One-Part Moisture Cured Aminosiloxanes

This invention relates to a composition, stable in the absence of moisture, consisting essentially of (A) a polymer having at least one nitrogen-hydrogen bond; and (B) a readily hydrolyzable, anhydrous additive selected from the group consisting of titanates, zirconates, vanadates, germanates and mixtures thereof. The uniqueness of this invention is that the polymer is crosslinked upon exposure to moisture such as water vapor, but is reverted to noncrosslinked polymer after exposure to liquid water. Furthermore, the components can be stored together, in the absence of moisture, with no gelation.

Polymers crosslinked upon exposure to moisture, but reverted to polymer after exposure to water, would find use in hair care applications, and reversible rubber or elastomer applications. In hair care applications, a composition would be applied to hair to serve as a hair set and conditioner. Upon washing, the composition would be reverted to polymer and act, again, as a hair conditioner. An object of this invention is to provide a composition capable of performing the above.

A composition described in the article entitled "New Types of Hair Setting Sprays having Semi-Permanent Properties" authored by Fulvia Sardo in Volume 87, American Cosmetics and Perfumery, pages 43-46 (December, 1972), discloses the use of alkyltitanates in combination with silanol endblocked dimethylpolysiloxanes as a hair set. This composition, however, has limited use, at best, as a hair conditioner and setting treatment. Furthermore, there is no mention of the composition's capability of reversion to its polymer.

Canadian Pat. No. 1,112,181 discloses a hair set composition consisting essentially of aminoalkylalkoxysilanes and a titanate ester. This composition also has limited use as a hair conditioner with no mention of reversion capabilities.

U.S. Pat. No. 3,832,203 discloses a composition for treating leather comprising an organic solvent solution of (A) a titanate or zirconate, a copolymer of trimethylsiloxane and SiO.sub.2 units, a polysiloxane, and (B) an aminoalkyl substituted silane or siloxane. There is no mention of this composition being reversible and parts (A) and (B) cannot be stored together.

U.S. application for patent, Ser. No. 332,063, filed Dec. 18, 1981, now U.S. Pat. No. 4,388,437 discloses an organopolysiloxane composition, used for treating fibers, consisting essentially of an organopolysiloxane containing amine functionality, a surfactant, a titanate, zirconate or germanate, an organic acid, and water. The surfactant is needed to emulsify the siloxane. The acid is essential to adjust the pH to a desired range to control the rate of adsorption of the emulsion on the fiber. There is no mention of this composition's reversion capabilities.

An object of this invention is to provide a composition stable in the absence of moisture, but upon exposure to moisture, crosslinking occurs. A further object of this invention is to provide a composition crosslinked upon exposure to moisture, but reverted to polymer after exposure to water.

This invention relates to a composition, stable in the absence of moisture, consisting essentially of (A) a polymer having at least one nitrogen-hydrogen bond; and (B) a readily hydrolyzable, anhydrous additive selected from the group consisting of titanates, zirconates, vanadates, germanates and mixtures thereof. The uniqueness of this invention is that the polymer is crosslinked upon exposure to moisture such as water vapor, but is reverted to noncrosslinked polymer after exposure to liquid water. Furthermore, the components can be stored together in the absence of moisture with no gelation.

So far as is known at this time, any polymer containing at least one nitrogen-hydrogen bond can be employed for the purposes of this invention. Examples of suitable polymers include polyamides, polyesters, polyethers, polyurethanes, polyalkylenes such as polypropylene, polyethylene and polystyrene, and siloxanes. If the polymer is present in solid form, such as polystyrene, the polymer will have to be dissolved in a compatible solvent, such as toluene or xylene, so the additive can be mixed. Specific examples of suitable polymers include ##STR1## which are examples of polyamides, polyesters, polyethers, polyurethanes, and polyalkylenes, respectively. A siloxane polymer is preferred however. Further preference is given to the siloxane polymer having the units containing the nitrogen-hydrogen bonds selected from the group consisting of ##STR2## and mixtures thereof wherein R is selected from the group consisting of monovalent hydrocarbon radicals, substituted monovalent hydrocarbon radicals, hydrogen, and a radical having the general formula --OX, wherein X is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals, and substituted monovalent hydrocarbon radicals; R' is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals, and substituted monovalent hydrocarbon radicals; wherein at least one R' per siloxy unit is hydrogen; and m and n have values of 1 to 4.

