Oleophobic and Hydrophobic Composition

Abstract

The invention pertains generally to providing an increased amount of both hydrophobicity and oleophobicity by the combination of at least one silane and at least one siloxane, the silane preferably being a trialkoxysilane of Formula (I) and at least one polysiloxane of Formula (II), the combined composition of silane and polysiloxane having no added perfluorinated compounds. The invention further includes an ability to darken the color of the surface to which it is applied by at least 5, preferably 10 “L” units, giving the surface more of a “wet” look.

Claims

1. A composition comprising: 30-90% of a trialkoxysilane of Formula (I); ##STR00118## wherein R.sub.1 of Formula (I) is selected from the group consisting of linear, cyclic or branched C.sub.12-30 alkyl, C.sub.12-30 alkenyl and C.sub.12-30 alkylaryl groups; and wherein R.sub.2, R.sub.3 and R.sub.4 of Formula (I) are selected independently from the group consisting of linear, cyclic or branched C.sub.1-6 alkyl, C.sub.1-6 alkenyl, C.sub.1-6 isoalkenyl, and C.sub.3-12 oxime forming groups; and 10-70% of a polysiloxane of Formula (II) ##STR00119## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5and R.sub.6 of Formula (II) are selected independently from the group consisting of H, OH, linear, cyclic or branched C.sub.1-18 alkyl, C.sub.1-6 alkenyl, C.sub.1-6 alkoxy, C.sub.1-6 aminoalkyl, C.sub.1-12 vinyl alkyl; C.sub.6-18 aryl, C.sub.3-18 epoxy-forming groups and di(C.sub.1-6 alkyl)hydrogensilyl; wherein A is independently O or C.sub.1-6 alkyl; wherein B is independently Si(R.sub.1)(R.sub.2) or R.sub.1; wherein x.sub.1ranges from 1 to 3000 inclusive; wherein x.sub.2ranges from 0 to 500 inclusive; wherein x.sub.3 is either 0 or 1; wherein x.sub.4 is either 0 or 1; wherein x.sub.5 is either 0 or 1; wherein x.sub.6 is either 0 or 1; a catalyst; and wherein the composition having no added perfluorinated compounds and the weight percentages of all added components above totalling 100%.

2. The composition according to claim 1 wherein the silane composition of Formula (I) is a methoxy or ethoxy-silane.

3. The composition according to claim 1 wherein the polysiloxane of Formula (II) is a polydimethylsiloxane.

4. The composition according to claim 1 wherein the polysiloxane of Formula (II) is a silanol terminated polydimethylsiloxane.

5. The composition according to claim 1 which further comprises: a catalyst.

6. The composition of according to claim 5 wherein the catalyst is selected from the group consisting of KOH, NaOH, HCl, C.sub.1-16 alkylbenzenesulfonic acids, a C.sub.1-6 trialkoxy silanes, a C.sub.1-12 alkylamines, C.sub.1-12 alkanoic acids, C.sub.1-12 alkanol, organotin compounds, organotitanate compounds and organozirconate compounds.

7. The composition of claim 5 which further comprises: at least one additional component selected from the group consisting of a solvent, a pigment or dye, a thickener, a fungicide, a bactericide and an organic or an inorganic pigment.

8. The composition according to claim 1 which is an emulsion.

9. A composition according to claim 1 which is synthesized by: mixing at least 30-90 wt. % of at least one silane of Formula (I) and at least one catalyst; ##STR00120## wherein R.sub.1 of Formula (I) is selected from the group consisting of linear, cyclic or branched C.sub.12-30 alkyl, C.sub.12-30 alkenyl and C.sub.12-30 alkylaryl groups; and wherein R.sub.2, R.sub.3 and R.sub.4 of Formula (I) are selected independently from the group consisting of linear, cyclic or branched C.sub.1-6 alkyl, C.sub.1-6 alkenyl, C.sub.1-6 isoalkenyl, and C.sub.3-12 oxime forming groups; and adding between 10-70 wt. % of at least one polysiloxane of Formula (II) to Formula (I) within 1 hour before application to a surface wherein Formula (II) is ##STR00121## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 Formula (II) are selected independently from the group consisting of H, OH, linear, cyclic or branched C.sub.1-18 alkyl, C.sub.1-6 alkenyl, C.sub.1-8 alkoxy, C.sub.1-6 aminoalkyl, C.sub.1-12 vinyl alkyl; C.sub.6-18 aryl, C.sub.3-18 epoxy-forming groups and di(C.sub.1-6 alkyl)hydrogensilyl; wherein A is independently O or C.sub.1-6 alkyl; wherein B is independently Si(R.sub.1)(R.sub.2) or R.sub.1; wherein x.sub.1 ranges from 1 to 3000 inclusive; wherein x.sub.2 ranges from 0 to 500 inclusive; wherein x.sub.3 is either 0 or 1; wherein x.sub.4 is either 0 or 1; wherein x.sub.5 is either 0 or 1; wherein x6 is either 0 or 1; a catalyst; and wherein the composition having no added perfluorinated compounds and the weight percentages of all added components above totalling 100%.

