DRY SUBSTRATE, E, METHOD OF PREPARATION OF THE DRY SUBSTRATE

专利摘要:
cooling substrates with hydrophilic containment layer and method of preparation. The present invention deals with cleaning products, such as facial tissue papers, which contain an internal temperature change composition and an external hydrophilic lotion composition and which can provide a cooling sensation when placed in contact with a wearer's skin. the temperature change composition, for example, may contain one or more phase change agents, which undergo (rrt) a phase change at slightly elevated temperatures. phase change agents, in one modality, can exhibit a relatively high heat of fusion. upon undergoing a phase change, the phase change agents absorb heat and thereby provide a cooling feeling to a user's skin. the hydrophilic lotion composition may contain a vehicle and a heat-reversible gelling agent. the hydrophilic lotion composition keeps the temperature-changing composition within the tissue paper and helps prevent skin irritation.
公开号:BR112012011937B1
申请号:R112012011937-0
申请日:2010-10-08
公开日:2021-06-22
发明作者:Scott W. Wenzel；Jeffery Richard Seidling；Frederick John Lang；Stephanie Diana Scharenbroch；Mark Anthony Barnes；Judy Marie Casper；Helen Kathleen Moen
申请人:Kimberly - Clark Worldwide, Inc.；
IPC主号:

专利说明:

HISTORIC
[001] Numerous health care and cosmetic products are applied to the skin in order to provide various benefits. Such products can include, for example, lotions, creams, moisturizers and the like. In some circumstances, the products are intended to provide a cooling feeling or cooling sensation to the skin when applied. Existing products typically provide cooling to the skin by combining skin cooling agents with other substances.
[002] There are several different ways of imparting a cooling sensation to the skin, including the use of evaporation, sensorineural components or physical agents such as phase change agents. An example of a cooling agent is menthol, which provides cooling in the form of a physiological or sensorineural effect on nerve endings in the human body, which sense heat. The feeling of cooling from menthol is not due to latent heat of evaporation, but appears to be the result of direct stimulation on the cold receptors in nerve endings.
[003] The use of phase change agents to impart cooling is discussed, for example, in PCT International Publication No. WO 2006/007564 entitled "Cosmetic Compositions and Methods for Sensory Cooling", which is incorporated herein by reference. In the '564 application, a cosmetic skin care composition in the form of a lotion is described which is intended for use in after sun products, after shave products and body moisturizing products. The lotion is intended to create a cooling sensation on the skin by incorporating components into the lotion that absorb heat from the skin. In particular, ingredients are incorporated into the lotion that absorb heat from the skin and fuse together. The components exhibit a relatively high heat of fusion, which is defined in the '564 application as the heat absorbed per unit mass of a solid chemical element at its melting point in order to convert the solid into a liquid therein. temperature. The '564 application states that the relatively high heat of fusion facilitates the absorption of heat from the skin to help melt the solid ingredient when applied to the skin, thereby cooling the skin temperature.
[004] The application of phase change agents to impart cooling to tissue papers is described, for example, in PCT Patent Application No. PCT/IB2009/051515 entitled "Tissue Products having a Cooling Sensation when Contacted with Skin", which is incorporated herein by reference. The '515 application describes the application of a phase change agent between multiple layers of a dry tissue paper web with a separate hydrophobic lotion layer on the outer surfaces of the tissue paper product to provide a cooling sensation. This approach is problematic as the components of the hydrophobic lotion can migrate to the hydrophobic phase change agent and disrupt its ability to cool. Alternatively, the phase change agent can migrate into the lotion on the outside of the tissue paper and can cause irritation to the skin.
[005] Therefore, there is a demand for a way to effectively maintain a phase change agent on or within a substrate, such as tissue paper, such that it will cool the skin without allowing irritation to the skin . There is also a demand for a substrate, such as tissue paper, containing the composition, such that the composition can be delivered to the nostril to moisturize, cool and soothe irritated nostrils, while maintaining this phase change agent within the substrate, preventing it to irritate the skin. Additionally, there is a need to effectively coat substrates, such that the phase change agent is kept within the tissue paper for extended periods of time. There remains demand for a cooling tissue paper that is non-irritating during use. RESUME
[006] In general, dry cleaning products are described herein and, particularly, dry substrates, when held against the skin, can provide a cooling sensation. In one embodiment, for example, the substrate may contain facial tissue paper. Facial tissue paper can be used to provide comfort to a user's nostrils. For example, when suffering from the common cold, a person's nostrils can become inflamed and irritated. In one embodiment, the present invention is directed to a tissue paper product, which can not only be used to clean someone's nostrils, but which can also provide the nostrils with a cooling sensation, providing comfort and relief without causing irritation to the skin.
