A substantially dry composition, especially for personal care products is provided which includes a colorant activatable in water to release a visual color, and an oil-soluble carrier. The colorant is insoluble in the carrier and the visual color is not imparted to the composition in its substantially dry state. Addition of water to the composition activates a color change which renders the visual color perceivable by a consumer. Color changes can be associated as a signal of performance by a consumer.

1. Field of the Invention
The invention relates to personal care products, especially cleansers, which develop color when the compositions are combined with water.
2. The Related Art
Consumers often measure efficacy of a personal care product through some physically perceivable sensorial signal. Skinfeel of a product is one of the most common signals. Silky, non-residue leaving cosmetics are much preferred over tacky ones, and consumers may relate those aesthetics to actual pharmacological performance.
Temperature may operate as a sensorial signal. Coolness can be imparted to toothpastes, aftershave lotions and shower gels through the presence of camphor, menthol or menthol releasing derivatives. Some formulations signal efficacy through a temperature increase. Inclusion of capsaicin gives a brief temperature rise sensation to the human neural system. Exothermic and endothermic reactions are other sources of temperature signaling. U.S. Pat. No. 6,270,783 B1 (Slavtcheff et al.) and WO 01/12150/A1 (Mohammadi) illustrate interactive effects of temperature changes in combination with color generation.
Products by Schering-Plough Healthcare Products, Inc. and related patents introduced a sunscreen lotion with an indicator brightly colorizing the lotion until applied to the human skin. Upon rub-in, the lotion decolorizes or turns clear. A user of the product can through visual means ensure even distribution of the sunscreen over the body. The mechanism is based upon an aqueous system with a pH sensitive indicator. On the skin, water from the lotion evaporates altering pH and eventually decolorizing the applied product. See U.S. Pat. No. 6,086,858 (McEleney et at.), U.S. Pat. No. 6,007,797 (Bell et al.), U.S. Pat. No. 6,146,618 (Bell et al.), U.S. Pat. No. 6,099,825 (McShane et al.), U.S. Pat. No. 6,290,936 B1 (Ross et al.), and U.S. Pat. No. 5,747,011 (Ross et al.).
Use of pH indicators has also been incorporated into a dental floss. See U.S. Pat. No. 5,357,989 (Gathani).
Another commercial embodiment of a color change signal is Biore(copyright) Self Heating Mask. The product lists the following ingredients: butylene glycol, sodium silico aluminate, kaolin, PEG-8, methyl gluceth-20, hydroxypropyl cellulose, dimethicone, hydroxypropyl methylcellulose, talc, acrylates copolymer, polyethylene and minor ingredients including encapsulated ultramarine pigments. Instructions on use of the product require wetting of the face which when contacted with the Biore(copyright) product causes self-heating by reaction of water with the silico aluminates and kaolin. The composition is applied by rubbing across the face. Massage through the rubbing action breaks the encapsulating material, releasing the ultramarine pigments thereby turning the composition a uniform blue color. Once developed, the blue color signals the consumer it is time to rinse away the product. Further information on this product appears in U.S. Pat. No. 6,309,655 B1 (Minnix). A drawback of this system is the requirement for actual physical breakdown of walls encapsulating the colorant. This procedure is messy and requires an active manipulation. Furthermore, blue beads are visible (ranging from greater than 200 to 800 microns) in the starting Biore(copyright) product even before application and wider release of the pigments.
New mechanisms for color change signals have been sought which are less restrictive than those of the known art.
Accordingly, it is an advantage of the present invention to be able to provide personal care products, with a color sensorial signal change.
Another advantage of the present invention is to be able to provide personal care products, especially non-lathering creamy cleansers which change from white to another color after the product is combined with water.
These and other advantages of the present invention will become more readily apparent from consideration of the following summary and detailed discussion.
A personal care, substantially dry composition is provided which includes:
(i) a colorant activatable in water to reveal a visual color; and
(ii) an oil soluble carrier;
wherein the colorant is insoluble in the carrier and does not impart the visual color to the composition in its substantially dry state.
Now it has been found that a color signal can be generated from a substantially dry composition that is an oil soluble carrier formulated with a water soluble inorganic or organic colorant. In the substantially dry state, the composition receives no color contribution from the colorant. However, once a consumer mixes water into the composition, such as in a skin cleansing process, a color change occurs.
The starting color of compositions according to this invention may essentially be any color. However, most preferred is a white or slightly off-white color, usually imparted by an opacifier such as titanium dioxide. Colorants when present as beads may be of a color different from that of the initial color. However, a consumer will essentially not perceive the bead or its color because of its small size. Thus, colorants that may be present in bead form will have an average particle size ranging from about 0.0001 to about 200 xcexcm, preferably no higher than about 150 xcexcm, more preferably no higher than about 100 xcexcm, optimally no higher than about 50 xcexcm. Advantageously, no more than 30% of the colorant beads should have a particle size greater than 200 xcexcm, preferably not more than 150 xcexcm.
