalent or trivalent form of the “alkyl” groups defined above. “ambient conditions” means at 21 ⁇ C and 101.3 kilopascals.
• amino group is a functional group that consists of a nitrogen atom attached by single bonds to hydrogen atoms, alkyl groups, aryl groups, or a combination of these three.
• Primary amino groups include two hydrogen atoms bonded to the nitrogen, secondary amino groups include one hydrogen atom bonded to the nitrogen, and tertiary amino groups include no hydrogen atoms bonded to the nitrogen.
• aryl refers to a monovalent group that is aromatic and, optionally, carbocyclic. The aryl has at least one aromatic ring. Any additional rings can be unsaturated, partially saturated, saturated, or aromatic. Optionally, the aromatic ring can have one or more additional carbocyclic rings that are fused to the aromatic ring.
• the aryl groups typically contain from 6 to 30 carbon atoms and optionally contain at least one heteroatom (i.e., O, N, or S). In some embodiments, the aryl groups contain 6 to 20, 6 to 18, 6 to 16, 6 to 12, or 6 to 10 carbon atoms. Examples of an aryl group include phenyl, naphthyl, biphenyl, phenanthryl, anthracyl, and pyridinyl. “arylene” refers to the divalent form of the “aryl” groups defined above. “arylalkylene” refers to an “alkylene” moiety to which an aryl group is attached.
• arylalkylenyl refers to a terminal aryl group attached to an “alkylene” moiety.
• catenated heteroatom means an atom other than carbon (for example, oxygen, nitrogen, or sulfur) that replaces one or more carbon atoms in a carbon chain (for example, so as to form a carbon-heteroatom-carbon chain or a carbon-heteroatom-heteroatom- carbon chain).
• curing refers to the joining of polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably.
• a cured or crosslinked polymer is generally characterized by insolubility but may be swellable in the presence of an appropriate solvent.
• curable composition refers to a composition that can be cured.
• epoxy group refers to a functional group that consists of an oxygen atom joined by single bonds to two adjacent carbon atoms, thus forming the three-membered epoxide ring.
• fluoro- (for example, in reference to a group or moiety, such as in the case of “fluoroalkylene” or “fluoroalkyl” or “fluorocarbon”) or “fluorinated” can mean partially fluorinated such that there is at least one carbon-bonded hydrogen atom or perfluorinated.
• hydrolyzable group or “hydrolyzable functional group” refers to a group that can react with water under conditions of atmospheric pressure. The reaction with water may optionally be catalyzed by acid or base. The hydrolyzable group is often converted to a hydroxyl group when it reacts. The hydroxyl group often undergoes further reactions (e.g., condensation reactions). As used herein, the term is often used in reference to one or more groups bonded to a silicon atom in a silyl group.
• halogen e.g., iodo, bromo, chloro
• alkoxy e.g., -O-alkyl
• aryloxy e.g., -O-aryl
• acyloxy e.g., -O-C(O)-alkyl
• amino e.g., -NR 1 R 2 , wherein each of R
• halogen refers to a halogen atom or one or more halogen atoms, including chlorine, bromine, iodine, and fluorine atoms or fluoro, chloro, bromo, or iodo substituents.
• oligomer means a molecule that comprises at least two repeat units and that has a molecular weight less than its entanglement molecular weight; such a molecule, unlike a polymer, exhibits a significant change in properties upon the removal or addition of a single repeat unit.
• oxy means a divalent group or moiety of formula -O-.
• perfluoro- (for example, in reference to a group or moiety, such as in the case of “perfluoroalkylene” or “perfluoroalkyl” or “perfluorocarbon”) or “perfluorinated” means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine.
• perfluoroether means a group or moiety having two saturated or unsaturated perfluorocarbon groups (linear, branched, cyclic (e.g., alicyclic), or a combination thereof) linked with an oxygen atom (that is, there is at least one catenated oxygen atom).
• polyfluoropolyether means a group having three or more saturated or unsaturated perfluorocarbon groups (linear, branched, cyclic (e.g., alicyclic), or a combination thereof) linked with oxygen atoms (that is, there are at least two catenated oxygen atoms).
• the phrase “consisting essentially of” indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they materially affect the activity or action of the listed elements.
• terms such as “a,” “an,” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration.
• the terms “a,” “an,” and “the” are used interchangeably with the phrases “at least one” and “one or more.”
• the phrases “at least one of” and “comprises at least one of” followed by a list refers to any one of the items in the list and any combination of two or more items in the list.
• compositions are useful in protecting surfaces from exposure to weather elements, dirt, and debris.
• Surfaces to be protected can include vehicular surfaces, and in particular automotive exterior surfaces.
• These compositions can be water- based emulsions, and generally oil-in-water emulsions.
• These water-based emulsions include an oil component and an aqueous component, stabilized by one or more surfactants.
• the oil component is comprised of a multifunctional polyorganosiloxane and optionally at least one silane.
• the aqueous component is comprised of an acid catalyst, a base, and water.
• the base acts as a blocking agent to the acid catalyst.
• At least one non- ionic surfactant can be present in either the oil component or aqueous component.
• Multifunctional polyorganosiloxanes useful in the compositions of the present disclosure include oligomers and polymers that can be linear or branched. Useful oligomers and polymers include those that have random, alternating, block, or graft structures, or a combination thereof. When the composition is stored and applied, it typically does not have a network, cage, or crosslinked structure.
• Useful polyorganosiloxanes can include divalent units each independently represented by formula I: , wherein each R is wherein alkyl and arylalkylenyl are unsubstituted or substituted with halogen and optionally interrupted by at least one catenated -O-, -S-, -NR 11 -, or combination thereof, or wherein aryl, arylalkylenyl, and heterocycloalkyenyl are unsubstituted or substituted by at least one alkyl, alkoxy, halogen, or combination thereof.
• R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof.
• Useful polyorganosiloxanes can also comprise siloxane repeating units according the formula (OR") p -Si(R') 3-p -[G-Si(R') 2 ] t -(W) s -[(R') 2 SiO] q -[Si(R') 2 -G] t -Si(R') 3-p -(OR") p ; (R"O) p -Si(R') 3-p -[(R') 2 SiO] q -(W) s -[(R') 2 SiO] q ]-Si(R') 3-p -(OR") p ; or R-[G-Si(R') 2 ] t -(W) s - [(R') 2 SiO] q -[Si(R') 2 -G] t -[Si(R') 3-p -(OR") p ], wherein
• R 11 is hydrogen or alkyl, for example, having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl). In certain embodiments, R 11 is methyl or hydrogen. In some embodiments, the halogen or halogens on the alkyl, aryl, arylalkylenyl, or heterocycloalkylenyl groups is a fluoro group. R is generally considered a non-hydrolyzable group, which is not capable of being hydrolyzed under the conditions described above for hydrolyzing hydrolyzable groups.