[007] The present invention is directed to a temperature change composition for cooling the skin during use of the product, in combination with a separate hydrophilic lotion layer, on the outer surfaces of the product. The operative temperature change composition contains an effective amount of at least one phase change agent. The temperature changing composition can be incorporated into the tissue paper product in such a way that substantially no temperature changing composition is present on the outer surfaces. The hydrophilic lotion layer helps to minimize phase change agents from substantially contacting the skin and/or transferring to the skin and causing irritation or being removed from the product prior to use.
[008] The phase change agent incorporated into the temperature change composition may vary depending on the particular application and the desired result. The phase change agent, for example, can contain an oil-soluble, hydrophobic material. Examples of phase change agents include hydrocarbons, waxes, oils, natural butters, fatty acids, fatty acid esters, dibasic acids, dibasic esters, 1-halides, primary alcohols, aromatic compounds, anhydrides, ethylene carbonates, polyalcohols water, and mixtures thereof. In one embodiment, for example, a plurality of phase change agents can be incorporated into the temperature change composition. Particular examples of phase change agents include tricaprin, paraffin, nonadecane, octadecane, stearyl heptanoate, lauryl lactate, lauryl alcohol, capric acid, caprylic acid, cetyl babassuate, Mangifera indica stone butter (mango), butter Theobroma cacao kernel (cocoa), Butyrospermum parkii butter, di-C12-C15-alkyl fumarate, stearyl caprylate, cetyl lactate, cetyl acetate, Cu-Cu-alkyl-methicone, glyceryl dilaurate, chloride-phosphate of PG-stearamido-propyl dimonium, jojoba esters and combinations thereof.
[009] Vehicles for use in the hydrophilic lotion composition may include, but are not limited to, water, glycerin, diglycerin, glycerin derivatives, glycols, glycol derivatives, sugars, ethoxylated and/or propoxylated ethers and ethers, urea, PCA sodium, alcohols, ethanol, isopropyl alcohol, and combinations thereof. Desirably the vehicle is propylene glycol.
Typically, the hydrophilic lotion composition contains a carrier in an amount of from about 1% by weight of the hydrophilic lotion composition to about 99.9% by weight of the hydrophilic lotion composition, more typically from about 2 % by weight of the hydrophilic lotion composition to about 95% by weight of the hydrophilic lotion composition, and more typically from about 5% by weight of the hydrophilic lotion composition to about 90% by weight of the hydrophilic lotion composition .
[0011] Thermo-reversible gelling agents, for use in the hydrophilic lotion composition, may include, but are not limited to, fatty acid salts such as sodium stearate, sodium palmitate, potassium stearate, hydroxy-stearic acid , poly(ethylene glycols) and derivatives such as PEG-20, PEG-150 distearate, PEG-150 pentaerythryl tetrastearate, distearet-75 IPDI, distearet-100 IPDI, fatty alcohols such as cetyl alcohol, fatty acids , such as stearic acid, and combinations thereof. In addition, thermo-reversible gelling agents can be formed by including an acid (eg, stearic acid) and neutralizing it within the hydrophilic lotion composition with a base (eg, sodium hydroxide) to make salts of fatty acids.
[0012] The use of a thermo-reversible gelling agent is very important. A temperature change composition formed with a thermo-reversible gelling agent allows the product to be exposed to extreme temperatures during product shipment and still function effectively at home when used by a consumer. The thermally reversible temperature shift composition described here will change from a solid state to a liquid state and will return to a solid state as temperatures change. Therefore, phase change materials, which provide a cooling effect, are still available after long periods of storage and transport at various temperatures. The foregoing temperature change compositions disclosed, for example, in PCT Patent Application No. PCT/IB2009/051515 entitled "Tissue Products having a Cooling Sensation When Contacted with Skin", are not thermally reversible and do not provide such benefits.
Typically, the hydrophilic lotion composition contains a thermo-reversible gelling agent in an amount from about 1% by weight of the hydrophilic lotion composition to about 99.9% by weight of the hydrophilic lotion composition, more typically from about 2% by weight of the hydrophilic lotion composition to about 95% by weight of the hydrophilic lotion composition, and more typically from about 5% by weight of the hydrophilic lotion composition to about 90% by weight of hydrophilic lotion composition.
[0014] In addition, a method of preparing dry substrates formed by a first and a second web is described. Each of these wefts can be formed by a single layer or by multiple layers. First, a temperature change composition is applied to the first side of the first web and the first side of the second web, and a hydrophilic lotion composition is applied to the second side of the first web and the second side of the second web. Then, the first weft and the second weft are wound together to form a combined weft so that the first side of the first weft faces the first side of the second weft. Therefore, the temperature change composition is between the first web and the second web of the dry substrate. The hydrophilic lotion composition is on the outer surfaces of the dry substrate to keep the temperature-changing composition within the tissue paper and to help prevent irritation to the skin during use.