Accordingly, an important element of the present invention is that of an oil soluble carrier which is a hydrophobic system of one or more components having a weighted arithmetic mean solubility parameter of less than or equal to 10.5. It is recognized, based on this mathematical definition of solubility parameters, that it is possible, for example, to achieve the required weighted arithmetic mean solubility parameter, i.e. less than or equal to 10.5, for a hydrophobic carrier comprising two or more substances if one of the substances has an individual solubility parameter greater than 10.5.
Solubility parameters are well known to the formulation chemist of ordinary skill in the art and are routinely used as a guide for determining compatibility""s and solubilities of materials in the formulation process.
The solubility parameter of a chemical compound, xcex4 is defined as the square root of the cohesive energy density for that compound. Typically, a solubility parameter for a compound is calculated from tabulated values of the additive group contributions for the heat of vaporization and molar volume of the components of that compound, using the following equation:   δ  =            [                                                  ∑              i                                      xe2x80x83                                                      xe2x80x83                                          E            i                                                ∑            i                                          m            i                              ]              1      /      2
wherein xcexa3i Ei=the sum of the heat of vaporization additive group contributions, and xcexa3i mi=the sum of the molar volume additive group contributions
Standard tabulations of heat of vaporization and molar volume additive group contributions for a wide variety of atoms and groups of atoms are collected in Barton, A. F. M. Handbook of Solubility Parameters, CRC Press, Chapter 6, Table 3, pp. 64-66 (1985), which is incorporated by reference herein in its entirety. The above solubility parameter equation is described in Fedors, F. R., xe2x80x9cA Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquidsxe2x80x9d, Polymer Engineering and Science, vol. 14, no. 2, pp. 147-154 (February 1974), which is incorporated by reference herein in its entirety.
Solubility parameters obey the law of mixtures such that the solubility parameter for a mixture of materials is given by the weighted arithmetic mean (i.e. the weighted average) of the solubility parameters for each component of that mixture. See, Handbook of Chemistry and Physics, 57th edition, CRC Press, p. C-726 (1976-1977), which is incorporated by reference herein in its entirety.
Formulation chemists typically report and use solubility parameters in units of (cat/cm3)1/2. The tabulated values of additive group contributions for heat of vaporization in the Handbook of Solubility Parameters are reported in units of kJ/mol. However, these tabulated heat of vaporization values are readily converted to cal/mol using the following well-known relationships:
1 J/mol=0.239006 cal/mol and 1000 J=1 kJ.
See Gordon, A. J. et al., The Chemist""s Companion, John Wiley and Sons, pp. 456-463, (1972), which is incorporated by reference herein in its entirety.
Solubility parameters have also been tabulated for a wide variety of chemical materials. Tabulations of solubility parameters are found in the above-cited Handbook of Solubility Parameters. Also, see xe2x80x9cSolubility Effects In Product, Package, Penetration, And Preservationxe2x80x9d, C. D. Vaughan, Cosmetics and Toiletries, vol. 103, October 1988, pp. 47-69, which is incorporated by reference herein in its entirety.
Nonlimiting examples of hydrophobic carriers include those selected from the group consisting of mineral oil, petrolatum, lecithin, hydrogenated lecithin, lanolin, lanolin derivatives, C7-C40 branched chain hydrocarbons, C1-C30 alcohol esters of C1-C30 carboxylic acids, C1-C30 alcohol esters of C2-C30 dicarboxylic acids, monoglycerides of C1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30 carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids, propylene glycol monoesters of C1-C30 carboxylic acids, propylene glycol diesters of C1-C30 carboxylic acids, C1-C30 carboxylic acid monoesters and polyesters of sugars, polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cyclomethicones having 3 to 9 silicon atoms, vegetable oils, hydrogenated vegetable oils, polypropylene glycol C4-C20 alkyl ethers, di C8-C30 alkyl ethers, and combinations thereof.
Mineral oil, which is also known as petrolatum liquid, is a mixture of liquid hydrocarbons obtained from petroleum. See The Merck Index, Tenth Edition, Entry 7048, p. 1033 (1983) and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1, p. 415-417 (1993), which are incorporated by reference herein in their entirety.
Petrolatum, which is also known as petroleum jelly, is a colloidal system of nonstraight-chain solid hydrocarbons and high-boiling liquid hydrocarbons, in which most of the liquid hydrocarbons are held inside the micelles. See The Merck Index, Tenth Edition, Entry 7047, p. 1033 (1983); Schindler, Drug. Cosmet., Ind., 89, 36-37, 76, 78-80, 82 (1961); and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1, p. 537 (1993), which are incorporated by reference here in their entirety.
Lecithin is also useful as a hydrophobic carrier. It is a naturally occurring mixture of the diglycerides of certain fatty acids, linked to the choline ester of phosphoric acid.
Straight and branched chain hydrocarbons having from about 7 to about 40 carbon atoms are useful herein. Nonlimiting examples of these hydrocarbon materials include dodecane, isododecane, squalane, cholesterol, hydrogenated polyisobutylene, docosane (i.e. a C22 hydrocarbon), hexadecane, isohexadecane (a commercially available hydrocarbon sold as Permethyl(copyright) 101 A by Presperse, South Plainfield, N.J.). Also useful are the C7-C40 isoparaffins, which are C7-C40 branched hydrocarbons. Polydecene, a branched liquid hydrocarbon, is also useful herein and is commercially available under the tradenames Puresyn 100(copyright) and Puresyn 3000(copyright) from Mobile Chemical (Edison, N.J.).