• R is R f C j H 2j -, wherein j is an integer of 2 to 8 (or 2 to 3), and R f is a fluorinated or perfluorinated alkyl group having 1 to 12 carbon atoms (or 1 to 6 carbon atoms); in some embodiments, R is R f ’C j H 2j -, wherein j is an integer of 2 to 8 (or 2 to 3), and R f ’ is a fluorinated or perfluorinated polyether group having 1 to 45 carbon atoms (in some embodiments, 1 to 30 carbon atoms), aryl, and combinations thereof.
• R f is a perfluoroalkyl group; and/or R f ’ is a perfluoropolyether group.
• Perfluoropolyether groups that can be linear, branched, cyclic, or a combination thereof.
• the perfluoropolyether group can be saturated or unsaturated (in some embodiments, saturated).
• Examples of useful perfluoropolyether groups include those that have -(C p F 2p )-, -(C p F 2p O)-, -(CF(R f )O)-, -(CF(R f )C p F 2p O)-, -(C p F 2p CF(R f )O)-, or -(CF 2 CF(R f )O)- repeating units or combinations thereof, wherein p is an integer of 1 to 10 (or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 3); R f is selected from perfluoroalkyl, perfluoroether, perfluoropolyether, and perfluoroalkoxy groups that are linear, branched, cyclic, or a combination thereof and that have up to 12 carbon atoms, up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, up to 4 carbon atoms, or up to 3 carbon atoms
• different repeating units can be combined in a block, alternating, or random arrangement to form the perfluoropolyether group.
• the terminal group of the perfluoropolyether group can be (C p F 2p+1 )- or (C p F 2p+1 O)-, for example, wherein p is as defined above.
• Examples of useful perfluoropolyether groups include C 3 F 7 O(CF(CF 3 )CF 2 O) n” CF(CF 3 )-, C 3 F 7 O(CF 2 CF 2 CF 2 O) n” CF 2 CF 2 -, CF 3 O(C 2 F 4 O) n” CF 2 -, CF 3 O(CF 2 O) n” C 2 F 4 O) q CF 2 -, and F(CF 2 ) 3 O(C 3 F 6 O) q (CF 2 ) 3 -, wherein n” has an average value of 0 to 50, or 1 to 50, or 3 to 30, or 3 to 15, or 3 to 10; and q has an average value of 0 to 50, or 3 to 30, or 3 to 15, or 3 to 10.
• the perfluoropolyether group comprises at least one divalent hexafluoropropyleneoxy group (-CF(CF 3 )-CF 2 O-).
• Such perfluoropolyether groups can be obtained through the oligomerization of hexafluoropropylene oxide.
• each R is independently alkyl, aryl, or alkyl substituted by a fluoro group and optionally interrupted by at least one catenated -O- group.
• Suitable alkyl groups for R in formula I typically have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Examples of useful alkyl groups include methyl, ethyl, isopropyl, n-propyl, n-butyl, and iso-butyl.
• each R is independently alkyl having up to six (in some embodiments, up to 4, 3, or 2) carbon atoms, F[CF(CF 3 )CF 2 O] a CF(CF 3 )C j H 2j - (wherein j is an integer of 2 to 8 (or 2 to 3) and a has an average value of 4 to 20), C 4 F 9 C 3 H 6 -, C 4 F 9 C 2 H 4 -, C 4 F 9 OC 3 H 6 -, C 6 F 13 C 3 H 6 -, CF 3 C 3 H 6 -, CF 3 C 2 H 4 -, phenyl, benzyl, or C 6 H 5 C 2 H 4 -.
• each R is independently methyl or phenyl. In some embodiments, each R is methyl. In some embodiments, the polyorganosiloxane in the provided composition has more than two (in some embodiments, at least 2.1, 2.2, 2.3, 2.4, 2.5.2.6, 2.7, 2.8, 2.9, 3, or more) -SiY p R 3-p groups, wherein Y is a hydrolyzable group, R is as defined above in any of its embodiments, and p is 1, 2, or 3 (in some embodiments, 2 or 3, or 3).
• Alkoxy and acyloxy are optionally substituted by halogen, and aryloxy is optionally substituted by halogen, alkyl (e.g., having up to 4 carbon atoms), or haloalkyl.
• alkoxy and acyloxy have up to 18 (or up to 12, 6, or 4) carbon atoms.
• aryloxy has 6 to 12 (or 6 to 10) carbon atoms.
• each Y is independently alkoxy, aryloxy, or acyloxy.
• each Y is independently alkoxy having up to ten carbon atoms.
• each Y is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms. In some of these embodiments, each Y is independently methoxy or ethoxy.
• the more than two (in some embodiments, at least 2.1, 2.2, 2.3, 2.4, 2.5.2.6, 2.7, 2.8, 2.9, 3, or more) -SiY p R 3-p groups may be pendent groups, terminal groups, or a combination of pendent and terminal groups. In some embodiments, the -SiY p R 3-p groups are pendent groups.
• the polyorganosiloxane is terminated with - SiR 3 groups, wherein R is defined as above in any of its embodiments.
• the polyorganosiloxane has up to 10, 9, 8, 7, 6, or 5 -SiY p R 3-p groups. In some embodiments, the polyorganosiloxane can have an average of more than two - SiYpR3-p groups in the polymer. In some embodiments, the ratio of divalent units represented by formula I to -SiY p R 3-p groups is at least 4, 5, 10 and up to 400, 300, 200, 100, or 75. In some embodiments, the polyorganosiloxane in the provided composition comprises m terminal units represented by formula -Q-SiY p R 3-p and n divalent units represented by formula II: , wherein n is at 2 (in some embodiments, at or more).
• the polyorganosiloxane includes the divalent units represented by formula II.
• each R is independently as defined above for a divalent unit of formula I, each Y and p as defined above in any of its embodiments, and each Q is independently alkylene, arylene, or alkylene that is at least one of interrupted or terminated by aryl, wherein the alkylene, arylene, and alkylene that is at least one of interrupted or terminated by aryl are optionally at least one of interrupted or terminated by at least one ether (i.e., -O-), thioether (i.e., -S-), amine (i.e., -NR 11 -), amide (i.e., -N(R 11 )-C(O)- or -C(O)-N(R 11 )-), ester (i.e., -O-
• R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstiuted or substituted by at least one alkyl, alkoxy, or combination thereof.
• R 11 is hydrogen or alkyl, for example, having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, or sec-butyl).
• R 11 is methyl or hydrogen.
• each Q is independently alkylene that is optionally at least one of interrupted or terminated by at least one ether, thioether, or combination thereof.
