Patent Grant
6995122
Our invention is directed to a method for imparting a substantive fragrance and, optionally, long-lasting anti-static properties to fabrics being washed in a washing machine during one or more washing cycles and/or fabrics being dried in a clothes dryer during one or more drying cycles, by means of tumbling the fabrics under heat (i) with one or more reusable convenient-to-handle three-dimensional sachets, each of which has the same or different dimensions and each of which (a) has a wall permeable to the passage of each of the components of a perfume composition and to the passage of anti-static agents, and (b) contains solid and/or visco-elastic particulate polymeric fragrance substances in the form of porous polymer particles each of which has an average effective diameter of from about 0.5 mm up to about 10 mm, preferably in the range of 0.5 mm≦Dp≦1.5 mm, or in the range of 3 mm≦Dp≦7 mm wherein Dp represents the average effective particle diameter, and (ii) optionally, one or more anti-static agents separate from the sachet. The fragrance substances are individual aroma chemicals and/or multi-component fragrance compositions. The polymer particles may optionally include anti-static agents which are individual anti-static chemicals and/or multi-component anti-static compositions. The fragrance substance and the optional anti-static agent are efficaciously releasably absorbed in each of the polymer particles. The polymer particles useful in the practice of our invention, which may be puffed, using a blowing agent, have infrastructures composed of at least one of an ethylene-vinyl acetate copolymer, a blend of from about 90:10 up to about 10:90 wt.:wt ethylene polymers:ethylene-vinyl acetate copolymers, one or more ester-terminated polyamides, a blend of one or more ester-terminated polyamides and one or more polysaccharides such as maltodextrins and/or one or more C1–C4 alkyl methacrylate polymers. The polymers useful in the practice of our invention may optionally contain one or more fillers, one or more fragrance release promoters and/or one or more plasticizers. Our invention is also directed to novel compositions of matter containing one or more ester-terminated polyamides and urea and/or polysaccharides such as maltodextrins. Our invention is further directed to a novel method for producing ester-terminated polyamide particles having absorbed therein efficaciously controllably releasable fragrances and, optionally, one or more anti-static agents.
The need for imparting substantive fragrances as well as anti-static properties to articles of clothing being washed and/or dried has been, over the past century, well-recognized in the prior art. Various attempts at fulfilling this need using various delivery systems have been disclosed in the prior art. There is a substantial presence in the international market place of fabric conditioning sheets containing perfumes and, in addition anti-static agents, for example products marketed under the trademark “ALL”, trademark of Lever Brothers Company of Edgewater, N.J., described in U.S. Pat. Nos. 6,133,226 and 6,297,210, the specifications of which are herein incorporated by reference, the product disclosed in U.S. Pat. No. 5,145,595, the specification of which is herein incorporated by reference, and “CLINGFREE” trademark of Reckitt Benckiser N.V. of Schiphol, Netherlands. Furthermore, U.S. Pat. Nos. 6,436,894 and 6,235,705 the specifications of which are herein incorporated by reference disclose a process for providing anti-static and scent to clothes being laundered in a dryer by placing with the clothing being dried, a reusable mesh bag containing ‘pearls’ having a diameter of between 0.1 inches and 1 inch (2.54 mm up to 25.40 mm) composed of polyethylene and polypropylene which have absorbed therein perfume and anti-static agents which serve to dissipate an electrostatic charge on the clothing in order to avoid clothing ‘cling’ subsequent to the washing and/or drying operations. The disclosure of U.S. Pat. No. 6,436,894 indicates that a whitening agent such as titanium dioxide as well as a blowing agent can be added to the ‘pearls’.
The use of currently marketed fabric softener “sheets” as exemplified herein as well as the use of particles, the infrastructures of which consist of unmodified polyethylene and/or polypropylene polymers disclosed in such patents as U.S. Pat. Nos. 6,436,894 and 6,235,705 has, however, been determined to be inadequate in providing efficacious delivery of the perfume and/or antistatic agents to fabrics being washed and/or dried. Furthermore, ‘pearls’ having effective diameters of greater than 10 millimeters as disclosed, for example, in U.S. Pat. Nos. 6,436,894 and 6,235,705, have been found to handicap the fabric washing and/or drying process as a result of intermittently causing the washing machine and dryer to go into an uncontrollable ‘off-balance’ mode during the washing and drying procedures.
