Ester-terminated and tertiary amide-terminated polyamide stick articles which are substantially hydrocarbon-free and which contain high concentrations of functional substances, such as fragrances and air freshener compositions. The articles are useful for providing the functional substances to a surface by means of rubbing the stick article onto the surface.
The prior art contains several references to functional substance-providing stick articles, for example (a) tertiary amide-terminated polyamide polyglyceryl-2 polyhydroxystearate pigment-containing sticks for lipstick applicators described in U.S. Pat. No. 6,469,131; (b) tertiary amide-terminated polyamide-salicylic acid octyl monoester-linoleic acid isostearyl monoester-mineral oil sunblock stick articles containing 0.60% fragrance described in Example 7 of U.S. Pat. No. 6,592,857; and (c) ester-terminated polyamide-mineral oil-functional ingredient stick applicators including fragrance and insect repellent applicators as described in U.S. Pat. No. 6,111,055.
Nevertheless, such references are either directed to polyamide stick articles having very low concentrations of functional ingredient in the scope of our invention, e.g., fragrance, or polyamide stick articles containing high concentrations of undesirable hydrocarbons, e.g., mineral oil. Thus, no teaching exists in the prior art of functional ingredient-providing hydrocarbon-free polyamide stick articles, or dispensing packages containing and employing such stick articles. Furthermore, no teaching exists in the prior art of the inclusion of such articles in dispensing-type packages where such article-containing packages are deployed for coating functional substance-containing and emitting films on inanimate solid laminar surfaces.
Our invention is directed to a substantially hydrocarbon-free functional substance-providing stick article having consistently-maintained functional composition and dimensional integrity comprising a stiff, substantially monophasic, thermally-reversible composition comprising:
In a preferred embodiment the compatible additive causes the stick article to have an operative value V of between 7 and 10 on a scale of 1–10 as measured by the “IFF SPDC Test” (“Substance-Providing Dimensional Compatibility Test” as described herein.
Our invention is further directed to a package for utilization of the above-mentioned functional substance-providing stick article comprising means for supporting said functional substance-providing stick article such that an end portion of said stick article can be exposed for use. The means for supporting said stick article include a container for surrounding the stick article, the container having an opening such that the stick article can be exposed for use, and a border of the stick-surrounding member forming the opening, said border forming a top end of the supporting means, such that said end portion can be elevated from said means for supporting and can protrude therefrom so as to be exposed for use, said stick article being contained within said stick-surrounding member.
Our invention is still further directed to a process for applying a controllably releasable functional substance which is one or more of a perfume composition, an insect repellant composition, a malodor control agent, an animal repellant composition, an anti-microbial composition, an insect attractant composition and/or an air freshener composition to an inanimate substantially solid surface, preferably a laminar surface comprising the steps of providing the above mentioned package; exposing for use the end portion of said stick article contained within said package; providing an solid surface to be treated; and applying the end portion of said stick article contained within said package to a finite area of said solid surface.
The term “substantially hydrocarbon-free” is intended herein to mean that the concentration of any hydrocarbon in the stick article of our invention, e.g., mineral oil, is less than 1% of the weight of the stick article of our invention; preferably less than 0.5% by weight of the stick article of our invention; and more preferably less than 0.1% by weight of the stick article of our invention.
The term “system-compatible functional composition” is herein intended to mean functional compositions, for example, fragrance compositions which, when made part of the support polymer-operativeness additive system do not compromise the transparency of the stick article by causing haze or cloudiness, due to, for example, phase separation or synerisis to occur as a result of the composition being admixed with the support polymer-operativeness additive system.
The term “consistently-maintained functional composition and dimensional integrity” is intended herein to mean that when the stick article of our invention is in use in applying a film to an inanimate solid laminar surface, the proportions of the constituents and the chemical properties of the functional composition, e.g., the fragrance composition that is evolved into the environment on use of the stick article of our invention are substantially identical to the proportions and chemical properties of the constituents originally present in the stick article and originally admixed with the support polymer-operativeness additive system; and the geometric dimensions thereof with reference to the “x”, “y” and “z” axes on use thereof are substantially identical to the geometric dimensions originally existent in the stick article.
The term, “stiff” is herein intended to mean that the stick article of our invention is self-supporting and non-flowable at ambient temperatures or less and at ambient pressures, e.g., at temperatures of less than or about equal to 35° C. and at pressures of about 1 atmosphere absolute.