• the alkylene can have 1 to 10, 1 to 6, or 1 to 4 carbon atoms.
• Q is alkylene having 1 to 10, 1 to 6, 1 to 4, 1 to 3, or 1 to 2 carbon atoms.
• Q is a poly(alkylene oxide) group.
• Suitable poly(alkylene oxide) groups include those represented by formula (OR 10 ) a’ , in which each OR 10 is independently - CH 2 CH 2 O-, –CH(CH 3 )CH 2 O–, –CH 2 CH 2 CH 2 O–, –CH 2 CH(CH 3 )O–, -CH 2 CH 2 CH 2 CH 2 O-, –CH(CH 2 CH 3 )CH 2 O–, –CH 2 CH(CH 2 CH 3 )O–, and –CH 2 C(CH 3 ) 2 O–.
• each OR 10 independently represents -CH 2 CH 2 O-, –CH(CH 3 )CH 2 O– or – CH 2 CH(CH 3 )O–.
• Each a’ is independently a value from 5 to 300 (in some embodiments, from 10 to about 250, or from 20 to about 200).
• the polyorganosiloxane in the provided composition comprises a terminal unit represented by formula -Q-SiY p R 3-p , wherein Q, R, and p are as defined above in any of their embodiments.
• Q may also be a bond.
• the polysiloxane includes one terminal unit represented by formula -Q-SiY p R 3-p . In some embodiments, the polysiloxane includes two terminal units represented by formula -Q-SiY p R 3-p . If the polysiloxane is branched, it can include more than two terminal units represented by formula -Q-SiY p R 3-p . In some embodiments, the polysiloxane includes at least one terminal unit represented by formula -Q-SiY p R 3-p .
• the polyorganosiloxane in the provided composition is represented by formula III: (R’)R 2 SiO[R 2 SiO] r [(Y p R 3-p SiQ)RSiO)] s SiR 2 (R’) [III]
• each R’ is independently R or a terminal unit represented by formula -Q-SiY p R 3-p ;
• R, Y, Q, and p are as defined above in any of their embodiments, s is at least 1, and r+s is in a range from 10 to 1000, 10 to 500, 10 to 400, 10 to 300, 12 to 300, 13 to 300, 13 to 200, 10 to 100, 10 to 50, or 10 to 30.
• each R’ is independently represented by formula -Q-SiY p R 3-p .
• at least 40 percent, and in some embodiments at least 50 percent, of the R groups are phenyl, methyl, or combinations thereof.
• at least 60 percent, at least 70 percent, at least 80 percent, at least 90 percent, at least 95 percent, at least 98 percent, or at least 99 percent of the R groups can be phenyl, methyl, or combinations thereof.
• at least 40 percent, and in some embodiments at least 50 percent, of the R groups are methyl.
• At least 60 percent, at least 70 percent, at least 80 percent, at least 90 percent, at least 95 percent, at least 98 percent, or at least 99 percent of the R groups can be methyl.
• each R is methyl.
• formula III is shown as a block copolymer, it should be understood that the divalent units of formulas I and II can be randomly positioned in the copolymer.
• polyorganosiloxanes useful for practicing the present disclosure also include random copolymers.
• the ratio of r units to s units and R’ groups represented by - Q-SiY p R 3-p or Y is at least 4, 5, 10 and up to 400, 300, 200, 100, or 75.
• the polyorganosiloxane in the provided composition includes at least one divalent unit represented by formula IV: , wherein Y is as is R or Y.
• the polyorganosiloxane has at least one -Si(R’) 2 Y end group, where R’ is R or Y, and Y is as defined above in any of its embodiments.
• each Y is independently alkoxy, aryloxy, or acyloxy.
• each Y is independently alkoxy having up to ten carbon atoms.
• each Y is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms.
• each Y is independently methoxy or ethoxy.
• each R’ is independently phenyl or methyl.
• each R’ is a methyl group.
• the polyorganosiloxane has less than 10 percent, less than 5 percent, less than 2.5 percent, or less than 1 percent by weight units represented by formula RSiO 3/2 , based on the total weight of the polyorganosiloxane.
• each Y is methoxy.
• the weight percent of methoxy groups in the polyorganosiloxane is not more than 25%, 20%, 15%, 10%, or 5%, based on the total weight of the polyorangosiloxane. In some embodiments, the weight percent of methoxy groups in the polyorganosiloxane is at least 0.05%, 0.1%, 0.5%, 1.0%, or 1.5%, based on the total weight of the polyorangosiloxane. In some embodiments, the provided composition includes at least 1 weight percent (wt%), at least 5 wt%, at least 10 wt%, at least 50 wt%, or at least 60 wt% of the polyorganosiloxane, based on the total weight of the composition.
• the composition includes up to 99 wt%, up to 95 wt%, or up to 90 wt% of the polyorganosiloxane, based on the total weight of the composition.
• solvents or water any of these percentages can be based on the total weight of the solids in the composition (that is, excluding solvent and/or water).
• Suitable solvents can include, for example, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), acetonitrile, ethylene glycol, propylene glycol, and glycerin.
• the polysiloxanes can be prepared by known synthetic methods, and many are commercially available (for example, from Wacker Chemie AG, Kunststoff, Germany, Shin- Etsu Chemical, Tokyo, Japan, Dow Corning Corporation, or from Gelest, Inc. (see, for example, the polysiloxanes described in Silicon Compounds: Silanes and Silicones, Second Edition, edited by B. Arkles and G. Larson, Gelest, Inc. (2008)).
• Polyorganosiloxanes can be prepared by using known synthetic methods including the platinum-catalyzed addition reaction of an olefin (e.g., vinyltrimethoxysilane) and a hydrosiloxane (small molecule, oligomer, or polymer).
• the polyorganosiloxane in the provided composition has a number average molecular weight of at least 300 grams per mole, at least 500 grams per mole, at least 1000 grams per mole, at least 2000 grams per mole, at least 3000 grams per mole, at least 4000 grams per mole, or at least 5000 grams per mole.
• Polysiloxanes disclosed herein typically have a distribution of molecular weights. The number and type of repeating units, end groups, and the molecular weights of polysiloxanes can be determined, for example, by nuclear magnetic resonance (NMR) spectroscopy (including 29 Si NMR spectroscopy) using techniques known to one of skill in the art.
• NMR nuclear magnetic resonance
• the number of -SiY p R 3-p groups in a polyorganosiloxane can be determined by NMR.
• Molecular weights, particularly for higher molecular-weight materials, including number average molecular weights and weight average molecular weights, can also be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using techniques known to one of skill in the art.