10. The process of claim 9 wherein the surface or substrate is selected from the group consisting of a porous mineral building material comprising natural stone, artificial stone and a cementitious material.

11. The process of claim 9 wherein the surface or substrate is selected from the group consisting of wood, paper and cardboard.

12. The process of claim 9 wherein the surface or substrate is selected from the group consisting of a leather, a textile and nonwoven.

13. The process of claim 9 wherein the surface or substrate becomes water resistant and olephobic.

14. The process of claim 9 wherein the surface or substrate permanently, or semi-permanently changes from a first color to a second darker color in appearance after application with the second color having a L value of at least equal to or greater than 5 units lower than the first color.

15. The process of claim 14 wherein the surface or substrate permanently, or semi-permanently changes from a first color to a second darker color in appearance after application with the second color having a L value of at least equal to or greater than 10 units lower than the first color.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0049] The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time of the filing of this invention. The examples and figures are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.

[0050] Unless the context clearly indicates otherwise: the word “and” indicates the conjunctive; the word “or” indicates the disjunctive; when the article is phrased in the disjunctive, followed by the words “or both” or “combinations thereof” both the conjunctive and disjunctive are intended.

[0051] As used in this application, the term “approximately” is within 10% of the stated value, except where noted.

[0052] As used in this application, “oleophobic” is defined as preventing the penetration and wetting of a nonpolar liquid at ambient temperature and as used in this application, “oil” is defined as a liquid substance that is both hydrophobic and lipophilic.

[0053] As used herein, the term “flexible” materials mean a woven or non-woven network of natural or artificial fibers.

[0054] As used herein, the term “water-resistant” means a reduction in water absorption into a substrate compared to an untreated control in which water absorption is reduced by at least 50% in a 1 hour soak test

[0055] Colors can be quantified using the L, a, b values approach. As used herein, when discussing the color change of the surface of the substrate permanently, or semi-permanently from a first color to a second darker color in appearance after application is meant that the L value of the second color is at least 5 units lower, preferably at least 10 units lower compared to the L value of the first color. A L value of 100 means white and a L value of 0 means black. When the L value is reduced by e.g. by 5, this is determined to be an enhancement.

[0056] As used herein, and unless otherwise stated, the term “alkylaryl” refers to an aryl group (such as defined above) onto which an aliphatic saturated hydrocarbon monovalent group is attached, and wherein the said aliphatic or aryl groups may be optionally substituted with one or more substituents independently selected from the group consisting of chlorine and bromine, amino, hydroxyl, sulfhydryl, alkyl, and nitro. Specific non-limiting examples of the unsubstituted or alkyl-substituted aryl groups are the aryl groups having 6 to 18 carbon atoms such as phenyl, diphenyl and naphthyl groups, and alkylaryl groups having 7 to 40 carbon atoms wherein the alkyl group may be straight-chain or branched and may be bonded to any position on the aryl group, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, diethylphenyl, dibutylphenyl and dioctylphenyl groups. The alkylaryl groups may additionally have substituents Including functional groups such as alkoxy, hydroxy, cyano, nitro, halides, carboxylic acids, etc.

[0057] Organo-functional silanes find their use in a variety of applications e.g. as coupling agents. The class of silanes useful for the invention are alkylsilanes with three hydrolysable groups (e.g., alkytrialkoxysilanes) of the following type illustrated in Formula (I);

##STR00005## [0058] wherein R.sub.1 of Formula (I) is selected from the group consisting of linear, cyclic or branched C.sub.12-30 alkyl, C.sub.12-30 alkenyl and C.sub.12-30 alkylaryl groups (e.g., alkyl benzyl) groups; and [0059] wherein R.sub.2, R.sub.3 and R.sub.4 of Formula (I) are selected independently from the group consisting of linear, cyclic or branched C.sub.1-6 alkyl, C.sub.1-6 alkenyl, C.sub.1-5 isoalkenyl, e.g., methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, phenyl, acetyl, e.g., iso-propene (—C(═CH.sub.2)(—CH.sub.3) (which forms acetone as leaving group) or propenoxy in addition to C.sub.3-12 oxime-forming groups as —N═C(—CH.sub.3)(—CH.sub.2CH.sub.3).