Although polymeric perfume particles having effective diameters of from 0.5 mm up to 10 mm and having infrastructures fabricated from ethylene-vinyl acetate copolymers are disclosed to be useful in time release fragrance sachets for air freshening, particularly for use in clothes storage cabinets in U.S. Pat. No. 6,213,409, the disclosure of which is herein incorporated by reference. U.S. Pat. No. 6,213,409 does not disclose processes for utilizing reusable sachets containing polymeric fragrance particles for the purpose of imparting substantive fragrances to fabrics during any of the cycles of fabric washing and/or fabric drying operations.
Our invention provides a method for imparting a substantive fragrance and, optionally, anti-static properties to fabrics in a washing machine and/or in an automatic clothes dryer comprising tumbling said fabrics under heat at a temperature in the range of from about 40° C. up to about 100° C. in said washing machine and/or in said dryer with (a) at least one three-dimensional sachet article which evolves, during the washing cycle and/or during at least one drying cycle, an effective amount of a fragrance-imparting composition at an effective rate and, optionally, an effective amount of an anti-static property-imparting composition at an effective rate and, optionally, (b) an effective amount of an anti-static property-imparting composition separate from said sachet article, said three-dimensional sachet article comprising:
Sachet articles useful in the practice of our invention may be fabricated in accordance with the teachings of U.S. Pat. No. 6,213,409. Two rectangular-shaped or triangular-shaped or circular-shaped or elliptically-shaped planar pre-fabricated portions of permeable polymer sheet or natural fiber, e.g. cotton-polyester polymer composite sheet having substantially identical dimensions, or non-woven fabric, for example non-woven polyester may be juxtaposed whereby their edges coincide about their respective perimeters. Initially, perfumed polymer particles are placed onto an intended surface of one of the pre-fabricated planar sheets, also herein referred to as “laminae”. In the alternative, the pre-fabricated laminae may be fabricated from two closely-woven mesh lamina composed of a natural fiber such as cotton and/or a water-insoluble synthetic polymer such as polyethylene and/or polypropylene. The pre-fabricated sheets can be sewn together around their entire perimeters and/or they can be heat-sealed around their entire perimeters subsequent to introduction of the perfumed polymer particles. The pre-fabricated sheets may optionally have absorbed therein additional perfume components or compositions, and in addition the sheets may optionally have absorbed therein anti-static agents. The perfumed polymeric particles may have optionally absorbed therein, one or more efficaciously-releasable anti-static chemicals or anti-static compositions.
The perfumed polymeric particles useful in the practice of our invention may be fabricated from one or more of the following materials:
Preferably alkyl methacrylate resins useful in the practice of our invention are those disclosed in U.S. Pat. No. 4,463,032 the specification of which is herein incorporated by reference, particularly poly-isobutyl methacrylate cross-linked with 1,4-butanediol diacrylate or triallyl cyanurate having a number average molecular weight in the range of from about 8×105 to about 1.1×106.
In addition, perfumed polymeric particles useful in the practice of our invention may be fabricated from at least one ester-terminated polyamide according to Example V, or a blend of at least one ester-terminated polyamide and at least one polysaccharide such as a maltodextrin, for example MALTRIN M180, dextrose equivalent=18, registered trademark of Grain Processing Corporation of Muscatine, Iowa, in a weight ratio range of from about 3:5 to about 5:3. Examples of polyamides useful in the practice of our invention are UNICLEAR 100 and UNICLEAR 100V, trademarks of the Arizona Chemical Company of Panama City, Fla., each having a number average molecular weight of about 6000 and a softening point in the range of from 88° C. up to 94° C. prepared by reacting “x” equivalents of C36 dicarboxylic acid, “y” equivalents of ethylene diamine and “z” equivalents of cetyl alcohol and/or stearyl alcohol wherein
for example, as disclosed in U.S. Pat. No. 5,998,570; and amide terminated polyamides described in U.S. Pat. Nos. 6,268,466 and 6,469,131, the specifications are herein incorporated by reference.