[0015] Other features and aspects of the present invention are discussed in greater detail below. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] A complete and enabling description of the present invention, including the best mode thereof, for the person skilled in the art is shown more particularly in the remainder of the descriptive report, including reference to the accompanying figures, in which: Figure 1 is a view of cross section of the illustrated dry substrate; Figure 2 is a cross-sectional view of another embodiment of a dry substrate prepared in accordance with the present invention; Figure 3 is a schematic illustration of an exemplary conversion operation for dry substrate prepared in accordance with the present invention; and Figure 4 is a schematic illustration of an exemplary printing operation for dry substrate prepared in accordance with the present invention.
[0017] The use of repeated reference characters in this descriptive report and drawings is intended to represent the same features or elements or features or analogous elements of the present invention. DETAILED DESCRIPTION
[0018] It should be understood by one skilled in the art that the present discussion is only a description of exemplary embodiments, and is not intended to be limiting of the broader aspects of the present invention.
[0019] Dry, as used herein, to describe tissue or cleaning paper products, means that the product is supplied without any moisture other than equilibrium moisture, which is generally associated with the product. "Balance moisture" is the moisture the leaf contains when exposed to environmental conditions for extended periods of time. The equilibrium humidity within the sheet will not change over time at the same relative humidity and temperature. Typically, dry products will have equilibrium moisture contents of less than 15%, such as, less than 10%, such as about 3% to about 8% under most environmental conditions, which are encountered during product routine.
[0020] The heat absorption factor, as used herein, expressed in J/m2, is defined as the product of the heat of fusion of the cooling composition, expressed in J/g, and the application rate of the applied cooling composition to the tissue paper product, expressed in g/m2.
[0021] The latent heat of fusion and melting points are determined by differential scanning calorimetry (DSC). Melting point, as defined herein, refers to the peak melting mass temperature as determined by DSC. Samples can be analyzed on a TA Instruments DSC 2920 Modulated DSC (standard cell) using the following experimental procedure: Approximately 5 mg of the respective material was weighed to the nearest 0.1 mg. Samples are processed in the temperature range of -50°C to 100°C with a heating/cooling rate of 10°C/min in an atmosphere of inert gas (N2). The heat of fusion (Alif) is computed from the integral under the respective melting peak, with the reported results being the average value from 3 heating/cooling cycles.
[0022] The present invention, generally speaking, is directed to dry cleaning products, such as dry tissue paper products, which exhibit improved perceived benefits. In particular, cleansers, when in contact with the skin, can provide a cooling sensation and feeling. A cooling sensation, for example, can provide comfort and a feeling of calm to irritated skin. It is also found that, when used with a toilet tissue, cooling can evoke a sensation of dampness, which can lead to a perception of improved cleanliness. In one embodiment, the cleanser can be designed to provide a cooling sensation without substantial transfer of the phase change chemical composition to the user's skin.
[0023] In one embodiment, for example, described herein is a dry cleaning product, such as a facial tissue paper product, which contains a temperature-changing composition. The temperature change composition includes at least one phase change agent, which undergoes a phase change when its temperature is raised. The phase change agent, for example, can have a relatively high heat of fusion, which allows it to absorb large amounts of thermal energy and regulate to a lower temperature than ambient. In particular, when the cleaning product is heated, such as being in contact with someone's skin, the phase change agent quickly heats to its melting point. Due to the high heat of fusion, significant amounts of heat can then be absorbed while the phase change agent is melted. In turn, a cooling sensation is provided to the user's skin.
[0024] Referring to Figure 1, an embodiment of a tissue paper product 10, prepared in accordance with the present invention, is shown. The tissue paper product 10 can contain any suitable base sheet made from several different types of fiber supplies. The tissue paper product 10 contains multiple tissue paper webs laminated or bonded or otherwise combined together.
[0025] Tissue paper webs, which can be used to construct the tissue paper product 10, for example, generally may contain pulp fibers alone or in combination with other fibers. Each tissue paper web can generally have a bulk density of at least 2 cm3/g, such as at least 3 cm3/g.
[0026] Fibers suitable for preparing tissue paper webs contain any natural or synthetic cellulosic fibers, including, but not limited to, non-wood fibers such as cotton, Manila hemp, kenaf, sabai grass, flax, esparto grass, straw, jute, hemp, bagasse, milkweed yarn fibers and pineapple leaf fibers; and wood or pulp fibers such as those obtained from deciduous or coniferous trees, including softwood fibers such as northern and southern softwood kraft fibers; hardwood fibers such as eucalyptus, maple, birch and birch. Pulp fibers can be prepared in high-yield or low-yield forms and can be pulped in any known method, including the high-yield pulping methods kraft, sulfite and other known pulping methods. Fibers prepared from organosolv pulping methods can also be used, including the fibers and methods described in U.S. Patent No. 4,793,898 issued December 27, 1988 to Laamanen, et al.; U.S. Patent No. 4,594,130 issued June 10, 1986 to Chang, et al.; and U.S. Patent No. 3,585,104 issued June 15, 1971 to Kleinert. Useful fibers can also be produced by pulping with anthraquinone, exemplified by U.S. Patent No. 5,595,628 issued January 21, 1997 to Gordon, et al.