[0060] In addition to Formula (I), a silane a polymer of the following structure is required of the type illustrated in Formula (II)

##STR00006## [0061] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and Roof Formula (II) are selected independently from the group consisting of H, OH, linear, cyclic or branched C.sub.1-18 alkyl, C.sub.1-6 alkenyl, (e.g., methyl, ethyl, n-propyl, isopropyl, phenyl), C.sub.1-6 alkoxy, C.sub.1-6 aminoalkyl, (e.g., aminoethyl (—(CH.sub.2).sub.2—NH.sub.2), aminopropyl (—(CH.sub.2).sub.3—NH.sub.2), or aminoethylaminopropyl (—(CH.sub.2).sub.3—NH—(CH.sub.2).sub.2—NH.sub.2); C.sub.1-12 vinyl alkyl (e.g., R.sub.y—CH═CH.sub.2 with R.sub.y═C.sub.1-10 alkyl groups); C.sub.6-18 aryl and C.sub.3-18 epoxy-forming groups (e.g., R.sub.z—COCH.sub.2 with R.sub.z═C.sub.1-10 alkyl groups); and di(C.sub.1-6 alkyl)hydrogensilyl (e.g., dimethylhydrogensilyl); [0062] wherein A is independently O or C.sub.1-6 alkyl; [0063] wherein B is independently Si(R.sub.1)(R.sub.2) or R.sub.1; [0064] wherein x.sub.1 ranges from 1 to 3000 inclusive, which equates to a viscosity of up to ˜200000 mPas, as higher viscosities are not useful for the application; [0065] wherein x.sub.2 ranges from 0 to 500 inclusive; [0066] wherein x.sub.3 is either 0 or 1; [0067] wherein x.sub.4 is either 0 or 1; [0068] wherein x.sub.5 is either 0 or 1; [0069] wherein x.sub.6 is either 0 or 1; [0070] a catalyst; and [0071] wherein the composition having no added perfluorinated compounds and the weight percentages of all added components above totalling 100%.

[0072] The polysiloxane can contain some branching of up to 3% (mol. % Si) of so-called silicone T or Q-units as described in Encyclopaedia of Polymer Science and Technology, Vol. 11, Silicones wherein the M unit═R.sub.3-Si-0—, the D unit ═R.sub.2—Si—O.sub.2—; and the T unit═R-Si—O.sub.3—; Q unit ═Si—O.sub.4—. Siloxane copolymers may be described according to their macrostructure, i.e. how the M, D, T and Q units are combined in the polymer. Several classes of copolymer can be recognized.

##STR00007##

[0073] The polysiloxane may contain some linear chain polysiloxanes (MDnM). These comprise linear polymers where M and D units may be replaced by MX, MX, Y, MX, Y, Z and by DX, DX, Y units respectively. Several combinations of these units will generate telechelic and chain-functionalized linear copolymers. Since almost any organic or inorganic group can be attached to the siloxane backbone, such copolymers exhibit a wide range of interesting properties and are used in many applications.

[0074] The polysiloxane may also contain branched chain polysiloxanes. These are linear chains containing T, TX or Q units as branching centres.

[0075] The polysiloxane may further contain cyclic polysiloxanes. Various combinations of D and T units can generate macrocyclics that may be classified into four subgroups, viz. monocyclic, polycyclic, spirocyclic and spherocyclic polysiloxanes. The three latter groups can be interpreted as arising from a cross-linking of monocyclic ring systems.

[0076] And lastly, the polysiloxane may contain cross-linked polysiloxanes. These molecular structures are three-dimensional networks where T and/or Q units are combined with D and/or M units. A variety of polymers of complex structures are thus produced such as ladder-structured polymers and silicone resins

[0077] Preferably R.sub.1, R.sub.2, R.sub.3 are methyl groups, R.sub.4 is a phenyl group, x.sub.1>x.sub.2 and R.sub.5 and R.sub.6 are hydrogen atoms. Most preferred R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are methyl groups and R.sub.5 and R.sub.6 are hydrogen atoms and A being a oxygen atom.