The term “monophasic” is herein intended to mean that the stick article of our invention on use or when not in use exists in one unitary phase without any phase separation resulting from the inclusion in the support polymer-operativeness additive system of a functional composition, e.g., a fragrance composition.
The term “thermally reversible” is herein intended to mean that the stick article of our invention retains the original proportions of the constituents of its composition and retains its original physical characteristics and original dimensions on use thereof, and subsequent to use thereof.
The term: “IFF SPDC Test” for “Substance-Providing Dimensional Compatibility Test”, is intended herein to mean the determination of an operative value V of the stick article of our invention measured according to the algorithm:
V=V1σ+V2λ+V3δ+V4κ+V5τ+V6γ+V7ρ
wherein σ is the degree of stiffness of the stick, as measured on a scale of 1–10, with V1 being the fraction indicating the priority of the degree of stiffness, with 0.05≦V1≦0.25; λ is the measure of pliability of the stick, as measured on a scale of 1–10, with V2 being the fraction indicating the priority of the degree of pliability, with 0.05≦V2≦0.25; δ is the measure of durability of the stick, as measured on a scale of 1–10, with V3 being the fraction indicating the priority of the degree of durability, with 0.05≦V3≦0.25; κ is the measure of the consistency of the stick, as measured on a scale of 1–10, with V4 being the fraction indicating the priority of the degree of consistency of the stick, with 0.05≦V4≦0.25; τ is the measure of the lack of tackiness of the stick, as measured on a scale of 1–10 with a value of ‘10’ indicating ‘0’ tackiness, with V5 being the fraction indicating the priority of the degree of lack of tackiness, with 0.05≦V5≦0.25; γ is the measure of the degree of glide of the stick, on use, as measured on a scale of 1–10 with V6 being the fraction indicating the priority of the degree of glide of the stick, on use, with 0.05≦V6≦0.25; and ρ is the measure of surface rinsability immediately after use of the stick with V7 being the fraction indicating the priority of the degree of surface rinsability immediately after use of the stick, with 0.05≦V7≦0.25, wherein ΣVi=1. A result range of 6≦V≦10 is a desired result for the operativeness of the stick articles of our invention. A result range of 7.5≦V≦10 is a more preferred result for the operativeness of the stick articles of our invention. A result range of 9≦V≦10 is a most preferred result for the operativeness of the stick articles, and hence the most preferred desirable result of the IFF SPDC Test for the stick articles of our invention.
Preferable ester-terminated polyamides useful in the practice of our invention are those disclosed in Pavlin et al., U.S. Pat. No. 5,998,570 the disclosure of which is herein incorporated by reference, and include those ester-terminated polyamides prepared by reacting “x” equivalents of a dicarboxylic acid wherein at least 50% of those equivalents are from polymerized fatty acid, “y” equivalents of ethylenediamine and “z” equivalents of an alcohol which is in the alternative, or in combination cetyl alcohol and/or stearyl alcohol wherein:
More preferably, the ester-terminated polyamide is one of a group having a weight-average molecular weight of about 6000 and a softening point in the range of from 88° C. to 94° C. prepared by reacting “x” equivalents of C36 dicarboxylic acid, “y” equivalents of ethylenediamine and “z” equivalents of an alcohol which is, in the alternative or in combination cetyl alcohol and/or stearyl alcohol wherein
Most preferable are the mineral oil-free ester terminated polyamiides, SYLVACLEAR 100LM, UNICLEAR 100 and UNICLEAR 100V, registered trademarks of the Arizona Chemical Company of Panama City, Fla.
Preferable tertiary amide-terminated polyamides useful in the practice of our invention are those disclosed in MacQueen et al., U.S. Pat. No. 6,268,466 issued on Jul. 31, 2001, the specification of which is herein incorporated by reference, and include those tertiary amide-terminated polyamides prepared by reacting “x” equivalents of dicarboxylic acid wherein at least 50% of those equivalents are from polymerized fatty acid, “y” equivalents of ethylenediamine and “z” equivalents of a monofunctional reactant having a secondary amine group as the only reactive functionality wherein
Most preferable are those tertiary amide-terminated polyamides disclosed in Example I of U.S. Pat. No. 6,268,466.