[0027] A portion of the fibers, such as up to 50% or less by dry weight, or from about 5% to about 30% by dry weight, may be made up of synthetic fibers such as rayon, polyolefin fibers, polyester fibers, bicomponent core-wrap fibers, multicomponent binder fibers, and the like. An exemplary polyethylene fiber is Pulpex®, available from Hercules, Inc. (Wilmington, DE). Any known bleaching method can be used. Types of synthetic cellulose fibers include rayon in all its varieties and other fibers derived from viscose or chemically modified cellulose. Chemically treated natural cellulosic fibers can be used, such as mercerized pulps, chemically stiffened or crosslinked fibers or sulphonated fibers. For good mechanical properties, when using papermaking fibers, it may be desirable for the fibers to be relatively undamaged and largely unrefined or only slightly refined. Although recycled fibers can be used, virgin fibers are generally useful for their mechanical properties and lack of contaminants. Mercerized fibers, regenerated cellulosic fibers, cellulose produced by microbes, rayon and other cellulosic material or cellulosic derivatives can be used. Suitable papermaking fibers can also include recycled fibers, virgin fibers or mixtures thereof. In certain modalities capable of high bulk and good compressive properties, the fibers may have a Canadian standard freedom of at least 200, more specifically at least 300, more specifically at least 400, and most specifically at least 400 minus 500.
[0028] Other papermaking fibers can include broken or recycled fibers and high yield fibers. High yield pulp fibers are those papermaking fibers produced by pulping processes providing a yield of about 65% or greater, more specifically of about 75% or greater, and even more specifically of about from 75% to about 95%. Yield is the resulting amount of processed fibers expressed as a percentage of the initial wood mass. Pulping processes include bleached chemothermomechanical pulp (BCTMP), chemothermomechanical pulp (CTMP), thermomechanical pressure/pressure pulp (PTMP), thermomechanical pulp (TMP), chemical thermomechanical pulp (TMCP), high yield sulfite pulps, and High-yield kraft pulps, all of which leave the resulting fibers with high levels of lignin. High yield fibers are well known for their stiffness in both dry and wet states relative to typical chemically pulped fibers.
[0029] In general, any process capable of forming a tissue paper web can also be used. For example, a papermaking process may use creping, wet creping, double creping, embossing, wet pressing, air pressing, air drying, air creping drying, non-creping air drying, hydroentanglement, air dispersion, as well as other steps known in the art.
[0030] The tissue paper web can be formed from a supply of fibers containing pulp fibers in an amount of at least about 50% by weight, such as at least about 60% by weight, such as from at least about 70% by weight, such as at least about 80% by weight, such as at least about 90% by weight, such as 100% by weight.
[0031] Also suitable for products are tissue paper sheets that are densified or pattern-printed, such as tissue paper sheets described in any of US Patent Nos: 4,514,345 issued April 30, 1985 to Johnson, et al. al.; 4,528,239 issued July 9, 1985 to Trokhan; 5,098,522 issued March 24, 1992 to Smurkoski, et al.; 5,260,171 issued November 9, 1993 to Smurkoski, et al.; 5,275,700 issued January 4, 1994 to Trokhan; 5,328,565 issued July 12, 1994 to Rasch, et al.; 5,334,289 issued Aug. 2, 1994 to Trokhan, et al.; 5,431,786 issued July 11, 1995 to Rasch, et al.; 5,496,624 issued March 5, 1996 to Steltjes, Jr., et al.; 5,500,277 issued March 19, 1996 to Trokhan, et al.; 5,514,523 issued May 7, 1996 to Trokhan, et al.; 5,554,467 issued September 10, 1996 to Trokhan, et al.; 5,566,724 issued October 22, 1996 to Trokhan, et al.; 5,624,790 issued April 29, 1997 to Trokhan, et al.; and 5,628,876 issued May 13, 1997 to Ayers, et al., the descriptions of which are incorporated herein by reference to the extent that they are not contradictory with the present invention. Such printed tissue sheets may have a network of densified regions, which have been printed against a drum dryer by a printing tissue, and regions which are relatively less densified (eg "domes" in the tissue sheet) corresponding the deflection conduits in the printing tissue, with the tissue paper sheet superimposed over the deflection conduits, was deflected by an air pressure differential across the deflection conduit to form a pillow-like region of low density or dome on tissue paper sheet.
[0032] The tissue paper web can also be formed without a substantial amount of internal fiber-to-fiber bond strength. In this regard, the fiber supply used to form the base web can be treated with a chemical debonding agent. The debonding agent can be added to the fiber slurry during the pulping process or it can be added directly to the headbox. Suitable debonders may include cationic debonders such as fatty dialkyl quaternary amine salts, fatty monoalkyl tertiary amine salts, primary amine salts, imidazoline quaternary salts, silicone quaternary salts and fatty alkyl amine salts unsaturated. Other suitable debonders are described in U.S. Patent No. 5,529,665 issued June 25, 1996 to Kaun, which is incorporated herein by reference. In particular, the Kaun '665 patent describes the application of cationic silicone compositions as release agents.