[0078] Optionally a catalyst is used in order to accelerate the hydrolysis and condensation reactions of the ingredients. The catalyst can be selected but is not limited to the following types: Acids, bases (including Lewis acids and bases) and metal organic compounds known to be catalytic active for alkoxy-silane hydrolysis, exchange and condensation reactions can be used. A non-limiting and exemplary listing of catalysts applicable to this invention include, but are not limited to: KOH, NaOH, HCl, DBSA (p-dodecylbenzenesulfonic acid which is a Brønsted acid surfactant-combined catalyst, composed of a polar head and a long non-polar chain, organotin compounds as DBTDL (dibutyltin dilaurate) or DMTDN (dimethyl tin dineodecanoate), titanates (e.g., tetra n-butyl titanate). Additional suitable condensation catalysts may be used, a non-limiting exemplary list may include condensation catalysts incorporating tin, lead, antimony, Iron, cadmium, barium, manganese, zinc, chromium, cobalt, nickel, aluminum, gallium germanium, titanium and zirconium. Examples include metal triflates. Useful organotin compounds are those where the valence of the tin is either +2 or +4. These tin compounds are known in the art to promote the reaction between alkoxy groups substituted on silicon and hydroxyl groups substituted on silicon. Typical tin compounds useful as condensation catalysts include stannous salts of carboxylic acids such as stannous stearate, stannous oleate, stannous naphthanate, stannous hexoate, stannous succinate, stannous caprylate, and stannous octoate; and stannic salts of carboxylic acids, such as dibutyltindilaurate, dibutyltindiacetate, dibutyltindioctoate, dibutyltindiformate, and dibutyltindineodecanoate, as well as partial hydrolysis products of the above. Organic tin metal catalysts such as triethyltin tartrate, tin octoate, tin oleate, tin naphthate, butyltintri-2-ethylhexoate, tinbutyrate, carbomethoxyphenyl tin trisuberate, isobutyltintriceroate, and diorganotin salts especially diorganotin dicarboxylate compounds such as dibutyltin dilaurate, dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate, dimethyltin bisneodecanoate, dibutyltin dibenzoate, stannous octoate, dimethyltin dineodeconoate, dibutyltin dioctoate of which dibutyltin dilaurate, dibutyltin diacetate, dibutyltindiacetylacetonate and dibutyltindimethoxylate are particularly preferred.

[0079] Zirconates (e.g., tetra n-butyl zirconate) are also applicable catalysts, an exemplary non-limiting list may include titanate and/or zirconate based catalysts according to the general formula Ti[OR.sub.5].sub.4 and Zr[OR.sup.5].sub.4 respectively where each R.sup.5 may be the same or different and represents a monovalent, primary, secondary or tertiary aliphatic hydrocarbon group which may be linear or branched containing from 1 to 10 carbon atoms. Optionally the titanate may contain partially unsaturated groups. However, preferred examples of R.sup.5 include but are not restricted to methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and a branched secondary alkyl group such as 2,4-dimethyl-3-pentyl. Preferably, when each R.sup.5 is the same, R.sup.5 is an isopropyl, branched secondary alkyl group or a tertiary alkyl group, in particular, tertiary butyl.

[0080] Alternatively, the titanate may be chelated. The chelation may be with any suitable chelating agent such as an alkyl acetylacetonate such as methyl or ethylacetylacetonate. Any suitable chelated titanates or zirconates may be utilised. Preferably the chelate group used is a monoketoester such as acetylacetonate and alkylacetoacetonate giving chelated titanates such as, for example diisopropyl bis(acetylacetonyl)titanate, diisopropyl bis(ethylacetoacetonyl)titanate, diisopropoxytitanium Bis(Ethylacetoacetate) and the like. Examples of suitable catalysts are additionally described in EP1254192 and WO200149774 which catalysts are incorporated herein by reference.

[0081] The invention will now be described by a series of examples. Mixtures were prepared by adding the ingredients to glass bottles and homogenising them on a roll mixer. All ingredients are commercially available and were used without further purification. All silanes, titanate, zirconate, DBTDL and PDMS silanols were obtained from ABCR GmbH; KOH, Methanol and CaCOa, were obtained from Carl Roth GmbH; Octoanic acid and dodecylbenzene sulfonic acid was obtained from Sigma Aldrich Germany, phenyl, vinyl, terminal hydrogen and ethoxy containing polymers were obtained from Gelest Inc; dimethyltin dineodecanoate was obtained from Momentive,; polymethylhydrogensiloxane was obtained from Dow Chemical. The different mixtures where applied to a concrete paver and a terracotta type bricks by means of a brush and then allowed to cure for at least 1 week at ambient temperature (23° C. and ˜60% RH). The application rate was 250 g/m.sup.2 unless indicated otherwise.

