The present invention provides a method of preventing the appearance of fine lines, wrinkles and discoloration on the skin. This is achieved by the topical application to the skin of a composition containing a first platelet of alumina treated with a metal oxide, a second platelet treated with a spherical scattering component, and a cosmetic or pharmaceutical carrier. The compositions can also contain a standard interference pigment, such as a white and a yellow interference pigment to further blend the color to closely match the natural skin tone. The combination of pigments and platelets creates a mosaic of color and optically manipulates light such that lines, wrinkles, disfigurations and discolorations on the skin appear to substantially vanish. In addition to the pigments and platelet components, a non-interference pigment can also be added to fine-tune the matching of color to the skin tone. The alumina platelet alone is metallic-looking; however, when it is tempered with the other platelet containing the spherical scattering component, the net effect is that the skin appears natural, luminous and flawless.

The present invention relates to compositions containing various pigments which manipulate light. More specifically, the invention relates to compositions containing pigments which optimize the optical diffusion effect of light, and consequently cause the appearance of wrinkles, lines and discolorations to vanish and make the skin surface appear luminous, natural and flawless.
Makeup and foundation are used to create the appearance of an even skin tone. However, many users complain that these cosmetic products accentuate the appearance of their wrinkles and fine lines. This occurs because makeup builds up inside the crevice formed by the wrinkle. Traditional makeup products contain iron oxides as pigments to match the color of the skin. Iron oxides, inherently particulate, migrate into the crevice formed by a wrinkle or fine line in the skin. Therefore, when the makeup is initially applied, and after application, the makeup spreads on the skin, fills in the line, and in effect, highlights the wrinkle. As a result, the undesirable wrinkles, or flaws, are more noticeable. Because of this phenomenon, many users refrain from using makeup altogether, or do not apply makeup around, for example, their eye area because this region of the skin tends to have more fine lines and wrinkles, such as crows feet. Thus, using traditional pigments alone, the desired result of makeup, to provide an smooth and even looking skin tone, is defeated.
Even when makeup is not used on the skin, lines and wrinkles are visible on the skin and are considered, in a society that aims to achieve eternal youth, or at least the appearance of such, unattractive. The prominent appearance of lines and wrinkles on the skin is due to optical geometry. When light is directed in the direction of an object several events can occur depending on the nature of the object. One is the light can be directed as a reflection completely in one direction determined by the angle of incidence. This is similar to the well-known reflection phenomenon seen with a mirror. Another occurrence is the light can scatter in many different directions, or in a manner referred to as diffuse reflection. And also, the light can transmit through the object, if the object possesses sufficient transparency. This phenomenon also involves the refraction of light. As the light passes through the object its speed (or velocity) and wavelength changes according to the index of refraction, defined by the ratio of the speed of light in vacuum to the speed of light in the object. The light bends as it passes through the object.
When the surface of the skin is smooth, light is absorbed, reflected and scattered off the skin and is observed as a color according to how much light is absorbed and scattered. However, when light is directed toward a wrinkle it is unable to be reflected or even scattered in a way that is observable to the eye except as darkness or the absence of light. The light is non-reflected (in effect it is absorbed) because it becomes trapped inside of the crevice of the wrinkle, similar to the inorganic pigments. Therefore, light bounces inside the crevice but cannot reflect back out to the observing eye. As a result of this blockage, i.e., the inability of the light to be reflected, the eye observes a darkness (non-reflection) where the line or wrinkle is located on the skin.
To prevent the appearance of lines and wrinkles, makeup or foundation formulations have been modified to incorporate pigments which manipulate the light, and modify the appearance of the surface to which it is applied. Light manipulation, therefore, has become an important development in makeup products. Many products use optical diffusing powders or pearls to perfect the appearance of the skin. To prevent the appearance of wrinkles on the skin, the main goal of optically diffusing pigments is to prevent light from being trapped inside the crevice of a wrinkle. An optical light diffusing pigment can be for example, titanium dioxide, which physically fills the crevice but reflects light. As a result the line is masked and not highlighted because of the reflective nature of the titanium dioxide. However, this method has been found to be undesirable because it is too opaque and reflective. Therefore, it has been suggested that pigment not only diffuse light but also have a certain amount of transparency to overcome the mask-like appearance of titanium dioxide. Emmert, R., Dr., xe2x80x9cQuantification of the Soft-Focus Effectxe2x80x9d, Cosmetics and Toiletries, vol. 111, no. 7, p. 57 (1996). A number of conclusions were reached with respect to maximizing the efficiency of an optical light diffusing pigment. To begin, it is recommended that light absorption be minimized. The total transmissivity has to be high because transparent materials appear natural. However, the nature of the transmitted light has to be diffuse such that the light transmitted appears to be evenly distributed across the entire area of the observed skin (i.e., refraction). Specular reflection, i.e., light reflected as with a mirror, should be minimized. It is believed that luster increases the appearance of wrinkles.
In general, it has been accepted that glittery and pearly type pigments are not useful in traditional type makeup or foundations. These pigments, which exhibit high specular reflection, are used primarily in special cosmetic products that are considered alternative or xe2x80x9cfunkyxe2x80x9d. They are used for special occasions, or by a small group of xe2x80x9ctrendyxe2x80x9d users. However, they are not used broadly in makeup products for daily use by the mainstream user. The present invention, however, contrary to the widespread belief that these types of pigments would increase the appearance of wrinkles, and therefore, be undesirable, has surprisingly found that, in combination with a number of different types of optical altering pigments, highly reflective pigments can be an essential part of an integrated pigment system designed to reduce the appearance of fine lines and wrinkles on the skin.
The present invention is a composition which comprises a first platelet of alumina treated with a metal oxide in combination with at least one second platelet treated with at least one spherical scattering component in a cosmetically or pharmaceutically acceptable vehicle. The compositions of the present invention optically blur the appearance of lines, wrinkles, deformations, and discolorations on the skin surface. As a result of the blurring, observation of these skin flaws is prevented. The combined pigments also provide a natural skin color that closely matches the skin tone of the user. The spherical scattering component can be a spherical silica which also may be covered by a layer of titanium dioxide (TiO2). Because of their shimmering and glittery appearance, these pigments are not known to be formulated in a foundation for daily wear. Surprisingly, it has been found that this combination of platelets, without reliance on the traditional amount of metal oxides used in daily wear foundations, is suitable as a pigment for a foundation that closely matches the natural color of the skin. Therefore, the present invention includes compositions that are substantially free of metal oxides. It has been surprisingly found that topical application of these compositions to the skin causes the appearance of skin flaws to be minimized or prevented from being visible in an everyday makeup formulation.