Also useful are C1-C30 alcohol esters of C1-C30 carboxylic acids and of C2-C30 dicarboxylic acids, including straight and branched chain materials as well as aromatic derivatives. Also useful are esters such as monoglycerides of C1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30 carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids, propylene glycol monoesters of C1-C30 carboxylic acids, and propylene glycol diesters of C1-C30 carboxylic acids. Straight chain, branched chain and aryl carboxylic acids are included herein. Also useful are propoxylated and ethoxylated derivatives of these materials. Nonlimiting examples include diisopropyl sebacate, diisopropyl adipate, isopropyl myristate, isopropyl palmitate, myristyl propionate, ethylene glycol distearate, 2-ethylhexyl palmitate, isodedecyl neopentanonoate, di-2-ethylhexyl maleate, cetyl palmitate, myristyl myristate, stearyl stearate, cetyl stearate, behenyl behenrate, dioctyl maleate, dioctyl sebacate, diisopropyl adipate, cetyl octanoate, diisopropyl dilinoleate, caprylic/capric triglyceride, PEG-6 caprylic/capric triglyceride, PEG-8 caprylic/capric triglyceride, and combinations thereof.
Also useful are various C1-C30 monoesters and polyesters of sugars and related materials. These esters are derived from a sugar or polyol moiety and one or more carboxylic acid moieties. Depending on the constituent acid and sugar, these esters can be in either liquid or solid form at room temperature. Examples of liquid esters include: glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the galactose tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucrose heptaoleate, sucrose octaoleate, and mixtures thereof. Examples of solid esters include: sorbitol hexaester in which the carboxylic acid ester moieties are palmitoleate and arachidate in a 1:2 molar ratio; the octaester of raffinose in which the carboxylic acid ester moieties are linoleate and behenate in a 1:3 molar ratio; the heptaester of maltose wherein the esterifying carboxylic acid moieties are sunflower seed oil fatty acids and lignocerate in a 3:4 molar ratio; the octaester of sucrose wherein the esterifying carboxylic acid moieties are oleate and behenate in a 2:6 molar ratio; and the octaester of sucrose wherein the esterifying carboxylic acid moieties are laurate, linoleate and behenate in a 1:3:4 molar ratio. A preferred solid material is sucrose polyester in which the degree of esterification is 7-8, and in which the fatty acid moieties are C18 mono- and/or di-unsaturated and behenic, in a molar ratio of unsaturates: behenic of 1:7 to 3:5. A particularly preferred solid sugar polyester is the octaester of sucrose in which there are about 7 behenic fatty acid moieties and about 1 oleic acid moiety in the molecule.
Nonvolatile silicones such as polydialkylsiloxanes, polydiarylsiloxanes, and polyalkarylsiloxanes are also useful oils. The polyalkysiloxanes correspond to the general chemical formula R3SiO[R2SiO]xSiR3 wherein R is an alkyl group (preferably R is methyl or ethyl, more preferably methyl) and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercially available polyalkysiloxanes include the polydimethylsiloxanes, which are also known as dimethicones, nonlimiting examples of which include the Vicasil(copyright) series sold by General Electric Company and the Dow Corning(copyright) 200 series sold by Dow Corning Corporation. Specific examples of polydimethylsiloxanes useful herein include Dow Corning(copyright) 225 fluid having a viscosity of 10 centistokes and a boiling point greater than 200xc2x0 C., and Dow Corning(copyright) 200 fluids having viscosities of 50, 350, and 12,500 centistokes, respectively, and boiling points greater than 200xc2x0 C. Also useful are materials such as trimethylsiloxysilicate, which is a polymeric material corresponding to the general chemical formula [(CH2)3SiO1/2]x[SiO2]y, wherein x is an integer from about 1 to about 500 and y is an integer from about 1 to about 500. A commercially available trimethylsiloxysilicate is sold as a mixture with dimethicone as Dow Corning(copyright) 593 fluid.
Also useful herein are dimethiconols, which are hydroxy terminated dimethyl silicones. These materials can be represented by the general chemical formulas R3SiO[R2SiO]xSiR2OH and HOR2SiO[R2SiO]xSiR2OH wherein R is an alkyl group (preferably R is methyl or ethyl, more preferably methyl) and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercially available dimethiconols are typically sold as mixtures with dimethicone or cyclomethicone (e.g. Dow Corning(copyright) 1401, 1402, and 1403 fluids).