[0033] In one embodiment, the debonding agent may be an organic quaternary ammonium chloride, and particularly a silicone-based amine salt of a quaternary ammonium chloride. For example, the debonding agent may be PROSOFT® TQ1003 marketed by Hercules Corporation. The debonding agent can be added to the fiber slurry in an amount of from about 1 kg per metric ton to about 10 kg per metric ton of fibers present within the slurry.
[0034] In an alternative embodiment, the debonding agent may be an imidazoline-based agent. The imidazoline-based debonding agent can be obtained, for example, from Witco Corporation (Greenwich, CT). The imidazoline-based debonding agent can be added in an amount of between 2 kg per metric ton and about 15 kg per metric ton.
[0035] In one embodiment, the debonding agent may be added to the fiber supply in accordance with a process as described in PCT Application having International Publication No. WO 99/34057, filed December 17, 1998, or in the Application Published PCT featuring International Publication No. WO 00/66835, filed April 28, 2000, both of which are incorporated herein by reference. In the above publications, a process is described in which a chemical additive, such as a debonding agent, is adsorbed onto cellulosic papermaking fibers at high levels. The process includes the steps of treating a fiber slurry with an excess of the chemical additive, allowing sufficient residence time for adsorption to occur, filtering the slurry to remove non-adsorbed chemical additives, and redispersion of the filtered pulp with fresh water. before the formation of a non-woven web.
[0036] Optional chemical additives may also be added to the aqueous papermaking supply or to the formed embryonic web to provide additional benefits to the product and process and that are not antagonistic to the intended benefits of the dry substrate. The following materials are included as examples of additional chemicals, which can be applied to the web in conjunction with the temperature shift composition or hydrophilic lotion composition. Chemicals are included as examples and are not intended to limit the scope of the invention. Such chemicals can be added at any point in the papermaking process, including being added simultaneously with the additive composition in the pulpmaking process, with the additive or additives being combined directly with the additive composition.
[0037] Additional types of chemicals that can be added to the paper web include, but are not limited to, absorbance aids usually in the form of cationic, anionic or nonionic surfactants, wetting agents and plasticizers such as poly(ethylene glycols) of low molecular weights and polyhydroxy compounds such as glycerine and propylene glycol. Materials that provide health benefits to the skin, such as mineral oil, aloe extract, vitamin E, silicone, general lotions, and the like, can also be incorporated into finished products.
[0038] In general, the products of the present invention can be used in conjunction with any known materials and chemicals that are not antagonized by their intended use. Examples of such materials include, but are not limited to, odor control agents such as odor absorbers, activated carbon fibers and particles, baby powder, baking soda, chelating agents, zeolites, perfumes or other masking agents of odor, cyclodextrin compounds, oxidants and the like. Superabsorbent particles, synthetic fibers or films can also be used. Additional options include cationic dyes, optical brighteners, humectants, emollients and the like.
[0039] Tissue paper webs, which can be treated with the temperature change composition and the hydrophilic lotion composition, may include a single homogeneous fiber layer or fiber layers, or may include a layered or layered construction. For example, the tissue paper web layer can include two or three layers of fibers. Each layer can have a different fiber composition.
[0040] Each of the fiber layers contains a dilute aqueous suspension of papermaking fibers. The particular fibers contained in each layer generally depend on the product being formed and the desired results. In one embodiment, for example, a middle layer contains southern softwood kraft fibers, either alone or in combination with other fibers, such as high-yield fibers. The outer layers, on the other hand, can contain softwood fibers, such as northern softwood kraft fibers.
[0041] In an alternative embodiment, the middle layer may contain softly fibers for strength, while the outer layers may contain hardwood fibers, such as eucalyptus fibers, for perceived softness.
[0042] The grammage of tissue paper webs may vary depending on the final product. For example, the process can be used to produce facial tissue papers, toilet papers, paper towels, industrial cleaners, and the like. In general, the grammage of tissue paper products can range from about 10 g/m2 to about 80 g/m2, such as from about 20 g/m2 to about 60 g/m2. For tissue and facial tissue, for example, the weight can range from about 10 g/m2 to about 60 g/m2. For paper towels, on the other hand, the weight can range from about 25 g/m2 to about 80 g/m2.