The present invention also includes methods of preventing the appearance of fine lines and wrinkles on the skin by blurring their ability to be observed. The alumina platelet treated with metal oxide and the platelet treated with the spherical scattering component are blended together based on their ability to manipulate light and provide a natural skin tone color. This combination of pigments when applied to the skin surprisingly produces a diffused reflection of light such that the observer views a smooth and flawless skin surface. The appearance of lines, wrinkles, minor deformations and minor discolorations on the skin are prevented from being visible. The compositions of the present invention optimize the optical diffusion of light and cause the appearance of lines, wrinkles, deformations and other discolorations to substantially vanish. As a result, the natural skin color is seen as smooth and flawless, and the coverage is sufficient to reduce the appearance of redness and other skin discolorations.
The combination of pigments in the present invention creates a mosaic of color on a microscopic level (like that of a checkerboard), that when viewed by the natural eye of an observer, appears as a blend of color and scattered light which obscures the ability to see lines, wrinkles, deformations and discolorations on the skin and renders them substantially invisible. The present invention comprises the first platelet of alumina treated with metal oxide, and the second platelet treated with a spherical scattering component. Together, the two different platelets form the mosaic which gently reflects light and matches the natural color of the skin. Each individual platelet is known; however, they each by themselves have drawbacks when used in a daily wear makeup or foundation. Generally, these pigments are not used in traditional makeup formulations intended for daily use because they are not suitable. The alumina-based pigment, for example, is a metallic pigment that achieves complete or near complete reflection. This highly intensive reflection does not look good on the skin as an everyday foundation. It does not match skin tone, and also does not adequately reduce the appearance of skin flaws. Because of the intense reflection, wrinkles are appear more noticeable. Pigments which are capable of specular reflection are shimmery or metallic looking, and therefore, are not typically selected for use in a natural looking makeup or foundation as in the present invention. These types of pigments are suited for makeup products used at times that glitter is desirable. These times are usually holidays and special occasions, like weddings, graduations or other special ceremonies when a sparkle and shine is desirable for the occasion. This is not the purpose of a daily wear foundation.
Although these pigments alone are not suitable for a foundation that matches the natural tone of the skin, in combination with the other platelet component of the present invention, the high glitter of the alumina based pigment is toned down. The combined pigments resemble the natural tone of the skin, and lines, wrinkles and other types of blemishes appear to substantially vanish. The metallic, pearly, and glittery appearance of the alumina platelet is due to its ability to reflect light completely or substantially. The alumina platelet treated with metal oxide produces a deep red and brown finish that is mirror-like (i.e., it is shimmery). Preferably, the alumina platelet is treated with iron oxide and is available commercially from Cardre Inc., South Plainfield, N.J., as Pearl Copper 1000. It is a brown lustrous powder (similar to a rubbed penny) and has a particle size of about 10 to about 20 microns, preferably about 14 to 18 microns. The alumina-based pigment of the present invention is preferred because it produces a metallic effect unlike traditional pearl pigments. The alumina platelet is a planar mirrored particle that is copper colored rather than a tone superimposed with color. When the alumina platelet is combined with other platelet materials or interference pigments in a topical cosmetic or pharmaceutical composition, the appearance of flaws in the skin is altered. The alumina platelets provide color and a metallic look to the mosaic of platelets blended and balanced in the present invention. The alumina platelet is present in an amount of about 0.1 to about 10.0 percent by weight of the composition. Preferably, it is about 0.5 to about 5.0 percent. The other part of the mosaic is the flat finish pigments provided by the second platelet treated with the spherical scattering component.
The second platelet can be, for example, mica, bismuth oxychloride, sericite, alumina, aluminum, copper, bronze, silver or silica. The spherical scattering component can be spherical powders that achieve a soft focus look such as calcium aluminum borosilicate, PMMA, polyethylene, polystyrene, methyl methacrylate crosspolymer, nylon-12, ethylene/acrylic acid copolymer, boron nitride, Teflon, or silica. Examples of available platelets with soft focus materials incorporated include products available from Ikeda (Velvetveil) a mica coated with spherical silica beads, (Soft Vision) a mica coated with silica beads and further coated with TiO2, (Ganzpearls GSC-30SR, and GSC-30MC) a sericite and crosslinked polystyrene, and a mica and crosslinked polystyrene, respectively. The second platelet is present in a total amount of about 0.1 to about 10.0 percent, preferably about 0.2 to about 5.0 percent. When the second platelet is Soft Vision the haze is about 70 to 90 percent (ratio of diffused light to total transmission of light), total transmission of light is about 60 to 80 percent, and the haze is greater than the total transmission of light.
In one embodiment, the composition also comprises a standard interference pigment. Interference pigments, for purposes of the present specification and claims, are defined as thin platelike layered particles having a high refractive index, which, at a certain thickness, produce interference colors, resulting from the interference of typically two, but occasionally more, light reflections, from different layers of the plate. The most common examples of interference pigments are micas layered with about 50 to 300 nm films of TiO2, Fe2O3, or Cr2O3. Such pigments are often pearlescent. Pearl pigments reflect, refract and transmit light because of the transparency of pigment particles and the large difference in the refractive index of mica platelets and, for example, the titanium dioxide coating. The reflected light appears as a luster, because light is split by pigment particles at different depths to create a multidimensional shimmer, commonly referred to as pearlescent. The pigments are very reflective, and as mentioned above, are not suitable alone in a makeup product designed to resemble the natural skin tone.
Useful interference pigments are available commercially from a wide variety of suppliers, for example, Rona (Timiron(trademark) and Dichrona(trademark)), Presperse (Flonac(trademark)), Englehard (Duochrome(trademark)), and Kobo (SK-45-R and SK-45-G). Examples of preferable interference pigments are Flonac MS-30C, mica treated with TiO2 and iron oxide (yellow), and MU-10C, mica treated with TiO2 (white). Preferably, interference pigments of different colors or types are combined in the present invention to blend an appropriate shade or intensity of color to match the natural skin tone. The size of the interference pigment can be varied, depending upon the effect desired. Generally, a smaller pigment is less pearly, and therefore preferred, as the larger pigments will confer a substantial amount of sparkle. A useful size range of the interference particles is from about 1 to about 200xcexc, and preferably is about 3 to about 100xcexc. The interference pigment is used in an amount of from about 0.05 percent to about 50 percent by weight, with the high end of the range being most appropriate for use in a pressed powder product. However, in most types of products, the amounts of interference pigment will range from about 0.5 percent to about 20 percent, the lower end of the range being used in products using no non-interference pigments or lightly pigmented products, and the higher end of this range being used in more heavily pigmented products. Also, when the vehicle is a water-in-oil or water-in-silicone emulsion, it may be desirable to coat the alumina platelet, the second platelet or the interference pigments with a hydrophobic coating, or other suitable coating to facilitate wetting out. Thus, pearl pigments may be uncoated or coated.
The interference pigments may also be coated to improve the feel of the pigment on the skin. The coating of, for example, spherical powders (on the exterior surface of the pigment) can roll between the surface of the mica and the skin. Even though the mica can be treated to improve its color, feel, stability, and light diffusion properties, the resulting look is unnatural, flat and dull. Because light bounces off the spherical powders in so many different directions, some of the light bounces back into the system of spherical powders and is lost. Therefore, this component alone is also not desirable in a makeup or foundation composition.