Also useful herein are polyalkylaryl siloxanes, with polymethylphenyl siloxanes having viscosities from about 15 to about 65 centistokes at 25xc2x0 C. being preferred. These materials are available, for example, as SF 1075 methylphenyl fluid (sold by General Electric Company) and 556 Cosmetic Grade phenyl trimethicone fluid (sold by Dow Corning Corporation). Alkylated silicones such as methyldecyl silicone and methyloctyl silicone are useful herein and are commercially available from General Electric Company. Also useful herein are alkyl modified siloxanes such as alkyl methicones and alkyl dimethicones wherein the alkyl chain contains 10 to 50 carbons. Such siloxanes are commercially available under the tradenames ABIL WAX 9810 (C24-C28 alkyl methicone) (sold by Goldschmidt) and SF1632 (cetearyl methicone) (sold by General Electric Company).
Vegetable oils and hydrogenated vegetable oils are also useful herein. Examples of vegetable oils and hydrogenated vegetable oils include safflower oil, castor oil, coconut oil, cottonseed oil, menhaden oil, palm kernel oil, palm oil, peanut oil, soybean oil, rapeseed oil, linseed oil, rice bran oil, pine oil, sesame oil, sunflower seed oil, hydrogenated safflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated menhaden oil, hydrogenated palm kernel oil, hydrogenated palm oil, hydrogenated peanut oil, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated linseed oil, hydrogenated rice bran oil, hydrogenated sesame oil, hydrogenated sunflower seed oil, and mixtures thereof.
Also useful are C4-C20 alkyl ethers of polypropylene glycols, C1-C20 carboxylic acid esters of polypropylene glycols, and di-C8-C30 alkyl ethers. Nonlimiting examples of these materials include PPG-14 butyl ether, PPG-15 stearyl ether, dioctyl ether, dodecyl octyl ether, and mixtures thereof.
Amounts of the oil soluble hydrophobic carrier may range from about 20 to about 99.9%, preferably from about 50 to about 99, more preferably from about 60 to about 95, optimally from about 70 to about 85% by weight of the composition.
Generally, glycols such as propylene glycol and butylene glycol will not be useful as the carriers, especially where they are present in any substantial amount. By this is meant, amounts higher than 50%, or at least amounts higher than 20%, and in some systems in amounts higher than 10% by weight of the composition.
By the term xe2x80x9csubstantially dryxe2x80x9d is meant a composition which has a water content no higher than about 15%, preferably no higher than about 10%, more preferably no higher than about 5%, and optimally between 0 and 4% by weight of the composition.
Another important element of the compositions according to the present invention is that of a water-soluble colorant. A colorant is a material which when placed in water will cause that system to be visually perceivable by a consumer as having a color other than white or cream. Suitable signal colors can be yellow, green, blue, red, orange, black and intermediary shades such as pink. Water-solubility is related to a solubility parameter as discussed above having a value greater than about 10.5, preferably greater than 12.
Amounts of the water-soluble colorant may range from about 0.000001 to about 2%, preferably from about 0.00001 to about 1%, more preferably from about 0.0001 to about 0.5%, even more preferably from about 0.001 to about 0.1%, optimally from about 0.005 to about 0.01% by weight of the composition.
Colorants may be inorganic or organic, with the latter being preferred. Organic colorants include copper salts such as copper sulphate, manganese salts such as potassium permanganate or molybdenum salts such as molybdenum phosphate. Suitable organic colorants are FDandC and DandC dyes. Illustrative are FDandC Blue #1, FDandC Blue #2, FDandC Green #3, FDandC Red #3, FDandC Red #4, FDandC Red #40, FDandC Yellow #5, FDandC Yellow #6, DandC Blue #4, DandC Green #5, DandC Red #6, DandC Red #22, DandC Red #28, DandC Red #33, DandC Yellow #10, Ext DandC Violet #2, Ext DandC Yellow #7, DandC Green #8, DandC Orange #4, DandC Yellow #8, DandC Brown #1, DandC Violet #2 and mixtures thereof. Most preferred is FDandC Green #3.
Although compositions of the present invention may contain components which generate heat upon contact with water (e.g. zeolite), the compositions of the present invention in preferred embodiments do not contain sufficient amounts of these materials to generate any consumer perceivable heat. Likewise, in certain preferred embodiments of the present invention, the compositions will not contain sunscreens in sufficient amount to be legally termed (U.S. FDA-Monograph at 21 CRF 352.10) as a sunscreen product.
Besides the water-insoluble carrier and water-soluble colorants, compositions of the present invention may contain various other types of functional ingredients. These include surfactants, skin benefit agents, thickeners, opacifiers, preservatives, fragrances and mixtures thereof. These materials in total may range in amount from about 0.1 to about 80%, preferably from about 5 to about 60%, more preferably from about 10 to about 40%, optimally from about 15 to about 30% by weight of the composition in total.