The apparent volume of tissue paper web can also range from about 2 cm3/g to 20 cm3/g, such as from about 5 cm3/g to 15 cm3/g. Sheet "apparent volume" is calculated as the quotient of the gauge of a sheet of dry tissue paper, expressed in micrometers, divided by the dry weight, expressed in grams per square meter. The resulting apparent leaf volume is expressed in cubic centimeters per gram. More specifically, caliper is measured as the total thickness of a stack of ten representative sheets and dividing the total thickness of the stack by ten, with each sheet within the stack being placed with the same side facing up. Gauge is measured in accordance with TAPPI test method T411 om-89 "Thickness (Gage) of Combined Paper, Cardboard and Boards" with Note 3 for stacked sheets. The micrometer used to perform the T411 om-89 is an Emveco 200-A Tissue Caliper Tester, available from Emveco, Inc. (Newberg, OR). The micrometer features a load of 2.00 Kilopascal (132 grams per square inch), a pressure foot area of 2,500 square millimeters, a pressure foot diameter of 56.42 millimeters, a hold time of 3 seconds, and a rate of decrease of 0.8mm per second.
[0044] In products with multiple layers, the weight of each web of paper that is present in the product may also vary. In general, the total grammage of a multilayer product will generally be the same as indicated above, such as from about 20 g/m2 to about 80 g/m2. Therefore, the grammage of each layer can be from about 5 g/m2 to about 60 g/m2, such as from about 10 g/m2 to about 40 g/m2.
[0045] In accordance with the present invention, the tissue paper product 10 contains a temperature change composition to impart a cooling sensation to a user's skin. The operative temperature change composition contains an effective amount of at least one phase change agent. The temperature shifting composition can be incorporated into the tissue paper product in such a way that substantially no temperature shifting composition is present on the outer surfaces. For example, referring to Figure 1, there is shown a tissue paper product 10, which comprises a first web of tissue paper 22, laminated or bonded or otherwise combined with a second web of tissue paper 24. As shown, positioned between the first tissue paper web 22 and the second tissue paper web 24 is a temperature change composition 26. By positioning the temperature change composition 26 between the tissue paper webs, the temperature change composition is substantially minimized from coming into contact with or being transferred to a user's skin. However, when the tissue paper product 20 is held against the skin, body heat will be absorbed by the temperature-changing composition 26 through the tissue paper webs, thus rising in temperature. The increase in temperature will cause a phase change to occur in the phase change agent, providing a cooling sensation to the user's skin.
[0046] The temperature change composition includes at least one phase change agent, which undergoes a phase change when heated, which in turn provides a cooling sensation to the skin. The temperature shift composition can be incorporated into tissue paper product 10 using any suitable method or technique. For example, the temperature change composition can be sprayed over the tissue paper product, extruded over the tissue paper product, or printed over the tissue paper product using, for example, flexographic printing, gravure printing direct or indirect gravure printing. In yet another embodiment, the temperature shift composition can be applied to the tissue paper product using any suitable coating equipment, such as a knife coater or slit coater. Since the temperature shift composition is solid at room temperature, in one embodiment it may be desirable to melt the composition prior to application to the tissue paper web. The application of such fused materials to a finished tissue paper web is well known in the art. Sometimes it may also be advantageous to cool the web directly after applying the molten phase change agent, especially when the treated product is wound onto a spiral wound roll either into a finished product or for further processing. Cooling the web below the melting point of the phase change agent reduces the potential for the spirally wound web to become "locked". As used herein, "blocked" refers to the tendency of sheets that turn adjacently on the spirally wound roll to adhere to one another and restrict the ability to unwind the web from the spirally wound roll.
[0047] In general, a phase change agent includes any substance that has the ability to absorb or release thermal energy to reduce or eliminate heat flux in or within a temperature stabilization range. The temperature stabilization range can include a particular transition temperature or transition temperature range. A phase change agent will preferably be able to change a thermal energy flow over a period of time, where the phase change agent is absorbing or releasing heat, typically as the phase change agent transitions between two states (eg, liquid and solid states, liquid and gas states, solid and gas states, or two solid states). This action is typically transient, meaning it will occur until latent heat from the phase change agent is absorbed or released during a heating or cooling process. Thermal energy can be stored in or removed from the phase change agent, and the phase change agent typically can be effectively recharged by a source of heat or cold. Temperature change compositions may exhibit a phase change at temperatures between about 23°C and about 35°C, such as is suitable for use in cooling the skin. Materials can also be chosen with transition temperatures between about 23°C and about 32°C, between about 26°C and about 32°C, or within any other suitable range. The phase change temperature is selected such that the phase change occurs between the product's ambient temperature and the user's external skin temperature.
[0048] The temperature change composition may contain a mixture of phase change agents that have a mixture of transition temperatures. When a mixture of phase change agents is used, the components can be selected so as to have a collective melting point within the limits mentioned above. In some cases, the melting points of the individual phase change agents comprising the temperature change composition may fall outside the melting point limits for the phase change temperature of the temperature change composition. However, the mixture of phase change agents will exhibit a phase change within the desired temperature limits. When the temperature-changing composition is held against the skin, either directly or indirectly, the composition heats to skin temperature from room temperature. The phase change agent then melts at your specified phase change temperature. That fusion requires heat, which is taken from the skin, giving a feeling of cooling. Once the material is molten, the cooling sensation dissipates. By having a range of phase change temperatures (melting points in this case) of the phase change agents, one can extend the range of temperatures at which cooling is felt. In one example, a combination of phase change agents, having phase change temperatures at 18°C, 28°C and 35°C, are combined to create a temperature change composition having a melting point between 23°C. C and 32°C.