In the present invention, the presence of interference pigments assists in the color adjustment of the alumina platelets. Together the pigments and the platelets produce a sum of reflected light off of the skin that appears gentle and soft and blurs the flaws of the skin. Even though more light bounces off the skin and back toward the eye observing the skin surface, the skin looks flawless and luminous from many directions and angles because the second platelet diffuses light bounced off of the skin by the alumina platelet and the interference pigments. Instead of light being trapped in crevices of wrinkles and creating dark lines, the overall net effect of the blended mosaic of pigments and platelets softens the appearance of imperfections and blemishes, and camouflages redness or other discolorations with the color which matches the natural skin tone.
The combination of the alumina platelets, platelets treated with the spherical scattering component and standard interference pigments, when applied to the skin, provides a natural looking appearance. Thus, the compositions of the present invention are substantially free of metal oxides because the color is provided by the alumina platelet in combination with the other components. As used in the present specification and claims, substantially metal oxide free means less than about 7 percent metal oxide, and preferably less than about 5 percent metal oxide. However, because of the many varied skin tones and colors, for a foundation, or other makeup product to match the skin, it may be desirable to add a non-interference pigment to fine tune the closeness of the color to the wearer""s skin. Thus, although the present invention achieves color, this fine-tuning is provided by the presence of at least one non-interference pigment. The amount of non-interference pigments used in the present invention is less than the amount used in tradition because unlike traditional foundations which rely almost entirely on metal oxides to provide color, the present invention produces a natural color that matches skin tone with the alumina platelet and the interference pigment. Therefore, unlike the look seen with traditional foundations, which contain high amounts of metal oxides (about 20 percent, for example,) which get trapped in lines and wrinkles, the skin appears flawless with the alumina-based pigment blended with the other components. Further, traditional foundation formulae containing lower amounts of pigment as used in the present invention are sheer and unable to provide the coverage achieved with the present invention. The coverage experienced with the present invention is full without looking ashy or causing a buildup in the lines, wrinkles, and other skin flaws.
Inorganic pigments, organic pigments, or a combination thereof can be used as the non-interference pigment. Examples of useful inorganic pigments include iron oxides (yellow, red, umber, brown or black), ferric ammonium ferrocyanide (blue), manganese violet, ultramarine blue, chrome oxide (green), talc, lecithin modified talc, zeolite, kaolin, lecithin modified kaolin, titanium dioxide (white), zinc oxide and mixtures thereof. Metal oxides, particularly iron and titanium oxides, and kaolin are preferred non-interference pigments in the composition of the invention. In addition to providing color to match the color of the skin, titanium dioxide, zinc oxide, and iron oxide function as particulate inorganic sunscreens.
Organic pigments can include natural colorants and synthetic monomeric and polymeric colorants. Exemplary are phthalocyanine blue and green pigment, diarylide yellow and orange pigments, and azo-type red and yellow pigments such as toluidine red, litho red, naphthol red and brown pigments. Also useful are lakes, which are pigments formed by the precipitation and absorption of organic dyes on an insoluble base, such as alumina, barium, or calcium hydrates. Particularly preferred lakes are primary FDandC or DandC Lakes and blends thereof. Water soluble colorants (such as FDandC Blue #1), oil soluble colorants (such as DandC Green #6), and stains, such as bromo dyes and fluorescein dyes can also be employed. The amount and type of the non-diffusing pigment used will vary depending upon the nature of the final product and the desired intensity of color; generally, however, the amount of non-diffusing pigment will be about 1 to about 10 percent, and preferably about 1 to about 5 percent, by weight of the total composition. In addition, microfine particulate pigments can be used at somewhat higher levels than those of normal particle size without significantly increasing the level of opacity of the composition on the skin can.
The blended pigment and platelet components of the present invention can be used in any type of skin treatment or makeup product. Skin treatment products, such as lip products, acne treatments, moisturizers, anti-aging products, lifting treatments, cellulite treatments and eye treatments, will ordinarily contain only the metal oxide treated alumina platelet blended with the second platelet treated with the scattering component; however, makeup products will typically contain the additional standard interference and non-interference pigment. The makeup products of the invention include, but are not limited to, foundations, blushes, pressed or loose powders, concealers, bronzers, eyeshadows, eyeliners, lipsticks, and lipglosses. The products of the invention can take any form which is typical of cosmetic products, for example, hot pour formulations, water-in-oil emulsions, oil-in-water emulsions, gels, sticks, sprays, anhydrous formulations, and pressed or loose powders. There is no limitation on the type of vehicle that can be employed. In particular, the preferred identity of the vehicle will be largely controlled by the type of product into which the components are to be incorporated. For a liquid foundation, for example, a water-in-oil emulsion is preferred for aesthetic reasons, and although the oil portion of the vehicle can be any which is typically used for this purpose, it is preferred that the oil component comprise a silicone oil, either volatile or non-volatile. Preferably, the present invention is used in a liquid or powder foundation.
The formulation also can comprise other components that may be chosen depending on the carrier and/or the intended use of the formulation. Additional components include, but are not limited to, water soluble sunscreens (such as Eusolex 232); oil soluble sunscreens (such as octyl methoxycinnamate); and organic sunscreens (such as camphor derivatives, cinnamates, salicylates, benzophenones, triazines, PABA derivatives, diphenylacrylate derivatives, and dibenzoylmethane derivatives.); antioxidants (such as BHT); chelating agents (such as disodium EDTA); emulsion stabilizers (such as carbomer); preservatives (such as methyl paraben); fragrances (such as pinene); flavoring agents (such as sorbitol); humectants (such as glycerine); waterproofing agents (such as PVP/Eicosene copolymer); water soluble film-formers (such as hydroxypropyl methylcellulose); oil-soluble film formers (such as hydrogenated C-9 Resin); moisturizing agents, such as cholesterol; cationic polymers (such as Polyquatemium 10); anionic polymers (such as xanthan gum); pigment wetting agents, such as Arlacel(trademark) P100, or Emerest(trademark) 2452; vitamins (such as tocopherol); and the like.
The compositions can also encompass one or more active components, and as such can be either cosmetic or pharmaceutical compositions. Examples of useful actives include, but are not limited to, those that improve or eradicate age spots, keratoses and wrinkles, analgesics, anesthetics, anti-acne agents, antibacterials, antiyeast agents, antifungal agents, antiviral agents, antidandruff agents, antidermatitis agents, antipruritic agents, antiemetics, antimotion sickness agents, anti-inflammatory agents, antihyperkeratolytic agents, anti-dry skin agents, antiperspirants, antipsoriatic agents, antiseborrheic agents, hair conditioners and hair treatment agents, antiaging agents, antiwrinkle agents, antiasthmatic agents and bronchodilators, sunscreen agents, antihistamine agents, skin lightening agents, depigmenting agents, wound-healing agents, vitamins, corticosteroids, tanning agents, sunscreens or hormones. More specific examples of useful active agents include retinoids such as retinol, and esters, acids, and aldehydes thereof; ascorbic acid, and esters and metal salts thereof, tocopherol and esters and amide derivatives thereof; shark cartilage; milk proteins; alpha- or beta-hydroxy acids; DHEA and derivatives thereof; topical cardiovascular agents; clotrimazole, ketoconazole, miconozole, griseofulvin, hydroxyzine, diphenhydramine, pramoxine, lidocaine, procaine, mepivacaine, monobenzone, erythromycin, tetracycline, clindamycin, meclocyline, hydroquinone, minocycline, naproxen, ibuprofen, theophylline, cromolyn, albuterol, hydrocortisone, hydrocortisone 21-acetate, hydrocortisone 17-valerate, hydrocortisone 17-butyrate, betamethasone valerate, betamethasone diproprionate, triaminolone acetonide, fluocinonide, clobetasol, proprionate, benzoyl peroxide, crotamiton, propranolol, promethazine, and mixtures thereof.