Surfactants useful for the present invention may be of the anionic, nonionic, cationic or amphoteric variety as well as combinations thereof. Typical anionic surfactants include salts of acyl isethionates (e.g. sodium cocoyl isethionate), acyl taurates, acyl sarcosinates, acyl lactylates, alkyl ether sulphates, alkyl sulphates and soaps. Useful nonionic surfactants include the C10-C20 fatty alcohols or acid hydrophobes condensed with from 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe; C2-C10 alkyl substituted phenols condensed with from 2 to 20 moles of alkylene oxide; mono- and di-fatty acid esters of ethylene glycol; fatty acid monoglyceride; sorbitan, mono- and di-C8-C20 fatty acids; block copolymers (ethylene oxide/propylene oxide); and polyoxyethylene sorbitan as well as combinations thereof. Alkyl polyglycosides and saccharide fatty amides (e.g. methyl gluconamides) are also suitable nonionic surfactants. Useful cationic surfactants include trimethyl fatty ammonium salts such as trimethyl stearyl ammonium sulphate. Amphoteric surfactants are illustrated by such materials as cocoamidopropyl betaine and lauroamophoacetates. The amount of surfactant used may range from about 0.01 to about 30%, preferably from about 0.5 to about 10% by weight of the composition.
Skin benefit agents useful in the present invention include alpha and beta hydroxycarboxylic acids as well as their salts and esters, vitamins, lipoic acids, herbal extracts, cationic polymers, self tanning agents, depilatories, skin tightening agents and mixtures thereof. Illustrative alpha-hydroxycarboxylic acids include glycolic acid, malic acid, lactic acid, gluconolactone and mixtures thereof. Salicylic acid is the most preferred beta hydroxycarboxylic acid. Suitable vitamins include the Vitamin A family of retinol, retinyl C2-C20 fatty acid esters and retinoic acid; Vitamin B materials such as niacinamide; Vitamin C and its derivatives such as ascorbic acid, ascorbyl tetraisopalmitate, magnesium ascorbyl phosphate and ascorbyl glucoside; Vitamin E such as tocopherol and C2-C20 fatty acid tocopherol esters; and folic acid. Cationic polymers most preferred are Polymer JR(copyright) and Jaguar C(copyright) (e.g. Jaguar C18(copyright)). Self-tanning agents principally include dihydroxyacetone. Useful skin tightening agents are kojic acid, resorcinol, arbutin, placental extract, chamomile extract, lactic acid and mixtures thereof. Amounts of the skin benefit agent may range from about 0.00001 to about 15% by weight of the composition.
Thickeners may be included in the compositions at levels from about 0.0001 to about 10%, preferably from about 0.1 to about 1% by weight of the composition. Illustrative materials include C12-C24 fatty acids, N-fatty glutamic acid dialkylamides, carboxyvinyl polymers such as the Carbomers, polyacrylamides such as Sepiget(copyright) 305, taurates, magnesium aluminum silicate (e.g. Veegum(copyright)), carboxymethyl cellulose and other cellulose derivatives, aluminum Starch Octenyl Succinates (e.g. Dry Flo(copyright)), bentonite clays (e.g. Bentone 38(copyright)) and any combinations thereof. Particularly preferred thickeners are stearic acid and N-lauroyl glutamic acid di-N-butylamide.
Opacifiers may also be included in the compositions. These materials may be polyethylene, polystyrenes, polyacrylates, polyamides and copolymers thereof. Most preferred is titanium dioxide, but especially water-dispersible titanium dioxide. Amounts of the opacifiers may range from about 0.001 to about 2% by weight of the composition.
Preservatives useful for the present invention include parabens such as methyl and propyl parabens, and commercially available materials such as Glydant and Glydant Plus(copyright). These may be present in amounts from about 0.0001 to about 1% by weight of the composition.
By the term xe2x80x9cpersonal carexe2x80x9d is meant products such as skin cleansers, hair treatments (e.g. shampoos, mousses and conditioners), depilatories, skin lightening products, and leave-on skin lotions and creams. These products may be delivered from wipes (e.g. nonwoven substrates), liquids, gels, pumps or stick format.
All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise illustrated.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material ought to be understood as modified by the word xe2x80x9caboutxe2x80x9d.
The term xe2x80x9ccomprisingxe2x80x9d is meant not to be limiting to any subsequently stated elements but rather to encompass non-specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words xe2x80x9cincludingxe2x80x9d or xe2x80x9chavingxe2x80x9d are used, these terms are meant to be equivalent to xe2x80x9ccomprisingxe2x80x9d as defined above.

Personal care composition with color change indicator

Unilever Home and Personal Care USA, division of Conopco, Inc.


The electric plug system for the automatic transmission of a motor vehicle consists of a socket situated on the transmission and of a plug engaging in the socket wherein the cylindrical end (10) of the socket that accommodates the plug traverses a bore (3) in the transmission which is placed in the oil pan. The socket has a radial flange (5) to which attaches a cylindrical segment (6) of small diameter followed by the cylindrical end of a diameter still further reduced. The cylindrical end and the cylindrical segment are surrounded by a centering sleeve which by a locking system on the outer side of the oil pan can be firmly connected with the latter.

According to the preamble of claim 1, this invention concerns an electric plug system for the automatic transmissions of motor vehicles and consists of a socket and a plug that engages in the socket to create a connection between the electronic transmission control device situated in the transmission and the electric feed lines integrated in the wire harness of the motor vehicle.