It should be understood that the divalent radicals represented as C.sub.m H.sub.2m and C.sub.n H.sub.2n can be either linear or branched hydrocarbon radicals. Specific examples of suitable divalent hydrocarbon radicals represented by C.sub.m H.sub.2m and C.sub.n H.sub.2n in the above formula include --(CH.sub.2).sub.2 --, --(CH.sub.2).sub.3 --, --(CH.sub.2)--, --CH.sub.2 CHCH.sub.3 CH.sub.2 -- and ##STR3##

Specific examples of suitable monovalent hydrocarbon and substituted monovalent hydrocarbon radicals for R, R', and X are alkyl radicals such as the methyl, ethyl, propyl, butyl, amyl, cyclohexyl, decyl, dodecyl, and octadecyl radicals; alkenyl radicals such as the vinyl and allyl radicals; aryl radicals such as the phenyl and biphenyl radicals; alkaryl and aralkyl radicals such as the tolyl and benzyl radicals; and the corresponding substituted hydrocarbon radicals such as the chloropropyl, 3,3,3-trifluoropropyl, dichlorophenyl, cyanobutyl, and nitrophenyl radicals.

A siloxane polymer having the nitrogen-hydrogen bond units in the siloxy unit having the general formula ##STR4## wherein R is a monovalent hydrocarbon radical, R' is hydrogen, m has a value of 3 or 4 and n has a value of 2 is preferred. R being an alkyl radical is further preferred with methyl being optimal. The composition of the other units in the siloxane polymer is not critical for the purpose of this invention. The other units of the siloxane polymer can be selected from the group consisting of RSiO.sub.3/2, R.sub.2 SiO, and R.sub.3 SiO.sub.1/2 units wherein R is as defined above. A siloxane polymer composed primarily of R.sub.2 SiO units is preferred. Furthermore the endblocking and the structure of the polymer is not critical for the purpose of this invention as long as the siloxane polymer contains at least one nitrogen-hydrogen bond. Also, the siloxane polymer containing at least one nitrogen-hydrogen bond can be blended with other functional siloxanes or non-functional siloxanes, such as dimethylsiloxane or dimethylcyclosiloxane. However, a greater amount of amine or amide present leads to greater crosslinking.

A siloxane polymer having the general formula ##STR5## wherein R is as defined above, R" is selected from the group consisting of monovalent hydrocarbon radicals, substituted monovalent hydrocarbon radicals and a radical having the general formula --OX wherein X is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals, and substituted monovalent hydrocarbon radicals, a+b has a value of 1 to 2000 with a having a value of 0 to 1999, and b having a value of 1 to 2000, is preferred. Specific examples of suitable monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals for R" are as defined above for R, R', and X. But, further preference is given to R" being a monovalent hydrocarbon radical, with R" being an alkyl radical being further preferred, and methyl being optimal. The value of a+b having a value of 50 to 400 with a having a value of 49 to 399 and b having a value of 1 to 30 is also further preferred. A siloxane polymer selected from the group consisting of ##STR6## is further preferred.

So far as is known at this time, any readily hydrolyzable, anhydrous additive selected from the group consisting of titanates, zirconates, vanadates, germanates and mixtures thereof can be employed for the purpose of this invention. Specific examples of suitable organic zirconates include octyleneglycolzirconate, tetra-2-ethylhexylzirconate, tetraisopropylzirconate, tertiarybutyltrimethylzirconate and mixtures thereof. Specific examples of suitable organic titanates include tetraethyltitanate, tetradecyltitanate, tetra-2-ethylhexyltitanate, tetradodecyltitanate, tetraisopropyltitanate, tetrabutyltitanate and mixtures thereof. Specific examples of suitable organic germanates include tetraethylgermanate, tetraisopropylgermanate, and tetradecylgermanate. Specific examples of suitable organic vanadates include vanadium triisopropoxide oxide and vanadium tri-n-propoxide oxide.

Titanates are preferred, however. Organic titanates selected from the group consisting of alkyl titanates and titanium chelates are further preferred. Alkyl titanates have the general formula Ti(OD).sub.4 wherein D is a monovalent hydrocarbon radical or a substituted monovalent hydrocarbon radical.