• the inclusion of a silane may not be necessary in all embodiments, and can in some cases reduce the stability of the emulsion. For end performance of the product, however, it can be beneficial to include a silane.
• the silane is an amino-functional silane.
• each R 4 is independently alkylene, arylene, or alkylene interrupted or terminated by arylene. In some embodiments, each R 4 is independently a divalent alkylene group. In some embodiments, each R 4 is independently a divalent alkylene group having up to 6 (in some embodiments, 5, 4, or 3) carbon atoms.
• Each Z is independently - O- or -NR 6 -, and r is 0, 1, 2, or 3. In some embodiments, r is 0. In some embodiments, each Z is -NR 6 -.
• r is 1, 2, or 3. In some embodiments, r is 1 or 2. In embodiments in which r is 1, 2, or 3, the second amino-functional silane includes diamino-functional silanes, triamino-functional silanes, and tetraamino-functional silanes, for example. In some embodiments in which r is greater than 0, -[R 4 -Z] r -R 4 - is represented by formula –CH 2 -CH 2 -N(R 6 )-CH 2 -CH 2 - or –CH 2 -CH 2 -N(R 6 )–CH 2 -CH 2 -N(R 6 )-CH 2 -CH 2 -CH 2 -.
• each R 5 can independently be alkyl, aryl, or alkylenyl interrupted or terminated by aryl.
• R 5 is alkyl or arylalkylenyl.
• R 5 is alkyl (e.g., methyl or ethyl).
• each R 6 is independently hydrogen, alkyl, aryl, alkylenyl interrupted or terminated by aryl, or -R 4 -[SiY p R 5 3 -p ], where R 4 is defined as in any of the above embodiments.
• one R 6 group is hydrogen or alkyl, and the other R 6 group is -R 4 -[SiY p R 5 3-p ]. In some of these embodiments, one R 6 group is alkyl, and the other R 6 group is -R 4 -[SiY p R 5 3 -p ]. In some of these embodiments, alkyl may have up to 6 (in some embodiments, up to 5, 4, 3, or 2) carbon atoms. In some embodiments, one R 6 group is hydrogen or methyl, and the other R 6 group is -R 4 -[SiYpR 5 3-p].
• one R 6 group is hydrogen, and the other R 6 group is -R 4 -[SiY p R 5 3-p ].
• each R 6 is hydrogen.
• at least one R 6 is alkyl having up to 6 (in some embodiments, up to 5, 4, 3, or 2) carbon atoms.
• one R 6 is methyl and one R 6 is hydrogen.
• Y and p are independently defined as above for formula I, in any of their embodiments.
• amino-functional silanes suitable for the provided composition include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3- trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, N-methyl-bis(3- trimethoxysilylpropyl)amine, N-methyl-bis(3-triethoxysilylpropyl)amine, [3-(2 aminoethylamino)propyl]trimethoxysilane, 3-[2-(2-aminoethylamino)ethylamino] propyltrimethoxysilane, [3-(2-aminoethylamino)propyl]triethoxysilane, 3-[2-(2- aminoethylamino)ethylamino]propyltriethoxysilane, N,N’-bis[3-trimethoxysilylpropyl
• the silane of the present disclosure is a cyclic azasilane.
• Such compounds may be represented by the following formula VI.
• R 7 Y In formula VI, R 7 is an is uninterrupted or interrupted by at least one catenated -N(R 8 )-, wherein each R 8 is independently hydrogen, alkyl, or alkenyl, in some embodiments, having up to 12, 6, 4, 3, or 2 carbon atoms and unsubstituted or substituted by -NR 6 2 , wherein is R 6 is independently as defined above; and each Y is independently as defined above in any of its embodiments in connection with formula I.
• Suitable cyclic azasilanes include 2,2-dimethoxy-N-butyl-1- aza-2-silacyclopentane, 2-methyl-2-methoxy-N-(2-aminoethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(2-aminoethyl)-1-aza-2-silacyclopentane, 2,2-dimethyl-N-allyl-1-aza-2- silacyclopentane, 2,2-dimethoxy-N-methyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-aza- 2-silacyclopentane, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, and N-methyl-1-aza-2,2,4- trimethylsilacyclopentane.
• the provided composition can include at least one of an amino-functional silane of formula V or cyclic azasilane of formula VI.
• the composition includes the amino-functional silane.
• the composition includes the cyclic azasilane.
• the composition includes both the amino- functional silane and the cyclic azasilane.
• the provided composition includes at least 1 wt%, at least 0.1 wt%, at least 0.01 wt%, or at least 0.001 wt% of at least one of the amino-functional silane or cyclic azasilane, including any of those described above, based on the total weight of the composition.
• the composition includes up to 10 wt%, up to 5 wt%, or up to 1 wt% of at least one of the amino-functional silane or cyclic azasilane, including any of those described above, based on the total weight of the composition. In embodiments that include solvent and/or water, any of these percentages can be based on the total weight of the solids in the composition (that is, excluding solvent and/or water).
• the provided composition can include polyorganosiloxanes other than the polyorganosiloxane described above. Other polyorganosiloxanes in the composition may or may not include reactive functional groups (e.g., hydrolyzable, vinyl, mercapto, amino, hydroxyl, or hydride functional groups).
• the polyorganosiloxane of the present disclosure is a first polyorganosiloxane and the oil component further includes a second polyorganosiloxane comprising divalent units represented by formula I, wherein each R is independently as defined above in any of its embodiments, wherein the second polyorganosiloxane does not include hydrolyzable groups.
• the second polyorganosiloxane may be a linear polyorganosiloxane consisting of divalent units represented by formula I and terminal - SiR 3 groups, wherein each R is independently as defined above in any of its embodiments. In some embodiments, each R is methyl.
• the second polyorganosiloxane is a polydimethylsiloxane having no reactive functional groups.
• the provided composition includes a third polyorganosiloxane comprising divalent units represented by formula I, wherein each R is independently as defined above in any of its embodiments, wherein the second polyorganosiloxane has at least one, in some embodiments, two -SiYpR3-p groups, wherein Y is a hydrolyzable group, R is as defined above in any of its embodiments, and p is 1, 2, or 3 (in some embodiments, 2 or 3, or 3).
• Suitable hydrolyzable groups include any of those described above for the polyorganosiloxane.
• each Y is independently alkoxy, aryloxy, or acyloxy. In some embodiments, each Y is independently alkoxy having up to ten carbon atoms. In some of these embodiments, each Y is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms. In some of these embodiments, each Y is independently methoxy or ethoxy.
• a third polyorganosiloxane can be combined with a polyorganosiloxane having at least three -SiY p R 3-p groups in ratios such that polyorganosiloxane composition overall still has an average of greater than two - SiY p R 3-p groups.