[0082] Oil repellence was tested by applying 3 drops of olive oil on the substrates. If the oil drops were still present after 1 hour the formulation was rated as oil repellent. If 1 or more drops were absorbed into the substrate the formulation was rated as non-oil repellent.

[0083] A series of examples were prepared in the ratios (weight percent) and using the components identified in Table I.

TABLE-US-00001 TABLE I (all percentages are in weight percent, the combination of components totalling 100 wt. %) Oil Oil repel- repel- lent lent Siloxane on on Ex Silane (cSt = centistokes) Catalyst brick paver 1 90% hexadecyl 9.9% PDMS silanol 0.1% dimethyltin yes yes trimethoxysilane 65 cSt dineodecanoate [00008] [00009] [00010] 2 80% hexadecyl 19.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 65 cSt dineodecanoate tested tested for for [00011] [00012] [00013] 125, 250 and 500 g/m.sup.2 125, 250 and 500 g/m.sup.2 3 70% hexadecyl 29.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 65 cSt dineodecanoate [00014] [00015] [00016] 4 60% hexadecyl 99.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 65 cSt dineodecanoate [00017] [00018] [00019] 5 80% hexadecyl 19.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 65 cSt dineodecanoate [00020] [00021] [00022] 6 80% hexadecyl 17% PDMS 3% aminopropyltriethoxysilane yes no trimethoxysilane silanol 65 cSt C.sub.2H.sub.5O—Si—(CH.sub.2).sub.3NH.sub.2 [00023] [00024] 7 80% hexadecyl 19.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 65 cSt dineodecanoate [00025] [00026] [00027] 8 80% hexadecyl 19.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 25 cSt dineodecanoate [00028] [00029] [00030] 9 80% hexadecyl 19.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 2000 cSt dineodecanoate [00031] [00032] [00033] 10  80% hexadecyl 19.9% PDMS 0.1% dimethyltin yes yes trimethoxysilane silanol 50000 cSt dineodecanoate [00034] [00035] [00036] 11  80% 19.9% AminoethylaminopropylMethoxysiloxane 0.1% yes yes hexadecyl dimethylsiloxane copolymer dimethyltin trimethoxysilane (2-4 mol % amino, 200-300 cst) dineodecanoate [00037] [00038] [00039] 17  80% hexadecyl 19.9% PDMS 1% tetra n-butyl titanate yes yes trimethoxysilane silanol 65 cSt Ti(OC.sub.4H.sub.9).sub.4 [00040] [00041] 18  70% hexadecyl 29.0% PDMS 1% tetra n-butyl titanate yes yes trimethoxysilane silanol 65 cSt Ti(OC.sub.4H.sub.9).sub.4 [00042] [00043] 19  78% n-octadecyl 19.0% PDMS 3% tetra n-propylzirconate (70% yes no trimethoxysilane silanol 65 cSt in n-propanol) Zr(OC.sub.3H.sub.7).sub.4 [00044] [00045] 20  80% hexadecyl 19.0% PDMS 1% n-octoanic acid yes no trimethoxysilane silanol 65 cSt CH.sub.3(CH.sub.2).sub.6COOH [00046] [00047] 21  70% hexadecyl 27% PDMS 3% 3-aminopropyltriethoxysilane yes no trimethoxysilane silanol 65 cSt C.sub.2H.sub.5O—Si—(CH.sub.2).sub.3NH.sub.2 (6 weeks [00048] [00049] cure) 22  70% hexadecyl 27% PDMS 3% N-(2-aminoethyl)-3- yes yes trimethoxysilane silanol 65 cSt aminopropyltrimethoxysilane (6 N-(3-(Trimethoxysilyl)propyl) weeks [00050] [00051] ethylene diamine (CH.sub.3O)Si(CH.sub.2).sub.3NHCH.sub.2CH.sub.2NH.sub.2 cure) 23  80% hexadecyl 19% PDMS 1% KOH in Methanol yes no trimethoxysilane silanol 65 cSt (10% wt) (500 g/m.sup.2 [00052] [00053] ap- plied) 24a 80% hexadecyl 19.8% triethoxysilylethyl terminated 0.2% dimethyltin yes no trimethoxysilane polydimethylsiloxane 8-12 cSt dineodecanoate [00054] [00055] [00056] 24b 70% hexadecyl 29.9% triethoxysilylethyl terminated 0.2% dimethyltin yes yes trimethoxysilane polydimethylsiloxane 8-12 cSt dineodecanoate [00057] [00058] [00059] 24c 80% hexadecyl 