Titanium chelates have the general formulae ##STR7## wherein G is a monovalent hydrocarbon or substituted monovalent hydrocarbon radical, X' is selected from the group consisting of hydrogen, --OCH.sub.2 CH.sub.3, --OH, monovalent hydrocarbon radicals, and substituted monovalent hydrocarbon radicals, Z and Y are divalent hydrocarbon or substituted divalent hydrocarbon radicals, and A and E are trivalent or substituted trivalent hydrocarbon radicals.

Specific examples of suitable monovalent hydrocarbon or substituted monovalent hydrocarbon radicals for D, X', and G are alkyl radicals such as the methyl, ethyl, propyl, butyl, amyl, cyclohexyl, decyl, dodecyl, and octadecyl radicals; alkenyl radicals such as the vinyl and allyl radicals; aryl radicals such as the phenyl and biphenyl radicals; alkaryl and aralkyl radicals such as the tolyl and benzyl radicals; and the corresponding substituted hydrocarbon radicals such as the chloropropyl, 3,3,3-trifluoropropyl, dichlorophenyl, cyanobutyl, and nitrophenyl radicals.

The hydrocarbon and substituted hydrocarbon radicals for Y and Z are divalent radicals. Though the above examples of suitable hydrocarbon and substituted hydrocarbon radicals for D, X' and G are in monovalent form, similar divalent radicals are suitable for Y and Z. Specific examples of suitable divalent hydrocarbon radicals include

The hydrocarbon and substituted hydrocarbon radicals for A and E are trivalent radicals. Though the above examples of suitable hydrocarbon and substituted hydrocarbon radicals for D, X', and G are in monovalent form, similar trivalent radicals are suitable for A and E. Specific examples of suitable trivalent hydrocarbon radicals include ##STR8##

Specific examples of suitable titanates having the general formula Ti(OD).sub.4 include tetraisopropyltitanate, tetra-n-butyltitanate, and tetrakis(2-ethylhexyl)titanate. Specific examples of suitable titanate having the general formula ##STR9## include titanium acetylacetonate and titanium ethyl acetylacetonate.

Titanates having the general formula Ti(OD).sub.4 wherein D is an alkyl radical are preferred. Further preference is given to the titanate having the general formula Ti(OD).sub.4 wherein D is selected from the group consisting of isopropyl, 2-ethylhexyl, and n-butyl radicals.

If desired the composition may also contain an anhydrous organic solvent. Examples of suitable solvents include aliphatic hydrocarbon and aliphatic halogenated hydrocarbon solvents such as hexane, heptane, and 1,1,1-trichloroethane; and aromatic hydrocarbon solvents such as toluene and xylene. The solvent, 1,1,1-trichloroethane, is preferred.

Compositions containing 0.97 to 90 percent by weight of the siloxane, 0.03 to 15 percent by weight of the metallic additive, and 1 to 99 percent by weight of a solvent are preferred. Compositions containing from 3 to 20 percent by weight of the siloxane, 0.1 to 3 percent by weight of the metallic additive and 77 to 96.9 percent by weight of a solvent are further preferred.

If desired, the composition may also contain 0.01 to 50 percent by weight of an alkoxy silane having at least two alkoxy groups per silicon for added durability. Specific examples of suitable alkoxy silanes include methyl trimethoxysilane and a silane having the general formula NH.sub.2 CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 CH.sub.2 Si(OCH.sub.3).sub.3.

In addition to the essential ingredients, the composition of this invention may include minor quantities of optional materials which are added for specific purposes. Such other ingredients include, but are not limited to, medicaments such as anti-dandruff compounds, solvents, perfumes, sequestering agents, conditioning agents such as quaternary ammonium compounds, thickening agents, fillers, opacifiers, anti-static agents, and antimicrobial preservatives, of which silicone is one.

The method of preparation of the components of the present invention are well known to those skilled in the art and detailed elsewhere in the literature. Hence no time or space need be devoted here to a repetition of such information. As far as is known at this time, the order or method of mixing the components employed is not critical for the purpose of this invention.