Compositions containing optical diffusing pigments


The present invention relates to an at least single-layer, biaxially oriented film support for magnetic recording media which is predominantly composed of crystallizable polyester, having a thickness in the range from 1 to 40 xcexcm. The film has, over its total roll length and roll width and after it has been made up into customer rolls, an electrostatic charge build-up which is in the range from xe2x88x9280 kV/m to +80 kV/m, the contact pressure at the roll cutters during make-up being set in the range from 300 N/m to 350 N/m. The film is drawn between electrical discharge means, which are arranged close to the roll, along the film path in the make-up machine, and is particularly suitable for high-quality audio, video or computer tapes and for floppy disks or thermal tapes.

The invention relates to a single-layer or multilayer biaxially oriented film support for magnetic recording media which is predominantly composed of crystallizable polyester. The film is distinguished by the fact that, after coating, it has a low laser defect rate and is therefore very suitable for high-quality magnetic recording media. The invention furthermore relates to a process for the production of the film.
Owing to their superior properties, such as tensile strength, their ultimate tensile strength, their modulus of elasticity, their transparency, their chemical and thermal stability and the like, biaxially oriented films of polyester, in particular of polyethylene terephthalate, polyethylene naphthalate or polycyclohexanedimethanol terephthalate, are used in large amounts in numerous industrial areas, and also as film supports for magnetic recording media, such as, for example, for audio, video and computer tapes and floppy disks, thermal printing tapes, etc.
For the various fields of use, the polyester films must meet specific requirements, which are usually achieved with the aid of the raw material formulations or by means of specific process engineering during the film production.
Thus, for example in the case of film supports for magnetic tapes, in addition to uniform and good sliding behavior and high abrasion resistance, particularly high requirements are set with respect to the homogeneity of the surface and the static behavior, because undesired protuberances on the surface of the support films, electrostatic errors and high static charge build-up within the magnetic layer applied to this surface lead to information losses and so-called laser defects which reduce the quality of the tape and limit the potential uses of the information medium. Overcoming or reducing the effect of, said electrostatic errors and high electrostatic charge build-up on the surface by incorporating inorganic and/or organic inert particles having a defined particle size distribution forms part of the prior art. Examples of such inert particles, which may be used alone or in combination, are CaCO3, TiO2, Al2O3, ZrO2, BaSO4, calcium phosphate, kaolin, SiO2 or natural and synthetic silicates.
To improve their infinity to the polymer matrix and hence to improve the quality, i.e. the properties of the moldings produced using these inert particles, these inert particles are subjected to a surface treatment, depending on their chemical composition.
A description of the possibilities of surface modification of carbonate fillers with the aim of influencing the interactions at in particular the CaCO3/polymer interfaces is given in Plaste und Kautschuk [Plastics and Rubber], 37th year, Part 8/1990, page 269 et seq.
U.S. Pat. No. 3,227,675 describes the treatment of clays (kaolins) with organosilicon compounds for better incorporation into a polymer matrix.
DE-A-35 34 143 describes monodisperse SiO2 particles which are preferably intended for chromatographic purposes and whose functional groups present on the surface have been reacted with organotrialkoxysilanes without the existing properties of the particles being adversely affected.
A process for the modification of synthetic silicate fillers with sulfur-containing organosilicon compounds for improving their incorporation into vulcanizable rubber blends is described in EP-A-0 177 674.
U.S. Pat. No. 4,567,030 likewise describes monodisperse mixed oxide particles which can be used as fillers and whose surfaces may have been modified for improving the resistance to moisture and the xe2x80x9cdispersibility in a resinxe2x80x9d, i.e. for reducing the agglomerate formation with an aminopropyltrimethoxysilane or silanes which contain ethylenically unsaturated groups. In EP-A-0 236 945, it is pointed out that, for reducing agglomerate formation during polymerization, the monodisperse mixed oxide particles are expediently subjected to a treatment with a silane, titanium or aluminum coupling reagent.
None of these publications describes methods which makes it possible to reduce the laser defect rate, which very greatly influences the quality of the coated magnetic tape.
Laser defects are coating errors. They are thin, round to oval areas in a magnetic layer or, in the advanced stage, even round or oval holes in the magnetic layer (transparent areas). In the case of laser defects, the polyester film is completely or partly exposed. The edge of the magnetic layer is highly fissured, which indicates a process similar to local tearing away of the magnetic layer. The defect has a diameter of between 0.2 and 0.8 mm. During the actual coating of the magnetic tape, some of the laser defects are not yet fully developed. The errors are fully displayed when the magnetic tape is cut into so-called xe2x80x9cpancakesxe2x80x9d. The laser defects are detected by means of a laser scanner. A 100% check is performed. On detection of a laser defect, the entire pancake is rejected in each case. It would be of great advantage for the magnetic tape coating industry to use a film support which, after coating, leads to few or, better still, even no laser defects at all. Usually, the rejection rate owing to laser defects is between 3 and 5%.
It was therefore the object of the present invention to provide an at least single-layer, biaxially oriented film support for magnetic recording media having a total thickness of from 1 xcexcm to 40 xcexcm, which essentially comprises polyester and which is distinguished by the fact that the laser defect rate is less than 2%, in particular less than 1%.
The object is achieved by an at least single-layer polyester film of the generic type stated at the outset and having a thickness of from 1 xcexcm to 40 xcexcm, wherein the film has, over the total roll length and roll width and after it has been made up into customer rolls, an electrostatic charge build-up which is in the range from xe2x88x9280 kV/m to +80 kV/m, in particular form xe2x88x9270 kV/m to +70 kV/m and preferably from xe2x88x9260 kV/m to +60 kV/m, in combination with a contact pressure at the roll cutters which is in the range from 300 N/m to 350 N/m, in particular from 310 N/m to 340 N/m.
If the contact pressure of the roll cutters is  greater than 350 N/m, electrostatic errors (static marks) occur to a greater extent and lead to a higher laser defect rate.
If the contact pressure at the roll cutters is  less than 300 N/m, the quality of the film in the roll is substantially adversely affected, which leads to considerable problems during further processing.
More than surprising is the fact that a film support for magnetic recording media which, after making up into customer rolls, has an electrostatic charge build-up of from xe2x88x9280 kV/m to +80 kV/m, in particular from xe2x88x9270 kV/m to +70 kV/m, preferably from xe2x88x9260 kV/m to +60 kV/m over the total roll length and roll width and was wound into customer rolls with a contact pressure at the roll cutters which is in the range from 300 N/m to 350 N/m, in particular from 310 N/m to 340 N/m, has a laser defect rate of xe2x89xa62% and in particular xe2x89xa61%.
In an attempt to reduce the laser defect rate, the person skilled in the art would have first improved the internal purity of the polyester raw material and investigated the production plant for contamination by foreign substances (oil, lubricants, oligomers, etc.). Furthermore, the person skilled in the art would have then reduced the production and make-up speeds in order thus to achieve a possible reduction in the laser defect rate.
It was therefore more than surprising for the person skilled in the art that an at least single-layer film support for magnetic recording media can be produced, with said electrostatic charge build-ups in combination with said contact pressure at the roll cutters, at high speeds of up to 400 m/min in an outstanding quality with a laser defect rate of xe2x89xa62%, in particular xe2x89xa61%.
The outstanding values for the electrostatics in combination with said contact pressure and the production speeds of up to 400 m/min are achieved by virtue of the fact that specific electrical discharge rods having improved discharge performance are used.
Electrical discharge rods form Eltex/Weil am Rhein of the R50/R51 type are particularly suitable. Earth conductors which are isolated and which reinforce the electrical field of the active tips and hence permit higher speeds and greater distances with very good discharge performance are advantageous.
The films may be single-layer or multilayer and may have a symmetrical or asymmetrical structure, differently formulated polyesters or formulated or unformulated polyesters and those of the same chemical composition but with different molecular weight and different viscosity being capable of being purified by coextrusion.
The film according to the invention essentially comprises a crystallizable polyester, a crystallizable polyethylene naphthalate (PEN) or mixtures thereof.
Crystallizable polyesters or crystallizable polyethylene naphthalates are understood as meaning
crystallizable homopolymers
crystallizable compounds
crystallizable copolymers
crystallizable recycled material
other variations of crystallizable thermoplastics.
The polyesters can be prepared both by the transesterification process, for example with the aid of transesterification catalysts, such as, for example, Zn, Mg, Ca, Mn, Li or Ge salts, and by the direct esterification process (PTA process), in which antimony compounds are used as polycondensation catalysts and phosphorus compounds as stabilizers. The RSV value of the polyesters is preferably in the range from 0.4 to 1.0 d/g.
Examples of polyesters are polycondensates of terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid with glycols having 2 to 10 carbon atoms, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylene-dimethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, polyethylene naphthalate/bibenzoate or polyethylene p-hydroxybenzoate.
The polyesters may be composed of up to 50 mol %, in particular of up to 30 mol %, of comonomer units, a variation in the glycol component and/or in the acid component being possible. As acid component, the copolyesters may contain, inter alia, 4,4-bibenzoic acid, adipic acid, glutaric acid, succinic acid, sebacic acid, phthalic acid, isophthalic acid, 5-Na-sulfoisophthalic acid or polyfunctional acids, such as trimellitic acid, etc.
The polyester films can be produced by known processes from a polyester raw material with, if required, further raw materials and/or further additives customary for film supports for magnetic recordings, in conventional amounts of from 0.1 to not more than 20% by weight, both as a monofilm and as multilayer, possibly coextruded films having identical or differently formed surfaces, it being possible, for example, for one surface to be pigmented and the other surface to contain little or no pigment. Furthermore, one or both surfaces of the film may be provided with a conventional functional coating by a known method.
In the preferred extrusion process for the production of the polyester film, the molten polyester material is extruded through a slot die and quenched as a substantially amorphous polyfilm on a chill roll. This film is then heated up again and is oriented in the longitudinal and transverse direction or in the transverse and longitudinal direction or in the longitudinal direction, in the transverse direction and again in the longitudinal direction and/or transverse direction. The orientation temperatures are in general Tg+10 K to Tg+60 K (Tg=glass transition temperature), the stretching ratio of the longitudinal stretching is usually from 2 to 6, in particular from 3 to 4.5, that of the transverse stretching is from 2 to 5, in particular from 3 to 4.5, and that of any second longitudinal stretching carried out is from 1.1 to 3. The first longitudinal stretching can, if required, be carried out simultaneously with the transverse stretching (simultaneous stretching). This is followed by heat setting of the film at oven temperatures of from 200 to 260xc2x0 C., in particular from 220 to 250xc2x0 C. The film is then cooled and rolled up.
The rolled-up film is made up into appropriate customer rolls on a make-up machine at speeds of from 300 to 400 m/min. The make-up procedure is effected using tailored winding tensions and contact pressures, characteristics depending on the film running length being employed both for tension and for contact pressure.
According to the invention, the contact pressure is from 300 N/m to 350 N/m, in particular from 310 N/m to 340 N/m. The winding tension is advantageously from 90 N/m to 200 N/m.
A plurality of electrical discharge means are installed along the film path in the make-up machine. In particular, discharge rods, preferably of the R50/R51 type from Eltex/Weil am Rhein, are installed on the roll.
After make-up, the customer rolls are tested, packed and delivered.
Owing to the surprisingly low laser defect rate after coating of the magnetic tape and after cutting of the magnetic tape into pancakes, the film support according to the invention is outstandingly suitable for magnetic recording media for high-quality audio, video and computer tapes and for floppy disks, thermal tapes, etc.
The invention is explained in more detail below with reference to embodiments, without being restricted to them.
The individual properties are measured according to the following standards or methods:
Light Transmittance
Light transmittance is understood as meaning the ratio of the total light transmitted to the quantity of incident light.
F5 Longitudinal Value
The value indicates the tensile strength of the film at 5% elongation. The measurement was carried out according to DIN 53 455.
Modulus of Elasticity
The modulus of elasticity was measured according to DIN 53 457. The F5 value and the modulus of elasticity were determined using a ZWICK apparatus, type 1445, the measuring length being 100 mm, the strip width 15 mm and the take-off speed 10 mm/min (modulus of elasticity) or 100 mm/min. The stated values are based on five individual measurements.
Ra Value
The Ra value expresses the surface roughness of the film in numerical terms as an arithmetic mean of all distances of the roughness profile R from the center line.
The measurement was carried out according to DIN 4768 by means of a perthometer SP 6 surface measuring apparatus from Feinpruf GmbH, Gottingen. The stated values are based on six individual measurements, the highest value being omitted from the calculation of the mean value. The cut-off was 0.25 mm in each case.
In addition, the center line average value was determined by means of the T20S/RP50 Hommel tester at a cut-off of 0.08 xcexcm (DIN 4762/1). Here, the following parameters were chosen:
Electrostatic Charge Build-Up
The electrostatic charge build-up is measured using a commercial, calibrated influence field meter (from Eltex/Weil am Rhein, type EMF 57) at a constant distance of 2 cm from the roll.