19% triethoxysilylethyl terminated 1% DBTDL (di-n-butyltindilaurate) yes no trimethoxysilane polydimethylsiloxane 8-12 cSt (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 [00060] [00061] 24d 70% n-octadecyl 29% triethoxysilylethyl terminated 1% DBTDL (di-n-butyltindilaurate) yes yes trimethoxysilane polydimethylsiloxane 8-12 cSt (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 [00062] [00063] 25a 80% hexadecyl 19.8% hydride terminated 0.2% dimethyltin yes no trimethoxysilane polydimethylsiloxane, 7-10 cSt dineodecanoate [00064] [00065] [00066] 25b 70% hexadecyl 29.7% hydride terminated 0.3% dimethyltin yes no trimethoxysilane polydimethylsiloxane, 7-10 cSt dineodecanoate [00067] [00068] [00069] 25c 80% hexadecyl 19% hydride terminated polydimethylsiloxane, 1% DBTDL (di-n-butyltindilaurate) yes no trimethoxysilane 7-10 cSt (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 [00070] [00071] 25d 70% n-octadecyl 29% hydride terminated polydimethylsiloxane, 1% DBTDL (di-n-butyltindilaurate) yes no trimethoxysilane 7-10 cSt (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 [00072] [00073] 26a 80% 19.8% silanol terminated (14-18% diphenylsiloxane) − 0.2% yes no hexadecyl dimethylsiloxane) − copolymer 50-60 cSt (95:5 mole ratio dimethyltin trimethoxysilane of dimethylsiloxane:diphenylsiloxane) dineodecanoate [00074] [00075] [00076] 26b 70% 29.6% silanol terminated (14-18% diphenylsiloxane) − 0.4% yes no hexadecyl dimethylsiloxane) − copolymer 50-60 cSt (95:5 mole ratio dimethyltin trimethoxysilane of dimethylsiloxane:diphenylsiloxane) dineodecanoate [00077] [00078] [00079] 26c 80% 19% silanol terminated (14-18% diphenylsiloxane) − 1% DBTDL (di-n-butyltindilaurate) yes yes hexadecyl dimethylsiloxane) − copolymer 50-60 cSt (95:5 mole ratio (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 trimethoxysilane of dimethylsiloxane:diphenylsiloxane) [00080] [00081] 26d 70% n- 29% silanol terminated (14-18% diphenylsiloxane) − 1% DBTDL (di-n-butyltindilaurate) yes no octadecyl dimethylsiloxane) − copolymer 50-60 cSt (95:5 mole ratio (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 trimethoxysilane of dimethylsiloxane:diphenylsiloxane) [00082] [00083] 27a 80% 19.75% (10-15% vinylmethylsiloxane) − 0.25% yes no hexadecyl dimethylsiloxane copolymer, silanol dimethyltin trimethoxysilane terminated, 25-40 cSt dineodecanoate [00084] [00085] [00086] 27b 80% 19.75% (10-15% vinylmethylsiloxane) − 0.25% no yes hexadecyl dimethylsiloxane copolymer, silanol dimethyltin trimethoxysilane terminated, 25-40 cSt dineodecanoate [00087] [00088] [00089] 27c 80% n- 19% (10-15% vinylmethylsiloxane) − 1% DBTDL (di-n-butyltindilaurate) yes no octadecyl dimethylsiloxane copolymer, silanol (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 trimethoxysilane terminated, 25-40 cSt [00090] [00091] 27d 70% n- 29% (10-15% vinylmethylsiloxane) − 1% DBTDL (di-n-butyltindilaurate) yes yes octadecyl dimethylsiloxane copolymer, silanol (C.sub.4H.sub.9).sub.2Sn[OCO(CH.sub.2).sub.10CH.sub.3].sub.2 trimethoxysilane terminated, 25-40 cSt [00092] [00093] 28  80% hexadecyl 19.7% polymethyl hydrogensiloxane − n 0.3% dimethyltin yes no trimethoxysilane sufficient to achieve (M.sub.n = 1700-3200) dineodecanoate (6 weeks [00094] [00095] [00096] cure) 29  80% octadecyl 19% PDMS 1% dimethyltin yes yes triethoxysilane silanol 65 cSt dineodecanoate [00097] [00098] [00099] 30  80% hexadecyl 19.0% PDMS 1% dodecylbenzenesulfonic yes not trimethoxysilane silanol 65 cSt acid tested [00100] [00101] [00102]

[0084] A series of comparative examples were tested in Table II.