[0049] Suitable phase change agents include, by way of example and not limitation, encapsulated phase change powders (eg LURAPRET, an encapsulated, purified paraffin available from BASF, and available MPCM 43-D from Microtek Laboratories), hydrocarbons (eg straight chain alkanes or paraffinic hydrocarbons, branched chain alkanes, unsaturated hydrocarbons, halogenated hydrocarbons and alicyclic hydrocarbons), waxes, natural butters, fatty acids, fatty acid esters, dibasic acids, esters dibasics, 1-halides, primary alcohols, aromatics, anhydrides (eg stearic anhydride), ethylene carbonate, polyhydric alcohols (eg 2,2-dimethyl-1,3-propane-diol, 2-hydroxy -methyl-2-methyl-1,3-propane-diol, pentaerythritol, dipentaerythritol, pentaglycerin, tetramethylol ethane, neopentyl glycol, tetramethylol propane, monoaminopentaerythritol, diaminopentaerythritol and tris(hydroxymethyl) acid a skeptical), polymers (eg, polyethylene, poly(ethylene glycol), polypropylene, poly(propylene glycol), poly(tetramethylene glycol), and copolymers such as polyacrylate or poly(meth)acrylate with an alkyl or hydrocarbon side chain with poly(ethylene glycol) side chain and copolymers comprising polyethylene, poly(ethylene glycol), polypropylene, poly(propylene glycol) or poly(tetramethylene glycol), and mixtures thereof. Desirable examples of phase change materials include tricaprin, paraffin, nonadecane, octadecane, stearyl heptanoate, lauryl lactate, lauryl alcohol, capric acid, caprylic acid, cetyl babassuate, Mangifera indica stone butter (mango), butter. Theobroma kernel cocoa (cocoa), Butyrospermum parkii butter, di-C12-C15-alkyl fumarate, stearyl caprylate, cetyl lactate, cetyl acetate, C24-C28-alkyl methicone, glyceryl dilaurate, chloride phosphate of PG-stearamido-propyl dimonium, jojoba esters and combinations thereof.
[0050] As described above, in one embodiment, the temperature change composition may contain a mixture of two or more phase change agents. In a particular embodiment, the temperature shift composition contains a mixture of stearyl heptanoate and n-octadecane.
[0051] Phase change agents can include phase change agents in an unencapsulated form and phase change agents in an encapsulated form. A phase change agent in a non-encapsulated form can be supplied as a solid in a variety of forms (eg bulk form, powders, pellets, granules, flakes, paste and so on) or as a liquid in a variety of forms (eg, molten form, dissolved in a solvent, and so on).
[0052] Another aspect of temperature change compositions is the heat of fusion of the temperature change composition comprising the phase change agents. Temperature shift compositions can exhibit melting heats of at least about 100 J/g. For example, in one embodiment, the temperature change composition contains a hydrocarbon as the phase change agent, such as a straight chain hydrocarbon. The hydrocarbon may contain, for example, more than 12 carbon atoms in the chain, such as from about 18 carbon atoms to about 19 carbon atoms in the chain. Particular examples of phase change agents include, for example, octadecane (melting heat of about 213.0 J/g), nonadecane, stearyl heptanoate, and mixtures thereof.
[0053] Perhaps most importantly, however, is the heat absorption factor of the products. The heat absorption factor, expressed in J/m2, is the product of the heat of fusion of the temperature change composition, expressed in J/g, and the application rate of the temperature change composition applied to the tissue paper product , expressed in g/m2. The heat absorption factor of the products can be at least 500 J/m2 such as at least 1000 J/m2 such as from about 1000 J/m2 to about 4000 J/m2 or greater. For many applications, the temperature change composition can be applied to a tissue paper web such that the phase change agents are present in the web in an amount of from about 4 g/m2 to about 40 g/m2.
[0054] In a specific embodiment, the cooling tissue paper product is a facial tissue paper comprising three or more layers, two outer layers and one or more inner layers. The temperature change composition is applied to at least one of the one or more inner layers. In another embodiment, the cooling tissue product is a facial tissue paper comprising two layers, comprising two outwardly facing surfaces and two oppositely facing internal surfaces. Phase change composition is applied to one or both of the oppositely facing inner surfaces. In another embodiment, the product is a multilayer tissue paper product in which the phase change composition is selectively applied to the inner portion of the multilayer product so as to minimize blocking.