Biaxially oriented film support for magnetic recording media


Provided are technologies capable of direct measurement of activity of a bioactive substance in cell using nanowires, more particularly, a method for measuring intracellular activity of a bioactive substance using a nanowire support to which cells are immobilized and a nanowire support to which target substances for the subject bioactive substance are immobilized, and a chip for measuring intracellular activity of a bioactive substance including nanowires to which cells are immobilized and nanowires to which a target substance for the subject bioactive substance is immobilized.

(a) Field of the Invention
This disclosure relates to technologies for direct measurement of activity of a bioactive substance in cell using nanowires. In particular, a method of measuring intracellular activity of a bioactive substance using a support having nanowires to which a cell is immobilized and another support having nanowires to which a target substance for a bioactive substance to be detected is immobilized, and a chip for measuring intracellular activity of a bioactive substance including a support having nanowires to which a cell is immobilized and another support having nanowires to which a targeting substance for a bioactive substance to be detected are immobilized, are provided.
(b) Description of the Related Art
In general, enzyme activity has been studied using purified enzymes and substrates, and the methods include spectrophotometric assays measuring absorbance changes according to changes of substrates due to enzyme activities to identify enzyme activities, fluorometric assays measuring enzyme activities using differences in fluorescence between a product produced by enzyme activity and an initial substrate, calorimetry assays measuring heat absorbed or emitted by chemical reactions to measure changes of substrates due to enzyme reactions using microcalorimeter, chemiluminescent assays measuring light emission due to chemical reactions to measure enzyme activities, chromatographic assays measuring a product generated by enzyme activity using chromatography, and radiometric assays identifying enzyme activities using radioisotopes as substrates, and the like.
Since most of the methods for measuring enzyme activity are conducted in vitro using purified enzymes and substrates, various external conditions (ionic strength, salt concentration, temperature, pH, enzyme concentration, and etc.) may be controlled to conduct assays under best conditions for enzyme activity, which differs from endogenous enzyme conditions in cells. Since the existence of large quantities of macromolecules in cells may influence functional and structural stability of protein, and enzyme reaction including rate of reaction, the result of activity analysis using purified enzyme cannot always be regarded as representing enzyme action in cells.
Moreover, since in many cases, another enzyme reversing the reaction of one enzyme exists (for example, protein kinase and phosphatase which respectively cause phosphorylation and dephosphorylation exist simultaneously in cells), enzyme activity in the cell context may not be predicted simply by in vitro cell activity analysis. Recently, for measurement of endogenous enzyme activity in cells, various methods involving instantaneous cell lysis followed by assays have been extensively employed. However, the possibility that enzyme environment and activity may be changed during the cell lysis and lysate preparation cannot be excluded, and thus a method for analysis of enzyme activity with maintaining cells alive is required.
Nanotechnology enables characterization and control of material in atomic and molecular unit, and it has recently been combined with biotechnology and developed as new technology for future. Many study results have been reported on low dimensional nanostructures, and particularly one-dimensional nanomaterials such as nanorods, nanowires, nanotubes, nanobelts and the like with excellent optical, electrical, chemical and physical properties have been applied in various fields.
So far, biomedical applications of nanotechnology have mainly been focused on elucidating characteristics of nanoparticles for bio-imaging technology, biosensor, and local drug delivery. Since early 2000's, an intracellular drug delivery technique named nanotube spearing using nanomaterial supernatants has been developed. In 2007, Peidong Yang et al. of UC Berkeley, U.S.A. reported a study result of incubation of mice embryonic stem cells using vertically grown silicon nanowires and DNA transfection upon penetrating cells with the nanowires (Kim W, Ng J K, Kunitake M E, Conklin B R, Yang P, J. (2007) Am. Chem. Soc. 128:8990-8991), and suggested a possibility of application of vertically grown nanowires to live cells for the first time, although the transfection efficiency was very low as less than 1%.

Korea Institute of Science and Technology


A pillow book holder capable of allowing a reader to read a book without unnecessary hand muscle strain while at the same time the pillow book holder is capable of falling without damaging itself, the book, or losing the page place.

This invention relates generally to book holders and, more specifically, to a pillow book holder having a transparent, plastic-type material coupled to a pillow, thus allowing a book to be inserted between the pillow and the transparent, plastic-type material.
People who read books, especially those people who read books while lying in bed, often find it difficult to hold their book open in a position that is both comfortable for their hand as well as for their eyes. Book readers are frequently forced to change their hand position in order to release the hand muscles that have become uncomfortably tensed from maintaining a book in an open position. This constant changing of position is not only annoying, but can also cause eyesight related problems as the eye muscles strain to focus on the words of a page as it is being moved.
Various book holders have been devised to take pressure off of the hands, but they are generally not suitable for reading in bed. In the common event that the reader should fall asleep while reading in bed, prior art book holders are not designed to fall without damage to the book holder or the book. Even if no damage were to come to the book or book holder from a fall, the reader""s page place in the book will very likely be lost.
A need therefore existed for a pillow book holder capable of allowing a reader to read a book without unnecessary hand muscle strain while at the same time the pillow book holder is capable of falling without damaging itself, the book, or losing the page place of the book.
An object of the present invention is to provide a pillow book holder capable of allowing a reader to read a book without the need to manually hold the pages open, thus limiting hand muscle strain.
It is a further object of the present invention to provide a pillow book holder capable of withstanding a fall without damage to the book holder, a book, or loss of page place.
In accordance with one embodiment of the present invention, a pillow book holder is disclosed, comprising, in combination, a pillow having a front side and a back side, and a transparent plastic-type material coupled to a portion of the front side of the pillow and dimensioned to receive a book between the transparent plastic-type material and the front side of the
In accordance with another embodiment or the present invention, a method for reading a book is disclosed, comprising, in combination, the steps of providing a pillow having a front side and a back side, providing a transparent plastic-type material coupled to a portion of the front side of the pillow and dimensioned to receive a book between the transparent plastic-type material and the front side of the pillow, inserting an open book between the front side of the pillow and the transparent plastic-type member, and reading the book.
The foregoing and other objects, features, and advantages of the invention will be apparent from the following, more particular description of the preferred embodiments of the invention, as illustrated in the accompanying drawings.


This invention discloses an intertoe towel operable for drying between the toes. The intertoe towel consists of an elongated, tubular body member made of plush absorbent fabric, an elongate flexible core disposed within the tubular member and a loop handle affixed to at least one end of the body member to facilitate pulling the towel between the toes.

The present invention relates to a device to aid in the practice of good foot hygiene, and more particularly, to an elongate, substantially tubular towel operable for drying the skin between the toes.
The human foot is a complex system containing within its relatively small size 26 bones, 33 joints, and a network of more than 100 tendons, muscles, ligaments, blood vessels and nerves. The components of the foot work together, sharing the tremendous pressures of daily living. An average day of walking, for example, brings a force equal to several hundred tons to bear on the feet. The overall comfort of a person depends to a significant degree on the comfort of the person's feet.
A variety of fungal species (i.e., dermatophytes) are known to infect the foot, including Trichophyton rubrum, Trichophyton tonsurans, Epidermophyton floccosum and Trichophyton mentagrophytes. Once these microorganisms establish themselves on the foot, eradication with current over-the-counter antifungal agents is necessary and recurrences of the disease can be expected.
The most common fungal infection of the foot is "athlete's foot", a skin disease, usually starting between the toes or on the bottom of the feet, which can spread to other parts of the body. Athlete's foot is usually caused by colonization of the foot by one or more of the above-referenced dermatophytes fostered in a warm, moist environment, such as exists between the toes. Prevention includes careful foot care practices and proper hygiene. A daily foot washing with soap and warm water and careful drying, especially between the toes is essential.
As important as this practice is, it is often difficult to realize because the feet and toes are situated furthest from the hands, making them difficult to reach. The problem becomes amplified when the individual has a reduced range of motion due to such factors as age and/or arthritis. Accordingly, there is a need for a device to aid in the practice of good foot hygiene, especially with regards to drying between the toes.