The mean effective diameter of the perfumed polymeric particles may be in the range of from about 0.5 mm up to about 10 mm. Preferably, the mean effective diameter is in two separate ranges: from about 0.5 mm up to about 1.5 mm and from about 3 mm up to about 7 mm, with the most preferable mean effective diameter of the perfumed polymer particle being 1 mm.
When the sachet is placed in an automatic washing machine, it is either placed in the washer simultaneously with the fabric to be washed and the detergent and optionally anti-static agent, or subsequent to the emplacement in the washing machine of the fabric and detergent, and optionally anti-static agent. Examples of detergent articles and compositions useful in conjunction with the sachet article of our invention and useful in practicing the process of our invention are set forth in the following U.S. Patents, the specifications of which are herein incorporated by reference: U.S. Pat. Nos. 4,424,134; 5,574,179; 6,528,477; 6,528,471; 6,528,474; 6,521,589; 6,521,588; 6,521,585; 6,551,983; 6,551,986; 6,551,982, 6,551,979; 6,551,981, 6,551,971; and 6,551,976 disclosing detergent tablets.
When the sachet article of our invention is placed in an automatic dryer initially, or subsequent to leaving the washer along with washed fabrics, or during one of several, e.g. ten dryer cycles, optionally, an anti-static agent introduction may accompany the introduction of the sachet article. In addition, the sachet envelope may contain such anti-static agents, and the polymeric fragrance particles may contain such anti-static agents. Examples of the anti-static agents useful in the practice of our invention are those set forth in U.S. Pat. Nos. 6,436,894; 6,235,705; 6,297,210; 5,145,595 and 6,133,226. Preferable anti-static agents include laurylalkanolamides and tertiary ethoxylated cocoamines and tallow amines such as ARMOSTAT 300 and ARMOSTAT 400, trademarks of Akzo Nobel Chemicals, B.V. of Amersfoort, Netherlands.
The polymeric fragrance particles useful in the practice of our invention may contain in addition, blowing agents, plasticizers, fragrance release promoters and fillers. A number of materials have dual functions. Each of these materials is introduced during the polymer extrusion unit operation along with the fragrance material, as set forth in U.S. Pat. No. 4,521,541. Examples of blowing agents are set forth at column 12, lines 52–68 and column 13, lines 1–22 and include, for example, azo bis(formamide) and dichlorodifluoromethane. The blowing agent, HYDROCEROL trademark of Clariant, A.G. of Muttenz, Switzerland which is a mixture containing 45% sodium bicarbonate, 45% by weight citric acid and 10% by weight beeswax as described in U.S. Pat. No. 4,769,397. Examples of fragrance release promoters are paraffin wax and polysaccharides such as maltodextrins, for example, MALTRIN M-180. Examples of fillers are CaCO3, activated carbon, silica and urea. Calcium carbonate also has substantial fragrance-release promotion properties when used with the polymeric fragrance particle-containing sachets in the process of our invention. The mixture of urea and ester-terminated polyamides is a novel composition used in our invention. Examples of plasticizers are isopropyl myristate, diethyl phthalate, dibutyl phthalate, benzyl benzoate, mineral oil, a methyl ester of a vegetable-derived C12–C18 carboxylic acid, for example, soybean methyl ester, the methyl ester of a mixture of 26% oleic acid, 49% linleic acid, 11% linolenic acid and 14% saturated fatty acids and a glyceryl ester of a vegetable-derived C10 carboxylic acid, preferably the triglyceride of a 50:50 mixture of caprylic acid and capric acid marketed under the trademark, NEOBEE-M5 by the Stepan Chemical Company of Northfield, Ill.