• second or third polyorganosiloxanes useful for the provided composition may be suitable for the second or third polyorganosiloxanes useful for the provided composition, depending upon, for example, the properties desired for the composition.
• second or third polyorganosiloxanes useful for practicing the present disclosure have a weight average molecular weight of 100 grams per mole to 100,000 grams per mole. If the composition includes at least one of the second or third polyorganosiloxane, in some embodiments, the provided composition includes at least 0.01 wt%, at least 0.1 wt%, or at least 1 wt% of at least one of the second or third polyorganosiloxane, including any of those described above, based on the total weight of the composition.
• the composition includes up to 10 wt%, up to 5 wt%, or up to 1 wt% of at least one of the second or third polyorganosiloxane, including any of those described above, based on the total weight of the composition. In embodiments that include solvent and/or water, any of these percentages can be based on the total weight of the solids in the composition (i.e., excluding solvent and/or water). In some embodiments, the composition does not include the second or third polyorganosiloxane. In some embodiments, the provided composition includes at least one additional silane having hydrolyzable functionality. The silane can be useful, for example, as a crosslinker and/or diluent.
• the provided composition includes a mixture of silanes having hydrolyzable functionality.
• the silane is represented by formula VII.
• R 3 f[SiX4-f]g [VII] wherein g is 1 to 6, f is 0, 1, or 2, with the proviso that when f is 0, g is 1;
• each R 3 is monovalent or multivalent, and is independently alkyl, aryl, or arylalkylenyl, wherein alkyl and arylalkylenyl are each uninterrupted or interrupted with at least one catenated - O-, -N(R 11 )-, -S-, -P-, -Si- or combination thereof, wherein aryl and arylalkylenyl are each unsubstituted or substituted by alkyl or alkoxy, and wherein alkyl, aryl, and arylalkylenyl are each unsubstituted or substituted with at least one epoxy, thi
• R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof.
• R 11 is hydrogen or alkyl, for example, having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, or sec-butyl).
• R 11 is methyl or hydrogen.
• Alkoxy and acyloxy are optionally substituted by halogen, and aryloxy is optionally substituted by halogen, alkyl (e.g., having up to 4 carbon atoms), or haloalkyl.
• alkoxy and acyloxy have up to 18 (or up to 12, 6, or 4) carbon atoms.
• aryloxy has 6 to 12 (or 6 to 10) carbon atoms.
• each X is independently selected from the group consisting of halide, hydroxyl, alkoxy, aryloxy, and acyloxy.
• each X is independently hydroxyl, alkoxy, amino, acetoxy, aryloxy, or halogen.
• each X is independently selected from the group consisting of halide (e.g., chloride), amino, and alkoxy having up to ten carbon atoms. In some of these embodiments, each X is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms. In some of these embodiments, each X is independently methoxy or ethoxy.
• halide e.g., chloride
• amino amino
• alkoxy having up to ten carbon atoms.
• each X is independently alkoxy having from 1 to 6 (e.g., 1 to 4) carbon atoms. In some of these embodiments, each X is independently methoxy or ethoxy.
• each X of formula VI is independently -OR 1 , wherein R 1 is hydrogen or a (C 1 -C 18 )alkyl, or - NR 1 R 2 (wherein each R 1 and R 2 is independently hydrogen or a (C 1 -C 18 )alkyl, in some embodiments, (C 1 -C 12 )alkyl, (C 1 -C 8 )alkyl, or (C 1 -C 4 )alkyl.
• each X is independently OR 1 (wherein R 1 hydrogen or a (C 1 -C 18 )alkyl), in some embodiments, (C 1 -C 12 )alkyl, (C 1 -C 8 )alkyl, or (C 1 -C 4 )alkyl.
• each R 1 is methyl.
• R 3 can include a straight chain, branched, or cyclic group, or a combination thereof.
• each R 3 independently includes 1 to 18, 1 to 12, 1 to 8, 1 to 6, or 2 to 6 carbon atoms.
• each R 3 is independently alkyl having 1 to 18, 1 to 12, 1 to 6, or 2 to 6 carbon atoms.
• each R 3 includes at least one catenated oxygen atom. In some embodiments, each R 3 is independently alkyl having at least one catenated oxygen atom. In some embodiments, each R 3 includes at least one epoxy, thiol, (meth)acrylate, vinyl, allyl, isocyanate, thiocyanate, ureido, or chloro group or a combination thereof. In some embodiments of formula VII, g is 1 or 2. In some embodiments, g is 1. In some embodiments of formula VII, f is 1.
• silanes represented by formula VII include methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, isooctyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, isobutyltrimethoxysilane, and tetraethyl orthosilicate.
• the silane in the composition is represented by formula VIII: L-[R 3b -SiX 3-f’ (R 3a ) f’ ] g’ [VIII]
• X is as defined above in any of its embodiments described in connection with formula VII.
• R 3a is monovalent alkyl, aryl, arylalkylenyl, wherein alkyl and arylalkylenyl are each uninterrupted or interrupted with at least one catenated -O-, - N(R 11 )-, -S-, -P-, -Si- or combination thereof, and wherein aryl and arylalkylenyl are each unsubstituted or substituted by alkyl or alkoxy.
• R 3b is divalent alkylene, arylene, or arylalkylene, wherein alkylene and arylalkylene are each uninterrupted or interrupted with at least one catenated -O-, -N(R 11 )-, -S-, -P-, -Si- or combination thereof, and wherein arylene and arylalkylene are each unsubstituted or substituted by alkyl or alkoxy.
• R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof.
• R 11 is hydrogen or alkyl, for example, having 1 to 4 carbon atoms (e.g., methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, or sec-butyl). In some embodiments, R 11 is methyl or hydrogen.
• L is epoxy, thiol, (meth)acrylate, vinyl, allyl, isocyanate, thiocyanate, ureido, or chloro.
• f’ is 0 or 1
• g’ is 1. In some embodiments, f’ is 0.
• R 3b is alkylene having 1 to 18, 1 to 12, 1 to 8, 1 to 6, or 2 to 6 carbon atoms and is uninterrupted or interrupted with at least one catenated -O- or -NR 11 - or combination thereof. In some embodiments, R 3b is alkylene having 2 to 6 carbon atoms. In some embodiments, the silane in the composition can be partially hydrolyzed and condensed. Such compounds may be represented by formula IX.
• each R 3c is independently monovalent alkyl, aryl, arylalkylenyl, wherein alkyl and arylalkylenyl are each uninterrupted or interrupted with at least one catenated -O-, -N(R 11 )-, -S-, -P-, -Si- or combination thereof, wherein aryl and arylalkylenyl are each unsubstituted or substituted by alkyl or alkoxy, and wherein alkyl, aryl, and arylalkylenyl are each unsubstituted or substituted with at least one epoxy, thiol, (meth)acrylate, vinyl, allyl, isocyanate, thiocyanate,
• R 11 is hydrogen, alkyl, aryl, or arylalkylenyl, wherein aryl and arylalkylenyl are unsubstituted or substituted by at least one alkyl, alkoxy, or combination thereof.