Automatic transmissions for motor vehicles such as have been manufactured in large numbers by the Applicant have an electronic transmission control device or an electrohydraulic control often provided with an electronic module which is to be connected with a cable harness situated outside the transmission. The electric feed lines in the proximity of the electronic module within the transmission can be designed as flat lines connected, for example, with a socket of the electronic transmission control which is placed in the transmission housing after which the electric connection to the vehicle cable harness is created by plugging a matching plug.
The transmission wall usually is, at the same time, the dividing wall between the transmission control situated within the transmission housing and connected with a socket carrying electric contacts which is inserted in the transmission wall. The matching plug which is plugged in the socket is connected in circuit with the inputs and outputs of a control electronic system for monitoring and controlling the electronic system contained in the automatic transmission.
An electric plug system for the automatic transmissions of motor vehicles has been disclosed in DE U 297 21 908. In this plug system, the plug part is part of an electric plate from which the electric plug contacts pointedly project toward the wall of the transmission.
The plug contact arrangement is delimited by a web-like enclosing edge. The enclosing edge forms a seat for the front section of the plug socket part and for accommodating a guide sleeve. The guide sleeve is disposed projecting support and the locking device. The locking device is movably disposed on the plug part for advancing the locking stop.
Even though it is thereby possible with simple means to obtain a tension-free assembly with simultaneous fastening free from play of the plug system on the transmission wall, here, the same as in the plug systems at present customary for automatic transmissions of motor vehicles, the socket is situated in the transmission housing in a place in which problems occur predetermined as result of the narrow installation space in the Cardan tunnel and the high temperatures that generate here due to the exhaust system.
The problem to be solved by this invention is to provide an electric plug system for automatic transmissions of motor vehicles which eliminates the problems associated with the small installation space and the high temperatures generated by the exhaust system, which is more accessible than the conventional plug systems and which is adequate as standard interface for the electric connection of the transmission with the control system in the motor vehicle for all types of vehicles known.
It is also provided according to the invention that the plug system consisting of a socket situated in the transmission and of a plug engaging in the socket be constructed as follows:
the bore is provided in the oil pan and has on its upper outer edge a conical chamfer while in its underside is provided with an annular collar;
the socket is provided on its end facing the interior of the transmission with a radial flange having an outer diameter larger than the diameter of the bore in the oil pan and substantially equal to the outer diameter of the annular collar;
to the flange attaches a cylindrical segment having an outer diameter substantially equal to the diameter of the bore, there being provided in this segment an annular groove in which a seal engages;
to the cylindrical section attaches a cylindrical end that penetrates the bore and projects out of it, there being provided on the outer wall of the cylindrical end two locking gates opposite each other and each forming a guideway;
the cylindrical end and the cylindrical segment are surrounded by a centering sleeve having an outer diameter substantially equal to the diameter of the bore, the centering sleeve being provided on its outer side with an annular groove in which a seal engages;
the centering sleeve is provided with a locking clamp tiltably supported on it and having two guide pilots which interact with the locking gate on the cylindrical end and
the locking clamp acts together with a fixing device provided on the outer side of the oil pan.
The inventive electric plug system essentially refers to the design of the socket, which is placed in the oil pan and is in direct communication with the electronic transmission control within the transmission, offers the advantage of a simple construction at reasonable cost and an assembly without problem. The placing on the oil pan instead of on the transmission wall makes possible access without problem and protects it against unacceptable temperature increases.


A polypropylene blend including from 0.5 to 50% by weight of a syndiotactic polypropylene having a multimodal molecular weight distribution and at least 50% by weight of an isotactic polypropylene.

The present invention relates to polypropylene fibres and to fabrics produced from polypropylene fibres.
Polypropylene is well known for the manufacture of fibres, particularly for manufacturing non woven fabrics.
EP-A-0789096 discloses such polypropylene fibres which are made of a blend of syndiotactic polypropylene (sPP) and isotactic polypropylene (iPP). That specification discloses that by blending from 0.3 to 3% by weight of sPP, based on the total Wj polypropylene, to form a blend of iPP-sPP, the fibres have increased natural bulk and smoothness, and non-woven fabrics produced from the fibres have an improved softness. Moreover, that specification discloses that such a blend lowers the thermal bonding temperature of the fibres. Thermal bonding is employed to produce the non-woven fabrics from the polypropylene fibres. The specification discloses that the isotactic polypropylene comprises a homopolymer formed by the polymerisation of propylene by Ziegler-Natta catalysis.
WO-A-96/23095 discloses a method for providing a non-woven fabric with a wide bonding window in which the non-woven fabric is formed from fibres of a thermoplastic polymer blend including from 0.5 to 25 wt % of syndiotactic polypropylene. The syndiotactic polypropylene may be blended with a variety of different polymers, including isotactic polypropylene. The specification includes a number of examples in which various mixtures of syndiotactic polypropylene with isotactic polypropylene were produced. The isotactic polypropylene comprised commercially available isotactic polypropylene, which is produced using a Ziegler-Natta catalyst. It is disclosed in the specification that the use of syndiotactic polypropylene widens the window of temperature over which thermal bonding can occur, and lowers the acceptable bonding temperature.