When carrying out the process of our invention, the release of fragrance vs. time or vs. dryer cycle number can be expressed as a mathematical model wherein the % weight loss of fragrance Y vs. number of drying cycles, X is in accordance with the model:
Y=A logeX+B
wherein A is in the range of from about 2.5 up to about 10.5 and B is in the range of from about 1.5 up to about 31.5 and, wherein the % weight loss of fragrance Y vs. the days of dryer operation, θ is in accordance with the model:
Y=−αe−βθ+γ
wherein α is in the range of from about 3.0 up to about 4.5; β is in the range of from about 0.030 up to about 0.045 and γ is in the range of from about 2.5 up to about 5.5. The aforementioned ranges of the values of A, B, α, β and γ were determined using the data and specific mathematical models for Table II in Example II, Table IV(c) in Example III, and Table V(c) in Example IV.
As stated, each of the efficaciously releasable components of the fragrance composition absorbed into the pores of the polymeric particles contained in the sachets of our invention has a C log10P (calculated logarithm of base 10 of the n-octanol/water partition coefficient) of between 1 and 8, according to the inequality: 1≦C log10P≦8. The range of fragrance composition in the polymeric particle is from about 5% by weight of the particle up to about 45% by weight of the particle. The values of log10P with respect to fragrance components are discussed in detail in U.S. Pat. Nos. 5,540,853 and 6,451,065 the specifications of which are incorporated herein by reference. Specific examples of fragrance components useful in the practice of our invention and the value of the C log10P's thereof are as follows:
Referring to the sachet articles useful in the practice of our invention as illustrated in
Use of the sachet article 10 in accordance with the process of our invention, is illustrated schematically in
The following fragrance is prepared for use with sachets employed in Examples I–V:
Sachets 10 as illustrated in
Ten 12 inch×36 inch towels, and 1 cup of PUREX, trademark of Dial Corporation, Phoenix, Ariz., non-fragranced detergent are placed in a General Electric washing machine (i) at ‘high’ water level, (ii) at ‘cold-warm’ water temperature and (iii) at ‘normal’ wash. The resulting washed towels are placed in a General Electric dryer along with one sachet produced as set forth supra, at ‘cotton’ setting for 60 minutes per cycle. At the end of each cycle, the towels are removed for sensory testing and sachets are removed for sensory testing and then replaced in the dryer for measurement at the end of the subsequent cycle. Hedonic and strength results on a scale of “0”, “least preferred” or weakest, to “5” most preferred or “having the most strength” are set forth in
Referring to
Referring to
Referring to
Referring to
Using the sachets of
The following Table II sets forth, for each of the sachet polymeric fragrance particle types of Table I, a mathematical regression model based on the data in Table I:
Referring to
Using the sachets of
In addition, using the sachets of
This example demonstrates the ability of the present invention to provide consistent release of fragrance after being used multiple times in a clothes dryer.
Using the sachets of
This example demonstrates the efficacy of the present invention in delivery of fragrance over time and the ability of the sachet to be used multiple times in the drying cycle.
500 grams of the ester-terminated polyamide, UNICLEAR 100V, is melted at 90° C. and placed in a vessel equipped with an agitator and heating coils in order to maintain constant temperature. Simultaneously, 200 grams of the perfume composition of Example A is heated to 90° C. The fragrance is then poured into the molten UNICLEAR 100V with agitation at 50 rpm. After agitation is continued, keeping a constant temperature, for a period of 0.5 hours, the resulting fragrance-ester-terminated polyamide mixture is poured into 3000 milliliters of distilled water held in an insulated open vessel equipped with an agitator and cooling coils, at 3° C. thereby effecting precipitation of polymeric fragrance pellets each of which has an effective diameter of from about 3 mm to about 7 mm.
The pellets of the present invention when utilized in procedures as set forth in Examples I, II, III and IV yielding substantially the same beneficial results as those when sachets A-1, A-3, A-4 and A-5 are used with the towels described in Example I.
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