The compatible operativeness additive, as stated supra may be at least one of the group of esters of mono-, di- and tri-carboxylic acids, esters of alkoxylated mono-, di- and tri-carboxylic acids, metal salts of hydroxy-mono-, di- and tri-carboxylic acids, metal salts of di- and tri-carboxylic acid partial esters, metal salts of alkoxylated mono-, di- and tri-carboxylic acids, metal salts of alkoxylated di- and tri-carboxylic acid partial esters and solutions thereof having a molecular weight in the range of from about 350 to about 1500, optionally in admixture with one or more sodium salts of a C12–C18 saturated or unsaturated carboxylic acid.
Examples of preferred operativeness additives which are esters of alkoxylated mono-, di- and tri-carboxylic acids useful in the practice of our invention are set forth in U.S. Pat. Nos. 5,302,377, 5,455,025, 5,597,555 and Published U.S. Patent Application U.S. 2003/0114520 A1 published on Jun. 19, 2003, for example, the tri-n-propoxy diester of myristyl alcohol and adipic acid (Di-PPG-3-myristyl adipate). A more preferred class of such esters are fatty alkoxylate esters which are diesters of an aliphatic or aromatic dicarboxylic acid formed by reacting said acid with a stoichiometric excess of one or more polyalkoxylated fatty alcohols, the fatty moieties of which contain from 12 to 22 carbon atoms.
A preferred operativeness additive is a metal salt of a hydroxy-carboxylic acid useful in the practice of our invention, zinc ricinoleate (the zinc salt of 12-hydroxy-9-octadecenoic acid) is set forth in U.S. Pat. No. 4,968,496 and Published Application for U.S. Letters Patent U.S. 2003/0007945 A1 published on Jan. 9, 2003. It is a highly preferred embodiment of the invention, the zinc ricinoleate is used in combination with one or more 1-hydroxy-2-ethoxyethyl ethers of C12–C14 alcohols in a ratio range of from about 1:1.5 to about 1.5:1 by weight.
The following Table I indicates a number of most preferred operativeness additives taken alone or in combination with one or more sodium salts of a C12–C18 saturated or unsaturated carboxylic acid and their respective ranges of usage in the stick article of our invention:
As stated supra, the functional products contained in the stick article of our invention include without limitation fragrances, antimicrobial substances, animal repellents, malodor treatment, insect attractants, and insect repellents. The functional products preferably have a C log10P in the range of from about 1 to about 6.5, without restriction on the molecular weight of each of said components wherein P is the n-octanol/water partition coefficient of the fragrance component. The concentration range of the functional product in the stick article of our invention is preferably from about 10% to about 45% by weight of the stick article of our invention.
The following functional products are provided as examples of the types of materials that can be incorporated in the present invention. Those with skill in the art will readily be able to use the described materials as well as various combinations of materials as well as other materials not provided herein without departing from the scope of the present invention. Suitable fragrance chemicals are found in for example U.S. Pat. Nos. 4,534,891, 5,501 805, 5,554,588, and 5,676,163. Another source of suitable fragrances is found in Perfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher, 1959. Examples of fragrance with anti-microbial properties useful in the present invention are set forth in U.S. Pat. Nos. 6,495,512 and 6,517,759. Suitable insect repellant materials include the materials disclosed in U.S. Pat. Nos. 5,441,988, 5,576,011, 5,409,958, 5,439,941, 5,683,687, 5,753,686, and 5,633,236. Suitable malodor treating substances are described in U.S. Pat. Nos. 4,009,253, 4,187,251, 4,310,512, 4,622,221, 4,719,105 and 6,432,891. Suitable insect attractant materials are found in U.S. Pat. Nos. 5,770,189, 5,990,244, 5,229,126 and malodor agents 6,551,998, 6,207,679, and 5,508,417.
The values of C log 10P of many functional product ingredients, for example, fragrance ingredients and/or antimicrobial ingredients, contained in personal treatment compositions and/or cosmetic compositions is discussed in published U.S. Patent Application US 2003/0110682 A1 published on Jun. 19, 2003, U.S. Pat. Nos. 5,540,853 and 6,451,065. Furthermore, values of log10P have been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc., Daylight CIS, Irvine, Calif. However, the log10P values are most conveniently calculated by the “CLOGP” program, also available from Daylight CIS. This program also lists experimental log10P values when they are available in the Pomona92 database. The “calculated log10P” (C log 10P) is determined by the Hansch and Leo “fragment” approach based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity and the chemical bonding. The C log 10P values which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental log10P values for the selection of functional ingredients, including perfume ingredients which are useful in the stick articles of our invention.