TABLE-US-00002 TABLE II (all percentages are in weight percent, the combination of components totalling 100 wt. %) Oil Oil repellent repellent Ex Silane Siloxane Catalyst on bricks on paver 31 90% n-octyl 9.9% PDMS 0.1% dimethyltin no no triethoxysilane silanol 65 cSt dineodecanoate [00103] [00104] [00105] 32 80% iso-butyl 19.9% PDMS 0.1% dimethyltin no no triethoxysilane silanol 65 cSt dineodecanoate [00106] [00107] [00108] 33 80% methyl 19.9% PDMS 0.1% dimethyltin no no trimethoxysilane silanol 65 cst dineodecanoate [00109] [00110] [00111] 34 99.9% hexadecyl none 0.1% dimethyltin no no trimethoxysilane dineodecanoate [00112] [00113] 35 3% methyl 96.9% PDMS 0.1% no no trimethoxysilane silanol 65 cst (centistokes) DBTDL [00114] [00115] [00116] 36 100% PDMS silanol 65 cSt no no [00117] 37 Capstone ST 200 diluted to 4% active yes yes content in Isopropanol (a commercial fluoroproduct from Chemours)

[0085] As shown from the combination of the results of Table I and Table II, the invention requires a combination of Formula (I) and Formula (II) with no addition of perfluorinated compounds to achieve both hydrophobicity and oleophobicity. This is clearly show in Example #34 where only a silane was employed with no siloxane. As also clearly demonstrated in the tables, R.sub.1 in Formula (I) needs to be a sufficient number of carbons (at least 12) for the beneficial impact to be realized as illustrated in Examples #31-#33. The value of some catalysts versus others is illustrated in #6 where oil-repellency was achieved on bricks only, but not on pavers.

[0086] The mixtures are also excellent water repellents as shown in the following example wherein the formulation form Example #2 was coated on bricks and concrete paver using different coverage rates. The water repellency was measured using the Rilem method, the amount of water absorbed into the subtrates at a given time is reported in ml (using horizontal test tubes). For comparison the results for an untreated reference substrate are reported as well. Rilem Test Method-Test No. II.4 Horizontal Application (Réunion Internationale des Laboratoires et Experts des Matériaux, systèmes de construction et ouvrages). The results are tabulated in Table III.

TABLE-US-00003 TABLE III Brick Concrete paver 125 250 Untreated 125 250 500 Untreated g/m.sup.2 g/m.sup.2 reference g/m.sup.2 g/m.sup.2 g/m.sup.2 reference 15 min 0 0 >4 0 0 0.1 >4 30 min 0 0 — 0 0 0.1 — 1 h 0 0 — 0.1 0 0.2 — 2 h 0 0 — 0.1 0 0.2 — 4 h 0 0 — 0.1 0 0.2 — 24 h 0.1 0.1 — 0.2 0.2 0.3 —

[0087] As illustrated in the table, to the untreated surface, the treatment on the brick and concrete paver caused significant less water to be absorbed. The formulation was stable when in a closed container for 8 weeks at 50° C.

[0088] The formulation enhances the surface leading to a darker, more homogenous wet like look of stones and concrete. This mixtures are as enhancing the color as shown in the following example wherein the formulation from Ex. #2 was coated on various substrates and the L,a,b values were measured. The following Table IV shows how the treatment significantly reduces the L values (average of 3 measurements), the reduction In “L” values being at least equal to or greater than 5 “L” units, more preferably at least equal to or greater than 10 “L” units. The application of the composition of Formulas (I) and (II) results in a surface with the desirable “wet” look, a visual appearance which is maintained even after drying of the composition.