Bottle aqueous household cleaning, fabric treatment and deodorizing compositions comprising surfactant, and a perfume which contains a substantial proportion of hydrophobic perfume ingredients having a ClogP of greater than 3. The bottles are made of high density polyethylene wherein the bottles have a continuous inner surface layer of nylon, polyetheneterephthalate or fluorinated polyethylene in order to prevent migration into and/or transmission through the high density polyethylene of the hydrophobic perfume ingredients.

The present invention relates to stable aqueous perfumed household cleaning and deodorizing compositions containing a surfactant and a perfume. The perfume is in a solubilized or emulsified state and contains a substantial proportion of hydrophobic perfume materials in order to impart a clean, desirable, scent to substrates upon which the product is used. The composition is packaged in a polyethylene bottle wherein the interior of the bottle has been modified in order to prevent undesirable changes in the perfume caused by absorption and/or transmission of the hydrophobic components into and/or through the polyethylene during storage.
It is recognized that consumers appreciate household cleaning, fabric treatment and deodorizing products which impart a pleasant odor to surfaces treated with said products. It has been found that in the formulation of perfumes for said products, the use of a substantial proportion of hydrophobic perfume materials in said perfumes is desirable.
For convenience and flexibility in use, it is highly desirable that household cleaning and deodorizing and fabric treatment compositions be in liquid form and packaged in plastic bottles. For cost reasons, polyethylene is a preferred material for manufacturing bottles for such compositions. It has been found however, that hydrophobic perfume materials have a tendency to be lost from the liquid product by absorption into and/or transmission through the polyethylene during storage of the composition. This results in a change in the odor character of the composition and a reduction in the fragrance benefit which would otherwise be obtained on surfaces treated with the composition.
All documents referred to herein are incorporated by reference and all percentages and proportions are by weight, unless otherwise specified.
The present invention relates to a bottled aqueous household cleaning, fabric treatment or deodorizing product comprising, in addition to water, from 0.01% to 50% of a surfactant and from 0.003% to 5% of a perfume wherein the perfume contains at least 10% of one or more hydrophobic perfume ingredients having a ClogP of greater than 3, and wherein the said product is present in a high density polyethylene bottle and wherein the bottle has a continuous inner surface layer of a material selected from the group consisting of:
a) nylon
b) polyethylene terephthalate and
c) fluorinated high density polyethylene
In accordance with the present invention it has been found that when aqueous household cleaning, fabric treatment or deodorizing compositions comprising water, surfactant and perfume are packaged in conventional high density polyethylene (HDPE) bottles there is a tendency for certain hydrophobic perfume ingredients (i.e. those having a ClogP of about 3 or greater) to be lost from the perfume. This is apparently by migration into and/or through the polyethylene bottle material. When the perfumes contain substantial amounts of such perfume ingredients, such loss considerably alters the intended fragrance character of the perfume. Bottles made of polyethylene terephthalate (PET) or glass do not exhibit this detrimental effect on perfumes. However, consumers prefer plastic containers over glass, and polyethylene is a less expensive plastic than PET. It has now been found that by use of HDPE bottles which have certain interior surface modifications, the loss of these hydrophobic perfume ingredients can be substantially eliminated.
The present invention is a bottled aqueous household cleaning, fabric treatment or deodorizing composition comprising, in addition to water, from 0.01% to 50% of a surfactant and from 0.003% to 5% of a perfume wherein the perfume contains at least 10% of one or more hydrophobic perfume ingredients having a ClogP of greater than 3, and wherein the said composition is present in a high density polyethylene bottle wherein the bottle has a continuous inner surface layer of a material selected from the group consisting of:
a) nylon
b) polyethylene terephthalate and
c) fluorinated high density polyethylene
A. Surfactants
Surfactants suitable for use in the compositions of the present invention can be any of those suitable for use in household cleaning, fabric treatment or deodorizing compositions. These include anionic, nonionic, cationic, ampholytic and zwitterionic detergents.
Examples of anionic detergents include C8-C22 alkyl sulfates, alkylbenzene sulfonates having from 9 to 15 carbon atoms in the alkyl group, alkyl ethyleneoxide ether sulfates having from 8-22 carbon atoms in the alkyl chain and from 1 to 30 ethylene oxide groups, and C8 to C22 fatty acid soaps. Examples of nonionic surfactants include condensates of from 3 to 30 moles of ethylene oxide with an aliphatic alcohol of 8 to 22 carbon atoms, condensates of 5 to 30 moles of ethylene oxide with an alkyl phenol wherein the alkyl contains 9 to 15 carbon atoms, and C8 to C22 alkyl dimethyl amine oxides. Examples of ampholytic and zwitterionic surfactants are found in U.S. Pat. No. 3,929,678, Laughlin et al, issued Dec. 30, 1975 at Col, 19, line 38 through Col. 22 line 48. Examples of cationic surfactants are tetraalkyl quaternary ammonium salts having at least one alkyl chain of 8 to 22 carbon atoms, wherein the other alkyl groups can contain from 1 to 22 carbon atoms and wherein the anionic counterion is halogen, ethylsulfate or methylsulfate. The term xe2x80x9chousehold cleaning and fabric treatment and deodorizing compositionsxe2x80x9d herein includes fabric laundering, softening and freshening compositions, and floor, rug and other household surface treatment compositions where it is desired to clean and/or impart a beneficial treatment or property to the surface. Surtactants are used at levels of from 0.01% to 50%, depending on the intended usage of the product. Typical levels are from 0.1% to 30% and 5% to 20%
Additional surfactants are disclosed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972.
B. Perfumes
The compositions of the present invention contain perfumes at levels of from 0.003% to 5%, preferably from 0.003% to 1% and more preferably from 0.05% to 0.2%. The perfumes contain a substantial portion of perfume ingredients (at least about 10%, preferably at least 50%, more preferably at least 70%) which have a ClogP of at least 3.
The logP of many perfume ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, Calif., contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the Pamona Med Chem/Daylight xe2x80x9cCLOGPxe2x80x9d program, Version 4.42 available from Biobyte Corporation, Claremont, Calif. This program also lists experimental logP values when they are available in the Pomona92 database. The xe2x80x9ccalculated logPxe2x80x9d (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.
The following table contains a listing of examples of perfume ingredients having a ClogP of at least 3 which are useful in the present invention.
C. Optional Ingredients
In addition to surfactant and perfume, aqueous cleaning, fabric treatment and deodorizing compositions of the present invention can contain the usual adjuvants found in such compositions. These include builders (e.g. phosphates, citrates, polycarboxylates, silicates, etc.), soil suspending agents (e.g. carboxymethyl cellulose), antimicrobial agents (e.g. cyclohexidine, biguanides, etc.), hydrotropes (e.g. sodium cumene sulfonate, propylene glycol), enzymes (e.g. proteases) and polar solvents (e.g. ethanol, ethylene glycol monobutyl ether).
In addition to the perfume ingredients which have a ClogP greater than 3, the perfume can contain perfume ingredients which have a ClogP of less than 3. Examples of such ingredients are shown in Table 2. Perfume ingredients which have a ClogP of less than 3 can be used at levels up to 90% in the perfumes herein.
Preferred compositions herein which have an especially good deodorizing effect on surfaces (e.g. fabrics, carpets, counter tops, etc.) treated with the composition, contain cyclodextrin. In addition to the perfume in the composition providing the desired odor, to the treated surface. Cyclodextrin has the ability to absorb odors such as present in perspiration, urine, etc. present on the treated surface.
Preferably, the cyclodextrins used in the present invention are highly water-soluble such as, alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin and/or derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof. The derivatives of cyclodextrin consist mainly of molecules wherein some of the OH groups are converted to OR groups. Cyclodextrin derivatives include, e.g., those with short chain alkyl groups such as methylated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those with hydroxyalkyl substituted groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl cyclodextrins, wherein R is a xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94CH3 or a xe2x80x94CH2CH2xe2x80x94OH group; branched cyclodextrins such as maltose-bonded cyclodextrins; cationic cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl ether, wherein R is CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94N(CH3)2 which is cationic at low pH; quaternary ammonium, e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloride groups, wherein R is CH2xe2x80x94CH(OH)xe2x80x94CH2xe2x80x94N+(CH3)3Clxe2x88x92; anionic cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates; amphoteric cyclodextrins such as carboxymethyl/quaternary ammonium cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure, e.g., the mono-3-6-anhydrocyclodextrins, as disclosed in xe2x80x9cOptimal Performances with Minimal Chemical Modification of Cyclodextrinsxe2x80x9d, F. Diedaini-Pilard and B. Perly, The 7th International Cyclodextrin Symposium Abstracts, April 1994, p. 49, said references being incorporated herein by reference; and mixtures thereof. Other cyclodextrin derivatives are disclosed in U.S. Pat. No. 3,426,011, Parmerter et al., issued Feb. 4, 1969; U.S. Pat. Nos. 3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter et al., and all issued Jul. 1, 1969; U.S. Pat. No. 3,459,731, Gramera et al., issued Aug. 5, 1969; U.S. Pat. No. 3,553,191, Parmerter et al., issued Jan. 5, 1971; U.S. Pat. No. 3,565,887, Parmerter et al., issued Feb. 23, 1971; U.S. Pat. No. 4,535,152, Szejtli et al., issued Aug. 13, 1985; U.S. Pat. No. 4,616,008, Hirai et al., issued Oct. 7, 1986; U.S. Pat. No. 4,678,598, Ogino et al., issued Jul. 7, 1987; U.S. Pat. No. 4,638,058, Brandt et al., issued Jan. 20, 1987; and U.S. Pat. No. 4,746,734, Tsuchiyama et al., issued May 24, 1988; all of said patents being incorporated herein by reference.