Suitable uses for this composition are in the field of hair care and anywhere there is need for a reversible rubber or elastomer. In the field of hair care, preference is given to applying the composition to preset and dried hair. The composition can be applied to the hair in any suitable form such as in thickened form by hand, in viscous form, by aerosol, or by pump spray. The composition after curing on the hair acts to hold any set in the hair even when exposed to atmospheric humidity, but when the hair is contacted directly with water such as by washing, the set is removed from the hair. Washing hair with a shampoo rather than just water is even more effective in removing the set from the hair. However, sufficient composition remains on the hair to act as a conditioner for the wet hair. Furthermore, if the hair is reset and dried, the composition again acts to hold the set in the hair although to a somewhat lesser extent than after the initial application of the composition. Although not intending to be bound by this theory, applicant believes that the cured composition when contacted directly with water such as by washing, reverts to the noncrosslinked, uncured polysiloxane which acts as the conditioner for the wet hair. When the hair is again dried however, applicant believes that the composition that remains on the hair again cures to sufficient extent to improve the set holding properties of the hair. The term "hair" as used in the present invention includes treated and untreated human hair, animal hair, and any type of fiber that needs gloss, ease of combing, set hold, feel of fullness, protection from the elements such as sun, and reduced fly-away. Treated hair includes hair that is chemically changed and/or damaged by permanents and dyes. Setting hair means to curl, wave, control, or straighten hair.

Now in order that those skilled in the art may better understand how the present invention can be practiced, the following examples are given by way of illustration and not by way of limitation. All parts and percents referred to herein are by weight unless otherwise specified.

The following formulations were prepared by weighing the components into a 4 oz. bottle, capping, and shaking: ##STR10##

After mixing, the fluids were clear and colorless and there were no apparent increases in viscosity. The caps were removed and a portion of the fluid poured into aluminum cups exposed to atmospheric air. The results are as follows:

After 24 hours of exposure, formulations A, B, C, D, E, F, G, H, and I were cured to a thickness of about 1/16 inch while the materials kept in the capped bottles were still unchanged.

Formulation J indicates the importance of the N--H bond. The composition was exposed to air for 24 hours and showed no surface skin.

Formulations, K, L, M, and N indicate the importance of the titanate being readily hydrolyzable. The tetraoctylene glycol titanium chelate and the triethanolamine titanium chelate used in the formulations are not readily hydrolyzable. These formulations were also exposed to air for 24 hours and showed no evidence of forming a surface skin. The absence of surface skin in these formulations after 24 hours of exposure to the atmosphere is a simple test that can be employed to distinguish organic titanates, zirconates, germanates, and vanadates that are not readily hydrolyzable.

Formulation D was shelf-aged for 16 days and then the above process was repeated giving similar results. A portion of its cured rubber, 1/16 inch thick, was also heat aged 3 days at 100.degree. C. with no apparent adverse effects. Another portion of this cured rubber was immersed in tap water and became soft after 3 hours. After 3 days of immersion, the cured rubber reverted to the polymer and a white precipitate.

A formulation was evaluated for the ability of the present invention to hold a set to hair. The formulation consisted of 10 percent by weight of ##STR11## 1 percent by weight of tetraisopropyltitanate, and 89 percent by weight of 1,1,1-trichloroethane. The components were mixed together and the formulation was then placed in an aerosol can with 50 cc of dichlorodifluoromethane propellant.

The test consisted of spraying the formulation onto undyed, preset, and dried hair and then exposing the hair to a water mist. An untreated specimen, also undyed, preset, and dried, was also exposed to the water mist.

The silicone treated hair held its set while the control completely lost its set after 24 hours exposure to atmospheric air.

The following formulations were prepared by weighing the components into a 1 ounce bottle, capping and shaking. The siloxane employed in the formulations had the general formula of ##STR12## Nine grams of the siloxane and 1 gram of the additive was employed. Vanadium triisopropoxide oxide, zirconium-n-propoxide, and germanium butoxide were the additives employed in Formulations A, B, and C, respectively.

After mixing, the formulations were clear with no apparent increase in viscosity. The caps were then removed and a portion poured into aluminum cups exposed to atmospheric moisture. The results are as follows:

After 24 hours of exposure, formulations A, B, and C were cured to a thickness of about 1/16 inch while the material kept in the capped bottles were still in an unchanged, fluid state.