Specific examples of preferred fragrance components useful in the stick articles of our invention, and the molecular weights and C log 10P values of each of said components are set forth in Table II below.
The stick articles of our invention, when used in a preferred manner in the practice of our invention are contained, for example, in a package as illustrated in
The stick article of our invention comprise means for supporting the functional substance-providing stick article of our invention such that an end portion of said stick article can be exposed for use, with the means for supporting said stick article including a stick-surrounding member for surrounding the stick article, the stick-surrounding member having an opening such that the stick article can be exposed for use, and a border of the stick-surrounding member forming the opening, said border forming a top end of the supporting means, such that said end portion can be elevated from said means for supporting and can protrude therefrom so as to be exposed for use, said stick article being contained within said stick-surrounding member. For example, the means for elevating includes a screw feed mechanism having an elevator screw such that upon rotation of the elevator screw the stick article is pushed up from the bottom such that the end portion protrudes and is exposed for use. As a second example, the means for elevating is a means for pushing up the stick article so that the end portion protrudes from the means for supporting and is exposed for use.
The present invention also provides a process for applying a controllably releasable functional substance such as a perfume composition, an insect repellant composition, a malodor treating material, an animal repellant composition, an anti-microbial composition, an insect attractant composition and/or an air freshener composition to a surface, preferably an inanimate laminar substantially solid surface. The process comprising the steps of providing a package as described above; exposing for use the end portion of said stick article contained within said package; providing surface to be treated; and applying the end portion of said stick article contained within said package to the surface. The present invention has the advantage of being able to deliver the functional ingredients directly to a surface, while not depositing a greasy or unsightly or staining residue. The present invention allows the functional materials to be directly deposited to a countertop, refuse container, wall, litter box or any other location where it would be desirable to provide a pleasant fragrance, anti-bacterial agents, or malodor protection.
The polymer system of the present invention also provides for a high loading of the functional ingredients while also providing these materials dispersed substantially uniformly throughout the polymeric system.
When carrying out such process, the percent weight loss, due to functional product loss, of stick article product per se, or product applied to an inanimate laminar surface, π vs. time, θ, measured in days, is according to the algorithm:
π=αLN(θ+1)+β
wherein α is a number in the range of from about 3.5 to about 7.5 and β is a number in the range of from about −1.0 to about +4.0 as more particularly described in the descriptions of
α=0.043T−18.96
and β is a function of absolute temperature as measured in degrees Rankine, T, and is according to the additional algorithm:
β=−0.6LN(580−T)+1.7.
Referring to
Referring to
Referring to
Referring to
All U.S. Patents and U.S. Published patent applications cited in this application are hereby incorporated by reference as if set forth in their entirely. The following examples are not meant to define or otherwise limit the scope of the invention. Rather the scope of the invention is to be ascertained according to the claims that follow the examples. Unless noted to the contrary, all percentages are given on a weight percent on a dry basis.
The following fragrance composition was prepared:
The following fragrance was prepared:
In each of the following Examples I–IV, fragrance formulation and compatible operativeness additive were premixed and added, with stirring to UNICLEAR-100-LM ester-terminated polyamide at a temperature of 40° C. The resulting mixture was then placed into molds designed to produce stick articles that fit into packages as illustrated in
The following mixtures were prepared and molded into stick articles as set forth supra:
The “V” value of the resulting coatings for each of Examples IA, IB, IC and ID was 9.75.
The following mixtures were prepared and molded into stick articles as set forth supra:
The “V” value of the resulting coating for Example IIA was 7.75. The “V” value of the resulting coating for Example IIB was 8.10.
The following mixtures were prepared and molded into stick articles as set forth supra:
The “V” value of the resulting coating for Example IIIA was 8.65. The “V” value of the resulting coating for Example IIIB was 8.35.
The following mixtures were prepared and molded into stick articles as set forth supra:
The “V” value of the resulting coating for Example IVA was 8.75. The “V” value of the resulting coating for Example IVB was 8.90. The “V” value of the resulting coating for Example IVC was 9.10.
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