Highly water-soluble cyclodextrins are those having water solubility of at least about 10 g in 100 ml of water at room temperature, preferably at least about 20 g in 100 ml of water, more preferably at least about 25 g in 100 ml of water at room temperature. The availability of solubilized, uncomplexed cyclodextrins is essential for effective and efficient odor control performance. Solubilized, water-soluble cyclodextrin can exhibit more efficient odor control performance than non-water-soluble cyclodextrin when deposited onto surfaces, especially fabric.
Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from about 1 to about 14, more preferably from about 1.5 to about 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin derivatives typically have a degree of substitution of from about 1 to about 18, preferably from about 3 to about 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-xcex2-cyclodextrin, commonly known as DIMEB, in which each glucose unit has about 2 methyl groups with a degree of substitution of about 14. A preferred, more commercially available, methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin, commonly known as RAMEB, having different degrees of substitution, normally of about 12.6. RAMEB is more preferred than DIMEB, since DIMEB affects the surface activity of the preferred surfactants more than RAMEB. The preferred cyclodextrins are available, e.g., from Cerestar USA, Inc. and Wacker Chemicals (USA), Inc.
It is also preferable to use a mixture of cyclodextrins. The amount of cyclodextrins used in the compositions will range from 0.01% to about 20%. If the composition is intended to be diluted before use it will contain from 3% to 20%, preferably 5% to 10%. Compositions intended to be used in undiluted form will generally contain from 0.01% to 5%, preferably 0.1% to 3%, more preferably 0.5% to 2%.
When formulating compositions with cyclodextrins, it is desirable to use surfactants which have especially good compatibility with cyclodextrin. Suitable cyclodextrin-compatible surfactants can be readily identified by the absence of effect of cyclodextrin on the surface tension provided by the surfactant. This is achieved by determining the surface tension (in dyne/cm2) of aqueous solutions of the surfactant in the presence and in the absence of about 1% of a specific cyclodextrin in the solutions. The aqueous solutions contain surfactant at concentrations of approximately 0.5%, 0.1%, 0.01%, and 0.005%. The cyclodextrin can affect the surface activity of a surfactant by elevating the surface tension of the surfactant solution. If the surface tension at a given concentration in water differs by more than about 10% from the surface tension of the same surfactant in the 1% solution of the cyclodextrin, that is an indication of a strong interaction between the surfactant and the cyclodextrin. The preferred surfactants herein should have a surface tension in an aqueous solution that is different (lower) by less than about 10%, preferably less than about 5%, and more preferably less than about 1% from that of the same concentration solution containing 1% cyclodextrin.
(a) Block Copolymers
Nonlimiting examples of cyclodextrin-compatible nonionic surfactants include block copolymers of ethylene oxide and propylene oxide. Suitable block polyoxyethylene-polyoxypropylene polymeric surfactants, that are compatible with most cyclodextrins, include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as the initial reactive hydrogen compound. Polymeric compounds made from a sequential ethoxylation and propoxylation of initial compounds with a single reactive hydrogen atom, such as C12-18 aliphatic alcohols, are not generally compatible with the cyclodextrin. Certain of the block polymer surfactant compounds designated Pluronic(copyright) and Tetronic(copyright) by the BASF-Wyandotte Corp., Wyandotte, Mich., are readily available.
Nonlimiting examples of cyclodextrin-compatible surfactants of this type include:
Pluronic Surfactants with the general formula H(EO)n(PO)m(EO)nH, wherein EO is an ethylene oxide group, PO is a propylene oxide group, and n and m are numbers that indicate the average number of the groups in the surfactants. Typical examples of cyclodextrin-compatible Pluronic surfactants are:
and mixtures thereof.
Tetronic Surfactants with the general formula:
wherein EO, PO, n, and m have the same meanings as above. Typical examples of cyclodextrin-compatible Tetronic surfactants are:
and mixtures thereof.
xe2x80x9cReversexe2x80x9d Pluronic and Tetronic surfactants have the following general formulas:
Reverse Pluronic Surfactants H(PO)m(EO)n(PO)mH
Reverse Tetronic Surfactants
wherein EO, PO, n, and m have the same meanings as above. Typical examples of cyclodextrin-compatible Reverse Pluronic and Reverse Tetronic surfactants are:
Reverse Pluronic surfactants:
Reverse Tetronic surfactants
and mixtures thereof.
(b) Siloxane Surfactants
A preferred class of cyclodextrin-compatible nonionic surfactants are the polyalkyleneoxide polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one or more hydrophilic polyalkylene side chains and have the general formula:
R1xe2x80x94CH3)2SiOxe2x80x94[(CH3)2SiO]axe2x80x94[(CH3)(R1)SiO]bxe2x80x94Si(CH3)2xe2x80x94R1
wherein a+b are from about 1 to about 50, preferably from about 3 to about 30 , more preferably from about 10 to about 25, and each R1 is the same or different and is selected from the group consisting of methyl and a poly(ethyleneoxide/propyleneoxide) copolymer group having the general formula:
xe2x80x94(CH2)nO(C2H4O)c(C3H6O)dR2
with at least one R1 being a poly(ethyleneoxide/propyleneoxide) copolymer group, and wherein n is 3 or 4, preferably 3; total c (for all polyalkyleneoxy side groups) has a value of from 1 to about 100, preferably from about 6 to about 100; total d is from 0 to about 14, preferably from 0 to about 3; and more preferably d is 0; total c+d has a value of from about 5 to about 150, preferably from about 9 to about 100 and each R2 is the same or different and is selected from the group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group, preferably hydrogen and methyl group.
Examples of this type of surfactants are the Silwet(copyright) surfactants which are available OSi Specialties, Inc., Danbury, Conn. Representative Silwet surfactants are as follows.
The molecular weight of the polyalkyleneoxy group (R1) is less than or equal to about 10,000. Preferably, the molecular weight of the polyalkyleneoxy group is less than or equal to about 8,000, and most preferably ranges from about 300 to about 5,000. Thus, the values of c and d can be those numbers which provide molecular weights within these ranges. However, the number of ethyleneoxy units (xe2x80x94C2H4O) in the polyether chain (R1) must be sufficient to render the polyalkyleneoxide polysiloxane water dispersible or water soluble. If propyleneoxy groups are present in the polyalkylenoxy chain, they can be distributed randomly in the chain or exist as blocks. Preferred Silwet surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof. Besides surface activity, polyalkyleneoxide polysiloxane surfactants can also provide other benefits, such as antistatic benefits, lubricity and softness to fabrics.
The preparation of polyalkyleneoxide polysiloxanes is well known in the art. Polyalkyleneoxide polysiloxanes of the present invention can be prepared according to the procedure set forth in U.S. Pat. No. 3,299,112, incorporated herein by reference. Typically, polyalkyleneoxide polysiloxanes of the surfactant blend of the present invention are readily prepared by an addition reaction between a hydrosiloxane (i.e., a siloxane containing silicon-bonded hydrogen) and an alkenyl ether (e.g., a vinyl, allyl, or methallyl ether) of an alkoxy or hydroxy end-blocked polyalkylene oxide). The reaction conditions employed in addition reactions of this type are well known in the art and in general involve heating the reactants (e.g., at a temperature of from about 85xc2x0 C. to 110xc2x0 C.) in the presence of a platinum catalyst (e.g., chloroplatinic acid) and a solvent (e.g., toluene).
(c) Anionic Surfactants
Nonlimiting examples of cyclodextrin-compatible anionic surfactants are the alkyldiphenyl oxide disulfonate, having the general formula:
wherein R is an alkyl group. Examples of this type of surfactants are available from the Dow Chemical Company under the trade name Dowfax(copyright) wherein R is a linear or branched C6-C16 alkyl group. An example of these cyclodextrin-compatible anionic surfactant is Dowfax 3B2 with R being approximately a linear C10 group. These anionic surfactants are preferably not used when the antimicrobial active or preservative, etc., is cationic to minimize the interaction with the cationic actives, since the effect of both surfactant and active are diminished.
The surfactants above are either weakly interactive with cyclodextrin (less than 5% elevation in surface tension, or non-interactive (less than 1% elevation in surface tension). Normal surfactants like sodium dodecyl sulfate and dodecanolpoly(6)ethoxylate are strongly interactive, with more than a 10% elevation in surface tension in the presence of a typical cyclodextrin like hydroxypropyl beta-cyclodextrin and methylated beta-cyclodextrin.
Typical levels of cyclodextrin-compatible surfactants in usage compositions are from about 0.01% to about 2%, preferably from about 0.03% to about 0.6%, more preferably from about 0.05% to about 0.3%, by weight of the composition. Typical levels of cyclodextrin-compatible surfactants in concentrated compositions are from about 0.1% to about 8%, preferably from about 0.2% to about 4%, more preferably from about 0.3% to about 3%, by weight of the concentrated composition.
Deodorizing compositions containing cyclodextrin are more fully described in pending Provisional Application No. 60/109834, filed Nov. 25, 1998. HDPE Bottles.
(d) High Density Polyethylene Bottles.
The modified HDPE bottles used in the present invention are modified by having, as their interior surface, a material selected from nylon, polyethylene terephthalate or fluorinated polyethylene, which acts as a barrier to prevent absorption into and/or transmission through the HDPE.
HDPE bottles of this type are known to the art. HDPE bottles with a nylon or PET inner layer can be made by the blow molding process wherein concentric layers of heat softened HDPE, an adhesive, and nylon or PET are formed into a parison and coextruded as a hollow tube into a mold cavity and forced by pressurized air against the walls of the cold mold cavity to form the bottle. The bottle solidifies by cooling to form an HDPE bottle which has an inner surface of nylon or PET.
HDPE bottles having an inner surface of fluorinated HDPE can be made by known methods whereby the inner surface of heated, preformed HDPE bottles are subjected to contact with fluorine gas. The fluorine reacts with the polyethylene to form a layer of fluorinated polyethylene. See Surface Treatment Improves Polyethylene Barrier Protection Package Engineering, November, 1981 p.64. Also U.S. Pat. No. 4,081,574, issued Mar. 28, 1964 and U.S. Pat. No. 3,998,180, issued Dec. 21, 1976.
The inner layer of nylon, PET or fluorinated polyethylene should be continuous and have a thickness of at least about 0.0005 in.