TABLE-US-00004 TABLE IV Granite Gray (salt and Gray Red Black concrete pepper) slate brick Granite paver Untreated L 57.05 53.34 49.66 43.27 55.41 a −0.32 −2.42 14.84 0.33 0.49 b 2.14 2.43 17.60 3.65 6.60 Treated L 33.85 38.86 36.76 27.18 38.02 a 0.04 −1.60 18.90 0.21 0.69 b 1.99 5.41 19.81 1.44 6.81 Δ L 23.20 14.48 12.90 16.09 17.39

[0089] The darkening (enhancement) of the substrate is permanent. Unlike water or a solvent which will evaporate or non-reactive oils that wash out or migrate deeper into a substrate, the treatment will chemically react ideally forming covalent bonds to the substrate. The visibility of the color change is dependent on the amount applied and colour/type of substrate. Concrete pavers and terracotta type bricks treated (with 250 g/m .sup.2) more than a year ago, and stored Inside and outside on a roof, still show the color enhancement.

[0090] The formulations can be provided in form of an emulsion:

[0091] Example 38: To 46 g of demineralised water, 2 g of Genapol 0X80 (Clariant) and 2 g of Tergitol TMN-6 (Dow Chemical) are added and mixed with an Ultraturrax mixer. 10 g of a silanol terminated PDMS (65cSt) and 40 g of hexadecyitrimethoxysilane were premixed in a beaker and slowly added (by means of a pipette) to the surfactant solution while continuing mixing with the Ultraturrax mixer at 24000 rpm. A white emulsion is formed. The emulsion was applied to a concrete paver and allowed to cure for 4 weeks. The paver shows oil repellence when tested with olive oil.

[0092] The formulation can also be provided in the form of a two-component system. This is useful when fillers are used which tend to settle from the mixture, shelf life of a mixture is short or fast cure is desired.

[0093] Example 39: Component A: 60 parts of hexadecyltrimethoxysilane mixed with 0.5 parts of UL 28; Component B: 29,5 g of a silanol terminated PDMS (65 cSt) and 10 g calcium carbonate powder (1 micron mean particle size). Component A and B are mixed within one (1) hour of preparation and applied to a surface of a paver and terracotta type brick (application rate for both 250 g/m.sup.2). The surfaces show oil repellence after 24 h when tested with olive oil.

[0094] Example 40: The mixture being as described in Table 1 Example #2 and applied to the following materials; polished Carrara marble, flamed finish green granite, polished brown marble (café Armani), honed finish tumbled travertine, honed finish Jerusalem limestone, Brown honed Sydney sandstone, Himalayan teak honed sandstone, Chinese grey slate, Encaustic tile (Made in Vietnam), Brighton Masonry Charcoal concrete paver, photocopy paper (Reflex Ultra White A4 80 gsm), unsanded maple hardwood, inside of leather belt (Trent Nathan New Zealand) allowed to cure for at least 1 week at ambient temperature (23° C. and ˜60% RH). Oil repellence was tested by applying 3 drops of olive oil on the substrates. If the oil drops were still present after 1 hour the formulation was rated as oil repellent. If 1 or more drops were absorbed into the substrate the formulation was rated as non-oil repellent.

TABLE-US-00005 Oil Example Substrate repellent a polished Carrara marble yes b flamed finish green granite yes c polished brown marble yes d honed finish tumbled travertine yes e honed finish Jerusalem limestone yes f Brown honed Sydney sandstone yes g Himalayan teak honed sandstone yes h Chinese grey slate yes i Encaustic tile yes j Brighton Masonry Charcoal yes concrete paver k photocopy paper yes l unsanded maple hardwood yes m leather yes

[0095] Example #37 in Table II illustrates a commercially available product for comparative purposes. The product is available from Chemours. The test shows that a product containing perfluorated carbon atoms repels olive oil in the test just as the compositions falling under this invention and which are free of perfluorinated carbon atoms.

[0096] The diversity of the composition for the “R” groups for the silane and siloxane compounds is quite broad, in which an amine side group is illustrated in Ex. #11; an ethoxy end group is illustrated in Ex. #24(a)-(d) and #29; hydrogen is illustrated as an end group in Ex. #25(a)-(d); a phenyl group is illustrated In Ex. #26(a)-(d); and a hydrogen side group in Ex. #28.

[0097] The diversity of applicable catalysts is equally broad, with some non-limiting examples including titanates (see Exs. #17 & 18); zirconates (see Ex. #19); carboxylic acids (see Ex. #20); amines (see Exs. #21 & 22); aminosilane (see Ex. #6); strong base (see Ex. #23 for KOH); and strong acids (see Ex. #30 for DBSA).

[0098] The diversity of substrates that can be treated Is shown in Example #40.

[0099] The best mode for carrying out the invention has been described for purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and merit of the claims. The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.