• R 11 is hydrogen or alkyl, for example, having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl).
• R 11 is methyl or hydrogen.
• each R 3c is independently alkylene having 1 to 18, 1 to 12, 1 to 6, or 2 to 6 carbon atoms and is uninterrupted or interrupted with at least one catenated -O- or -N(H)- or combination thereof. In some embodiments, each R 3c is independently alkylene having 2 to 6 carbon atoms. In some embodiments, the provided composition includes at least 0.01 wt%, at least 0.1 wt%, or at least 1 wt% of the at least one additional silane having hydrolyzable functionality, including any of those described above, based on the total weight of the composition.
• the composition includes up to 30 wt%, up to 25 wt%, or up to 15 wt% of at least one additional silane having hydrolyzable functionality, including any of those described above, based on the total weight of the composition. In embodiments that include solvent and/or water, any of these percentages can be based on the total weight of the solids in the composition (i.e., excluding solvent and/or water).
• the aqueous component of the present disclosure contains a polar counterpart that forms a stable water-based emulsion with the oil component.
• the provided composition enables a composition that can be cured using a water-soluble catalyst in a water-based composition.
• This water- composition is shelf-stable and yet can be conveniently cured upon demand without need for external application of heat or actinic radiation. Seemingly impossible, these technical benefits can be realized by disposing the water-soluble catalyst and blocking agent in the aqueous component.
• the blocking agent can evaporate in a controlled manner after application of the composition to a surface to be protected to activate the catalyst and cure the composition.
• This water-based catalyst can be capable of hydrolyzing the hydrolyzable groups in the polyorganosiloxane, amino-functional silane, cyclic azasilane, or any additional polyorganosiloxanes, such as an acid catalyst.
• Acid catalysts include, but are not limited to, phosphoric acid, phosphoric acid ethyl ester, monobutyl phosphate, mono-n-dodecyl phosphate, dibutyl phosphate, octylphosphonic acid, n-dodecyl phosphonic acid, phenylphosphonic acid, p-toluenesulfonic acid, 2-hydroxyethyl methacrylate phosphoric acid ester, bis-2-ethylhexyl phosphate, diphenyl phosphate, diphenyl phosphinic acidand combinations thereof.
• the acid catalyst is a phosphorus-based catalyst.
• phosphorus-based acids comprise acids of the formula (R 12 O) 2- p R 13 p P(O)OH where R 12 can be alkyl, aryl or H, R 13 can be alkyl, aryl and p ranges from 0 to 2.
• R 12 can be alkyl, aryl or H
• R 13 can be alkyl, aryl and p ranges from 0 to 2.
• the catalyst can be in a polymeric form wherein phosphorus is linked by P-O-P bonds or by P-O-alkylene-O-P bonds.
• the catalyst is more soluble in oil than in water as a neutral acid, and the formally charged conjugate base form is more soluble in water.
• the preference for a neutral catalyst to be dissolved in the aqueous phase vs. the oil phase can be estimated by the calculation of a partition coefficient between water and an immiscible solvent, such as octanol.
• the octanol/water partition coefficient is often represented as the log of the partition coefficient, and is referred to as Log P.
• the octanol/water partition coefficient can be calculated by software programs such as ACD ChemSketch, (Advanced Chemistry Development, Inc., Toronto, Canada) using the Log P module.
• the calculated Log P value of the neutral catalyst is greater than -2.15, -2.0, -1.5, -1.0, -0.5, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.75, 1 or 1.2.
• the calculated log P value is typically no greater than 12.5.
• the calculated log P value is no greater than 8, 7.5, 7, 6, 5, 4, 3, 2, 1.9, 1.8, 1.7.
• the provided composition includes at least 0.1 wt%, at least 0.01 wt%, or at least 0.001 wt% of a catalyst, including any of those described above, based on the total weight of the composition.
• the composition includes up to 5 wt%, up to 2.5 wt%, or up to 1 wt% of a catalyst, including any of those described above, based on the total weight of the composition. In embodiments that include solvent and/or water, any of these percentages can be based on the total weight of the solids in the composition (i.e., excluding solvent and/or water).
• the aqueous component contains a reversible blocking agent that can prevent premature activation of the catalyst and be removed after application to cure the monomeric components of the protectant composition.
• the blocking agent is, in a preferred embodiment, a base. In a preferred embodiment, the base is either a gas or a volatile liquid at ambient conditions.
• the base can have a boiling point from -60 degrees to 250 degrees Centigrade, from -40 degrees to 200 degrees Centigrade, from -40 degrees to 150 degrees Centigrade, or in some embodiments, less than, equal to, or greater than -60 degrees, -50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, or 250 degrees Centigrade.
• the inclusion of the blocking agent enables control over the chemical reactivity of the catalyst within the composition.
• the acid catalyst is an acid phosphate and the reversible blocking agent is ammonia.
• the acid phosphate exhibits catalytic activity only in its protonated form.
• ammonia a volatile base
• the ammonia remains in equilibrium with the acid phosphate, providing a stable emulsion.
• the provided composition was found to produce a rubbery, continuous film.
• the properties of the cured film was found to have properties comparable to those of control compositions that did not use blocking agents, showing that use of the volatile blocking agent did not impair performance properties of the product.
• performance properties can include hydrophobicity and scrub durability.
• the provided composition includes other components to impart particular desired properties.
• the composition can include conventional additives such as initiators, emulsifiers (including additional surfactants), stabilizers, antioxidants, flame retardants, adhesion promoters (for example, alkoxysilanes), release modifiers (for example, silicate resins including silicate MQ resin), colorants, thickeners (for example, carboxy methyl cellulose (CMC), polyvinylacrylamide, polypropylene oxide, polyethylene oxide/polypropylene oxide copolymers, polyalkenols), and combinations thereof.
• additives such as initiators, emulsifiers (including additional surfactants), stabilizers, antioxidants, flame retardants, adhesion promoters (for example, alkoxysilanes), release modifiers (for example, silicate resins including silicate MQ resin), colorants, thickeners (for example, carboxy methyl cellulose (CMC), polyvinylacrylamide, polypropylene oxide, polyethylene oxide/polypropylene oxide copolymers, polyalkenols
• the water is present in the composition in a range from 50 percent to 99 percent, from 55 percent to 95 percent, from 60 percent to 90 percent, or in some embodiments, less than, equal to, or greater than 50 percent, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99 percent by weight relative to the total weight of the composition.