Perfumed liquid household cleaning fabric treatment and deodorizing compositions packaged in polyethylene bottles modified to preserve perfume integrity


A windup window shade for motor vehicles has a rotatably seated windup shaft, on which a window shade web is fastened by an edge. The other edge is fastened on a traction rod, whose ends are guided in guide rails. The distance between the guide rails changes very greatly, viewed in the direction of movement of the window shade web, because of which the length of the traction rod can be changed in a telescope-like manner. It is composed of a center element and two end elements, wherein it is provided with the aid of a centering device that the center element always remains centered in respect to the end elements.

Modern automobile body shapes are distinguished by relatively large window areas. Because of strong sunlight, the large window areas result in considerable heat generation in the interior of the vehicle and, in connection with vehicles with air conditioning, this extensive heat
For this reason, motor vehicles are increasingly equipped with windup window shades.
In this connection it is known to attach two guide rails laterally next to the window, in which the end of a traction rod of the window shade web is guided. The length of the traction rod is adjustable in order to be able to accommodate various window widths. Actuation takes place by means of thrust members running in the guide rails.
The windows in front of which such windup window shades are arranged generally have an approximately trapezoidal shape. The shape is a result of the shape of the vehicle body, wherein the roof is relatively strongly recessed in relation to the mid-section of the vehicle. When the guide rails extend along the lateral edges of the rear window, the distance which the traction rod must bridge is unavoidably changed when it is moved along the guide rails.
Therefore the traction rod of the known windup window shades is made in three sections and consists of a center element, whose length corresponds to the width of the window shade web shape at the appropriate edge, and two end elements, which can be moved in a telescope-like manner in respect to the center element.
The center element and the end elements are pushed together over sliding connections, which necessarily cause a certain minimum amount of friction.
The friction differs at the two end elements. A differential force is created during the retraction and extension of the end elements, which is more or less strong and directed toward one of the two lateral guide rails. The window shade web is transversely warped and causes waves and folds. If the differential force increases because the warping increases, the transverse stiffness of the window shade web might possibly result in sufficient centering.
As a rule, such blinds are extended from the wider edge in the direction of the narrower edge, i.e. in the direction toward the roof. The center element is pushed into a more or less centered position when, it pushes against a guide rail. However, no use can be made of this centering during retraction, so that the window shade web is possibly wound up more or less lopsided, and over time the created folds or waves are imprinted on the wound-up body.
Based on the foregoing it is the object of the invention to further improve a windup window shade of the above mentioned type in such a way that there is no danger of decentering the edge of the window shade web, which moves in front of the window surface during retraction and extension.
In accordance with the invention, the above object generally is attained by a windup window shade for regulating the entry of light through a window into the interior of a motor vehicle, comprising; at least one windup shaft, which is rotatably seated; at least one window shade web, which is fastened by one edge on the windup shaft; at least one pair of guides, each of which extends laterally beside the extended window shade web, and each of which contains at least one guide groove; a length-adjustable traction rod, which is connected with an edge remote from the windup shaft and is composed of a center element and two end elements, with the end elements being guided in the guide grooves; a centering device, which, at least approximately, centers the center element with respect to the end elements; and, a drive mechanism for moving the traction rod along the guides and or rotating the windup shaft.
The windup window shade of the invention is provided with a centering device which assures that the center element of the traction rod remains at least approximately centered.
Two options are possible for the centering device. One option operates in accordance with the principle of a differential gearing, while the other variation provides springs, which assure a floating centering.
In the case of the differential gearing or drive, the movement of one end element in relation to the center element is transmitted in the opposite direction to the other end element, wherein the amount of the length of travel displacement equals the length of travel displacement of the first-mentioned end element. Regardless of which one is actuated, the two end elements are in this way pushed oppositely back and forth by the same amount in respect to the center element. In turn, this results in a forced centering of the center element if the end elements move in respect to each other.
The centering device with the aid of springs acts floatingly. One end of the springs is supported on the center element and assures that the center element is floatingly centered in respect to the end elements. The center element will be displaced in the linear direction until the force exerted by the two springs is equal. If the springs have a comparatively steep characteristic curve, they are in a position to center the center element with sufficient accuracy even if the frictional forces of the end elements in respect to the center element differ.
Which one of the two solutions is preferred is primarily a function of the installation conditions and the extent of the trapezoidal shape, i.e. the length which the end elements must travel. In connection with a great length of travel, the differential gearing arrangement possibly has advantages, while the spring solution is easier to implement.
If a differential gearing is used as the centering device, the differential gearing can operate interlockingly, or also by frictional connection. The frictionally-connected embodiment possibly does not operate as accurately as the interlocking arrangement, but can be assembled somewhat more easily.
In each case it is advantageous if the center element is formed from a tube, preferably a profiled tube, because the end elements are displaceable in the profiled tube in a manner fixed against relative rotation. The profiled tube keeps the window shade web separate from the centering device, and at the same time protects the centering device.
The guide means preferably are guide rails containing a guide groove. But the solution in accordance with the invention can also be employed in connection with windup window shades wherein the traction rod runs on rod-shaped guide rails and has eyes at the ends.
A spring drive and an electric motor are preferably provided for moving the windup window shade. Also preferred is the seating of the spring drive in the windup shaft, while the electric motor drives the traction rod. With this arrangement the window shade web is forcibly and without any increased outlay kept stretched between the windup shaft and the traction rod. But the other driving means is also conceivable, wherein the traction rod is biased in the direction of the extended position with the aid of the springs, while the windup shaft is driven by the electric motor.
The window shade web itself preferably consists of a woven material or a perforated and dyed plastic foil.
Further embodiments of the invention are disclosed and discussed. It is intended here that also those combinations of characteristics are considered to be within the scope of the invention, even if there is no explicit exemplary embodiment.

Windup window shade with a centering device for the traction rod