WO-A-96/23095 also discloses the production of fibres from blends including syndiotactic polypropylene which are either bi-component fibres or bi-constituent fibres. Bi-component fibres are fibres which have been produced from at least two polymers extruded from separate extruders and spun together to form one fibre. Bi-constituent fibres are produced from at least two polymers extruded from the same extruder as a blend. Both bi-component and bi-constituent fibres are disclosed as being used to improve the thermal bonding of Ziegler-Natta polypropylene in non-woven fabrics. In particular, a polymer with a lower melting point compared to the Ziegler-Natta isotactic polypropylene, for example polyethylene, random copolymers or terpolymers, is used as the outer part of the bi-component fibre or blended in the Ziegler-Natta polypropylene to form the bi-constituent fibre.
EP-A-0634505 discloses improved propylene polymer yarn and articles made therefrom in which for providing yarn capable of increased shrinkage syndiotactic polypropylene is blended with isotactic polypropylene with there being from 5 to 50 parts per weight of syndiotactic polypropylene. It is disclosed that the yarn has increased resiliency and shrinkage, particularly useful in pile fabric and carpeting. It is disclosed that the polypropylene blends display a lowering of the heat softening temperature and a broadening of the thermal response curve as measured by differential scanning calorimetry as a consequence of the presence of syndiotactic polypropylene.
U.S. Pat. No. 5,269,807 discloses a suture fabricated from syndiotactic polypropylene exhibiting a greater flexibility than a comparable suture manufactured from isotactic polypropylene. The syndiotactic polypropylene may be blended with, inter alia, isotactic polypropylene.
EP-A-0451743 discloses a method for moulding syndiotactic polypropylene in which the syndiotactic polypropylene may be blended with a small amount of a polypropylene having a substantially isotactic structure. It is disclosed that fibres may be formed from the polypropylene. It is also disclosed that the isotactic polypropylene is manufactured by the use of a catalyst comprising titanium trichloride and an organoaluminium compound, or titanium trichloride or titanium tetrachloride supported on magnesium halide and an organoaluminium compound, i.e. a Ziegler-Natta catalyst.
EP-A-0414047 discloses polypropylene fibres formed of blends of syndiotactic and isotactic polypropylene. The blend includes at least 50 parts by weight of the syndiotactic polypropylene and at most 50 parts by weight of the isotactic polypropylene. It is disclosed that the extrudability of the fibres is improved and the fibre stretching conditions are broadened.
U.S. Pat. No. 5,648,428 discloses a process for producing a polymer blend in a single reactor, specifically a polymer blend of isotactic polyolefin and syndiotactic polyolefin which may comprise polypropylene. The single reactor is provided with a catalyst system comprising a combination of at least one metallocene catalyst and at least one conventional supported Ziegler-Natta catalyst.
These known polypropylenes suffer from the disadvantage that the processability of the iPP/sPP blends needs to be improved, particularly for spinning fibres, so that higher spinning speeds can be employed before fibre breakage occurs or the incidence of breakage at any given spinning speed is reduced.
It is further known to produce syndiotactic polypropylene using metallocene catalysts as has been disclosed for example in U.S. Pat. No. 4,794,096.
WO-A-96/35729 discloses a process for preparing and using a supported metallocene-alumoxane catalyst which is used for the polymerisation or copolymerisation of olefins to produce an olefin polymer or copolymer having a broad and bimodal molecular weight distribution.
It is an aim of the present invention to produce a blend of iPP and sPP which has improved processability, particularly when forming spun fibres. It is a further aim of the present invention to provide fibres, and fabrics in particular non-woven fabrics made from those fibres, which have been produced from that blend.
The present invention provides a polypropylene blend including from 0.3 to 50% by weight of a syndiotactic polypropylene having a multimodal molecular weight distribution and at least 50% by weight of an isotactic polypropylene.
The SPP is typically bimodal.
The isotactic polypropylene (iPP) may have been produced using a Ziegler-Natta catalyst and may be a homopolymer or copolymer and may have a monomodal or multimodal molecular weight distribution.
Preferably, the syndiotactic polypropylene (sPP) concentration in the sPP/iPP blend is from 0.3 to 15 wt %, more preferably from 1 to 10 wt %. The fibre may be a two component sPP/iPP blend.
Preferably, the iPP is a homopolymer, copolymer, being either a random or block copolymer, or terpolymer of isotactic polypropylene.
Typically, the isotactic polypropylene has a melting temperature in the range of from 159 to 169xc2x0 C., more typically from 161 to 165xc2x0 C. The iPP employed in accordance with the invention has a molecular weight distribution typically having a dispersion index D of from 3.5 to 9, more preferably from 3.5 to 6.5. The dispersion index D is the ratio Mw/Mn, where Mw is the weight number average molecular weight and Mn is the number average molecular weight of the polymer. The iPP typically has a peak in the molecular weight distribution of around 35,000 to 60,000 kDa. The isotactic polypropylene may have an Mn of from 35,000 to 45,000 kDa.