• Water is useful both as a primary carrier component for the composition and hydrolysis of the silane groups.
• Suitable oil-in-water emulsions can include up to 99 wt%, up to 95 wt%, or up to 90 wt% water, based on the total weight of the composition.
• the composition includes at least 50 wt%, at least 60 wt%, or at least 75 wt% water, based on the total weight of the composition.
• Purified or deionized water may be useful.
• a wide variety of surfactants can be useful as emulsifiers in the provided emulsions.
• the emulsifier includes at least one of a nonionic surfactant or an anionic surfactant.
• the emulsifier includes a nonionic surfactant and optionally an anionic surfactant.
• Suitable nonionic surfactants include polyoxyethylene (POE) and polyoxypropylene (POP) aliphatic ethers having a linear or branched chain with 12 to 20 carbon atoms.
• the surfactant may include both POE and POP units in a random or block form.
• the surfactant may contain 1 to 100, 3 to 50, or 5 to 20 POE or POP units or a combination thereof.
• Suitable examples include POE (4 to 11) lauryl ether, POE (10 to 20) cetyl ether, POE (4 to 20) oleyl ether, POP (5) lauryl ether, POP (7) cetyl ether, POP (10) oleyl ether, and POE (3) POP (5) lauryl ether, wherein the numerical values in parentheses of POE and POP indicate the number of units of oxyethylene unit and oxypropylene unit.
• the nonionic surfactant is an alcohol ethoxylate, alcohol propoxylate, or combination thereof.
• non- ionic surfactants include products sold under the trade designations ECOSURF and TERGITOL (Dow Chemical Company, Midland, MI), MAKON and AMMONYX (Stepan Company, Northbrook, IL), SURFONIC (Huntsman Corporation, The Woodlands, TX), LUTENSOL and GLUCOPON (BASF SE, Ludwigshafen, Germany), TWEEN (Merck Group, Darmstadt, Germany), and SPAN (Croda International, Snaith, England).
• suitable anionic surfactants include sulfates of polyethoxylated derivatives of straight or branched chain aliphatic alcohols and carboxylic acids.
• the anionic surfactant can be the sulfate of any of the polyethoxylated derivatives of straight or branched chain aliphatic alcohols described above. Suitable surfactants are available from a variety of commercial sources.
• the surfactant comprises at least one of a five-mole ethoxylate of a linear, primary 12-14 carbon number alcohol available, for example, from Huntsman Corporation, The Woodlands, Tex., under the trade designation “SURFONIC L24-5”
• Surfactant an alcohol ethoxylate available, for example, from Dow Chemical Company under the trade designation “ECOSURF EH-6”, and a sodium salt of a fatty alcohol polyglycol ether sulphate, available, for example, from BASF Corporation, Florham Park, N.J., under the trade designation “DISPONIL FES 32IS”.
• the emulsion composition can include up to 35 wt%, up to 20%, up to 8 wt%, or in some embodiments, less than, equal to, or greater than 8 wt%, 10, 15, 20, 25, 30, or 35 wt% of a surfactant, including any of those described above, based on the total weight of the emulsion. In some embodiments, the emulsion composition includes at least 0.50 wt% or at least 1 wt% of a surfactant, including any of those described above, based on the total weight of the emulsion.
• the emulsion composition can include up to 90 wt%, up to 50 wt%, up to 8 wt%, or in some embodiments, less than, equal to, or greater than 8 wt%, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt% of reactive ingredients, including the polyorganosiloxane, the amino-functional silane, the silane having at least one hydrolyzable group, and the catalyst as described above in any of their embodiments, based on the total weight of the emulsion.
• the surfactant is a nonionic surfactant having a hydrophilic- lipophilic balance (HLB) value within a particular range.
• HLB hydrophilic- lipophilic balance
• Non-ionic surfactants are organic compounds that are amphiphilic, comprising a hydrophobic group (or “tail”) and a hydrophilic group (or “head”).
• a surfactant can be classified by the presence of formally charged groups in its head.
• the head of an ionic surfactant carries a net charge, while a non-ionic surfactant has no charged groups in its head.
• Surfactants can be characterized by various methodologies. One common characterization method is based on HLB.
• HLB refers to the value obtained by Griffin’s method (see Griffin WC, “Calculation of HLB Values of Non-Ionic Surfactants,” Journal of the Society of Cosmetic Chemists 5:259 (1954)). According to Griffin’s method, for fatty alcohol ethylene oxide condensation products, HLB is approximately E/5, where E is the weight percentage of oxyethylene content. This computation provides a numerical result on an HLB scale of 0 to 20, where “0” means highly lipophilic. This method can also be applied to other surfactants, such as silicone or siloxane condensation or addition products with polyethylene oxide.
• This method can be applied to silicone surfactants if there is no greater than one propylene oxide group per molecule.
• Some surfactants have a more complex structure where Griffin’s method does not accurately predict behavior related to composition. Such cases include where an average of more than one repeat unit of propylene oxide or butylene oxide per molecule are present, or when nitrogen, sulfur or charged groups are present in the molecule. In these cases, and in other cases where Griffin’s method cannot be utilized to determine an HLB value, computations can be conducted utilizing the software program Molecular Modeling Pro Plus from Norgwyn Montgomery Software, Inc. (North Wales, PA) to estimate the HLB value of a particular molecule. Computation methods are typically used to calculate the HLB of a single molecule.
• non-ionic surfactants comprise a mixture of molecules.
• the HLB can be calculated by the summation of the HLBs of the individual molecules multiplied by the number fraction of each molecule.
• the relative concentrations of individual molecules can be determined by various analytical techniques, such as mass spectrometry, liquid chromatography, NMR, other techniques or combinations of techniques.
• HLB refers to the HLB based on the number average molecular weight, as determined using mass spectrometry.
• the HLB of the non-ionic surfactant is greater than 8, 9, 9.5, 10, 10.5, or 11.
• the HLB of the non-ionic surfactant is less than 16.5, 16, 15.5, 15, or 14.5.
• the provided composition can be free of fluorinated silanes, for example, having a structure represented by formula R f -Q-SiY p R 3-p or Y p R 3-p Si-Q-R f -Q-SiY p R 3-p , wherein R f is a monovalent or divalent fluoroalkyl group or a perfluoropolyether group, and Q, Y, R, and p are as defined above in any of their emboidments.
• the composition is substantially free of these fluorinated silanes (that is, it has less than 1, 0.5, 0.1, or 0.05% by weight fluorinated silane, based on the total weight of the composition).
• the provided composition can be prepared by combining the various components, in some embodiments, with agitation or stirring. Shelf life of the emulsion can be maximized by storing it sealed at room temperature in a container with minimal headspace and avoiding exposing it to ambient air.