The isotactic polypropylene preferably has a melt flow index (MFI) of from 1 to 90 g/10 mins, more preferably from 10 to 60 g/10 mins. In this specification the MFI values are those determined using the procedure of ISO 1133 using a load of 2.16 kg at a temperature of 230xc2x0 C.
The properties of two typical iPP resins for use in the invention are specified in Table 1.
The multimodal sPP, preferably bimodal sPP, is preferably a homopolymer or a random copolymer with a comonomer content of from 0.1 to 1.5 wt %, more preferably from 0.1 to 1 wt %. The multimodal sPP may however be a block copolymer with a higher comonomer content or a terpolymer. If the comonomer content is above 1.5 wt %, the sPP tends to become sticky, thus resulting in problems when spinning the fibres or thermally bonding the fibres. The comonomer content is selected so as to decrease the melting point of the sPP/iPP blend below 130xc2x0 C. A lower melting point can also be obtained by using particular catalysts and/or process conditions during polymerisation of the sPP. Preferably, the sPP has a melting temperature of up to about 130xc2x0 C. The sPP typically has two melting peaks, one being around 110xc2x0 C. and the other being around 125xc2x0 C. The sPP typically has an MFI of from 0.1 to 1000 g/10 min, more typically from 1 to 60 g/10 min. The multimodal sPP may have an Mn of from 35,000 to 40,000 kDa. The properties of a typical bimodal sPP for use in the invention are specified in Table 1.
The sPP has a slightly narrower molecular weight distribution than for the iPP, wherein typically D may be from 3 to 6, more typically around 4 and has a peak of the molecular weight distribution at around 20,000 to 35,000 kDa. The sPP and the iPP may have substantially similar values for Mn. In view of the closeness between the peaks and the overlap of the molecular weight distributions of the sPP and the iPP, those two components can readily be blended together.
The present invention further provides a fibre produced from the polypropylene blend in accordance with the invention.
The present invention further provides a fabric produced from the polypropylene fibre of the invention.
The present invention yet further provides a product including that fabric, the product being selected from among others a filter, personal wipe, diaper, feminine hygiene product, incontinence product, wound dressing, bandage, surgical gown, surgical drape and protective cover.
The present invention is predicated on the discovery by the present inventor that when blended with iPP, multimodal sPP, preferably bimodal sPP, improves the processability of the polypropylene, particularly to form fibres in a spinning process, as compared to monomodal sPP.
The present inventor has found that when used in an amount of only about 2 wt % sPP in the sPP/iPP blend, the spinnability is increased when sPP is multimodal, preferably bimodal.
The use of multimodal e.g. bimodal sPP in blends with iPP in accordance with the invention tends to provide fibres which can be more readily-spun as compared to known fibres comprised of iPP blended with monomodal sPP. The molecular weight distributions of iPP and the multimodal sPP overlap, and as a result of the provision of sPP having a broad multimodal molecular weight distribution this provides increased overlap between the two distributions as compared to monomodal sPP, thereby improving the blend, and also provides a higher proportion of short chains in the combined molecular weight distribution for the blend. This has been found to result in an increase in the maximum spin speed before breakage for the fibres of the multimodal sPP/iPP blends in accordance with the invention.
The fibres produced in accordance with the invention may be either bi-component fibres or bi-constituent fibres. For bi-component fibres, iPP and sPP are fed into two different extruders. Thereafter the two extrudates are spun together to form single fibres. For the bi-constituent fibres, blends of sPP/iPP are obtained by: dry blending pellets, flakes or fluff of the two polymers before feeding them into a common extruder; or using pellets or flakes of a blend of sPP and iPP which have been extruded together and then re-extruding the blend from a second extruder.
When the blends of multimodal aPP/iPP are used to produce fibres in accordance with the invention, for the production of spunlaid fibres, a typical extrusion temperature would be in the range of from 200xc2x0 C. to 260xc2x0 C., most typically from 230xc2x0 C. to 250xc2x0 C. For the production of staple fibres, a typical extrusion temperature would be in the range of from 230xc2x0 C. to 330xc2x0 C., most typically from 280xc2x0 C. to 300xc2x0 C.
The fibres produced in accordance with the invention may be produced from multimodal sPP/iPP blends having other additives to improve the mechanical processing or spinnability of the fibres. The fibres produced in accordance with the invention may be used to produce non-woven fabrics for use in filtration; in personal care products such as wipers, diapers, feminine hygiene products and incontinence products; in medical products such as wound dressings, surgical gowns, bandages and surgical drapes; in protective covers; in outdoor fabrics and in geotextiles. Non-woven fabrics made with the bimodal sPP/iPP fibres of the invention can be part of such products, or constitute entirely the products. As well as making non-woven fabrics, the fibres may also be employed to make a woven knitted fabric or mat. The non-woven fabrics produced from the fibres in accordance with the invention can be produced by several processes, such as air through blowing, melt blowing, spun bonding or bonded carded processes. The fibres of the invention may also be formed as a non-woven spunlace product which is formed without thermal bonding by fibres being entangled together to form a fabric by the application of a high pressure-fluid such as air or water.