• the emulsion is preferably stable (i.e., resists phase separation) over a long period of time under ambient conditions. For example, the emulsion can be stable over a period of at least 6 months, at least 1 year, at least 2 years, at least 3 years, or even longer.
• the provided compositions remain stable—for example, the provided compositions show no precipitate formation even when heated to 45 ⁇ C for at least 2 weeks, 3 weeks, 4 weeks, 6 weeks, or even more than 8 weeks.
• a variety of methods may be useful for applying the composition.
• a small amount of coating composition can be applied to the surface to be treated. For example, approximately 6 drops/ft 2 (i.e., 65 drops/m 2 ) may be used, depending on the condition of the surface being treated (weathered or deteriorated surfaces may benefit from using a larger amount of the coating composition).
• the composition may be applied to a surface either directly using a variety of techniques (e.g., spraying, such as using a spray trigger mechanism), or the composition may be first applied to a spreading device (e.g., a cloth) and then applied to a surface.
• a spreading device e.g., a cloth
• the coating compositions may be evenly distributed on a surface by hand-wiping with a clean, dry cloth or pad (e.g., a suede or microfiber cloth, a foam pad, or a combination thereof) using, for example, overlapping circular strokes.
• the composition is applied onto the surface and allowed to remain on the surface for a period of from 0.5 minutes to 1 week, or in some embodiments, less than, equal to, or greater than 0.5 minutes, 1, 2, 5, 10, 20, 30, 60 minutes, 2 hours, 3, 6, 12, 24 hours, 2 days, 3, 4, 5, 6, or 7 days. From there, excess composition may be wiped off, and the base and water within the composition allowed to evaporate to activate the catalyst to cure the coated composition. Having an extended amount of time elapse between application and removal from the substrate may occur inadvertently as a result of user technique, and advantageously can be tolerated with the provided protectant compositions. In some embodiments, the composition can be applied more than once.
• the composition is allowed or induced to cure for 30 seconds to 30 minutes before the excess is wiped off.
• cure conditions of 70°F ⁇ 5°F (21.1°C ⁇ 2.8°C) and 50% ⁇ 3% relative humidity are used. Shorter or longer curing times may be used if desired by the user.
• the composition may then be allowed to cure for up to 10 days, 7 days, 3 days, 5 days, one day, or one hour at 70°F ⁇ 5°F (21.1°C ⁇ 2.8°C) and 50% ⁇ 3% relative humidity.
• multiple coats are applied, allowing sufficient time for each coat to cure.
• the composition provides a clear, streak-free, and in some cases, a glass-like, finish on the coated article.
• the composition provides excellent water-beading on substrate surfaces, encouraging a large number of well-rounded, hemispherical water drops to form or “bead up.”
• these drops often easily roll off the car, carrying and dirt or debris with them.
• compositions described herein may promote faster drying and a self-cleaning property of a surface that subsequently becomes wet.
• the composition facilitates the release of water from surfaces.
• Water applied to such a surface for example, from precipitation or rinse water used to wash and clean a substrate surface
• the composition typically provides sufficient durability to maintain acceptable performance and a desired appearance even after the coated surface has been subjected to repeated washing and rinsing cycles.
• a motor vehicle panel that has been treated according to some embodiments of the present disclosure may still promote excellent water-beading, encouraging a large number of small, well-rounded, hemispherical water drops to form or “bead up” even after more than 100 back-and-forth wiping motions (cycles) with a soft foam pad that has been saturated with a 9% aqueous automotive shampoo solution, or more than 200 cycles, or more than 250 cycles.
• the substrate of the article of the present disclosure and/or made by the method disclosed herein includes glass, plastic, rubber, wood, gelcoat, leather, fiberglass, fabric, metal, a painted surface, a polymeric film, or a combination thereof. In some embodiments, the substrate is transparent.
• Plastics useful as a substrate include polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), polycarbonate, and mixtures thereof. Carbon and graphite fibers and other materials can be useful as reinforcing agents in plastic composites. Both ferrous and nonferrous metal surfaces useful as a substrate in the method and article of the present disclosure. Examples of useful metals include aluminum, brass, bronze, chrome, copper, tin, zinc, iron, stainless steel and steel. Painted metal substrates and bare metal substrates may be useful substrates, depending on the desired application. Polymeric films useful as substrates in the article and method of the present disclosure include car wrap films.
• Table 1 Materials Designation Description
• Source Organosiloxane 1 Tri-functional alkoxysilane modified Siltech Corporation, polyorganosilane available under the Toronto, Ontario, Canada designation SILMER TMS C50 Organosiloxane 2 Hydroxylalkyl modified silicone Siltech Corporation available under the designation SILMER OH di-10 Organosiloxane 3 Di-functional silicone prepolymer with Siltech Corporation reactive hydroxyl terminal end groups available under the designation SILMER OH di-50 Organosiloxane 4 Alkoxysilyl oligomer available under Shin-Etsu Silicones of the designation SHINETSU X-40-9225 America, Inc., Akron, OH, United States Organosiloxane 5 Alkoxysilyl oligomer available under Shin-Etsu Silicones of the designation SHINETSU X-40-9250 America, Inc.
• Non-ionic surfactant available under Vitech the designation ECOSURF EH-6 and Company, Midland, MI, having a hydrophilic-lipophilic balance United States
• This Norwalk, CT, United mixture contains a portion of dibutyl States phosphate.
• Emulsion pre-blends (Pre-Blend 1 – Pre-Blend 12) were made by mixing quantities, as represented in Table 2, of a first (1 st ) surfactant and a second (2 nd ) surfactant (if included) with an initial quantity of water (Initial Water) until they were completely solubilized. Quantities of Organosilane (as represented in Table 2) and Silane (if included) were slowly added to the surfactant and water mixture under high shear to emulsify. The Pre-Blends were further diluted (Water Dilution) to create 10% concentrated samples.
• a magnetic stir bar was then added.
• the pH of the mixture was monitored using a SYMPHONY brand P10P Benchtop Electrochemical Meter (from VWR of Radnor, PA, United States) with a pH probe.
• An approximately 20% solution of concentrated ammonium hydroxide solution (identified in Table 3) in water or neat base was added dropwise to the jar under stirring until a final solution pH of 6.5 was obtained (Exception: when using the base pyridine, the pH was only raised to 5.6 due to the low basicity of pyridine). 50.0 g of the emulsion Pre-Blend was then added to the mixture.
• Table 3 Sample Composition and Cure Status Test Results ) ) s d s P C y n t s u t g ° ( a e l y e a t o P D ( B l - a s a S e t r a B e L .

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