[0055] A hydrophilic lotion composition 28 is applied to the outer surface of the tissue paper product and used in conjunction with temperature change composition 26. "Hydrophilic(a)" as used herein means miscible with water. The hydrophilic lotion composition creates a hydrophilic surface and restores absorbance to the treated sheet, while creating a high energy surface that is not wettable by the phase change material. In this way, the tissue paper product 20 can not only provide a cooling sensation to the user, but can also prevent the transfer of the phase change agent over the skin by trapping the phase change agents within the substrate. With prior temperature change compositions, described, for example, in PCT Patent Application No. PCT/IB2009/051515 entitled "Tissue Products having a Cooling Sensation When Contacted with Skin", the phase change materials transfer to the skin and cause irritation.
[0056] The hydrophilic lotion composition contains a vehicle and a thermo-reversible gelling agent, the lotion being positioned on at least one outer surface of the substrate and preferably on both outer surfaces of the substrate.
[0057] Vehicles for use in the hydrophilic lotion composition may include, but are not limited to, water, glycerin, diglycerin, glycerin derivatives, glycols, glycol derivatives, sugars, ethoxylated and/or propoxylated ethers and ethers, urea, PCA sodium, alcohols, ethanol, isopropyl alcohol, and combinations thereof. Desirably the vehicle is propylene glycol.
Typically, the hydrophilic lotion composition contains a carrier in an amount of from about 1% by weight of the hydrophilic lotion composition to about 99.9% by weight of the hydrophilic lotion composition, more typically from about 2 % by weight of the hydrophilic lotion composition to about 95% by weight of the hydrophilic lotion composition, and more typically from about 5% by weight of the hydrophilic lotion composition to about 90% by weight of the hydrophilic lotion composition .
[0059] Thermo-reversible gelling agents are defined as ingredients that are soluble, partially soluble or miscible in a hydrophilic vehicle at elevated temperatures, such as 50°C, which have the ability to thicken the vehicle when cooled to 25°C , but will be less viscous at 50°C when application to a substrate is required. Suitable hydrophilic vehicles include water, glycols and, in particular, propylene glycol. Thermo-reversible gelling agents for use in the hydrophilic lotion composition may include, but are not limited to, fatty acid salts such as sodium stearate, sodium palmitate, potassium stearate. These salts can be added to the composition or can be created in situ by addition of the fatty acid and neutralizing with an appropriate base. An example of in situ formation of the hydrophilic lotion composition is providing stearic acid and sodium hydroxide to produce sodium stearate.
Other desirable thermo-reversible gelling agents could include, but would not be limited to, poly(ethylene glycols) and derivatives such as PEG-20, PEG-150 distearate, PEG-150 pentaerythryl tetrastearate, distearate -75 IPDI, distearet-100 IPDI, fatty alcohols such as cetyl alcohol, fatty acids such as stearic acid, hydroxy-stearic acid and combinations thereof.
Typically, the hydrophilic lotion composition contains a thermo-reversible gelling agent in an amount from about 1% by weight of the hydrophilic lotion composition to about 99.9% by weight of the hydrophilic lotion composition, more typically from about 2% by weight of the hydrophilic lotion composition to about 95% by weight of the hydrophilic lotion composition, and more typically from about 5% by weight of the hydrophilic lotion composition to about 90% by weight of hydrophilic lotion composition.
[0062] In addition to the vehicle and the thermo-reversible gelling agent, the hydrophilic lotion composition may contain various other ingredients and components. Examples of other ingredients, which may be included within the hydrophilic lotion composition, are emollients, sterols or sterol derivatives, natural and synthetic fats or oils, viscosity enhancers, rheology modifiers, polyols, surfactants, alcohols, esters, silicones, clays, starch, cellulose, particulates, moisturizers, film formers, slip modifiers, surface modifiers, skin protectants, humectants, sunscreens, and the like.
[0063] Therefore, hydrophilic lotion compositions optionally may additionally include one or more emollients, which typically act to soften, smooth and otherwise lubricate and/or moisturize the skin. Suitable emollients which can be incorporated into the compositions include oils such as natural oils such as jojoba, sunflower, saffron, and the like, synthetic base oils such as petrolatum, mineral oils, alkyl dimethicones, alkyl -methicones, alkyl-dimethicone copolyols, phenyl-silicones, alkyl-trimethyl-silanes, dimethicone, cross-linked polymers of dimethicone, cyclomethicone, lanolin and its derivatives, glycerol esters and derivatives, propylene glycol esters and derivatives, esters and derivatives of fatty acids, alkoxylated carboxylic acids, alkoxylated alcohols, and combinations thereof.
Ethers such as eucalyptol, cetearyl glycoside, polyglyceryl-3 cetyl dimethyl isosorbic ether, polyglyceryl-3 decyl tetradecanol, propylene glycol myristyl ether, and combinations thereof, can also be suitably used as emollients.
[0065] The hydrophilic lotion composition may include one or more emollients in an amount from about 0.01% by weight of the hydrophilic lotion composition to about 70% by weight of the hydrophilic lotion composition, more desirably, from about 0.05% by weight of the hydrophilic lotion composition to about 50% by weight of the hydrophilic lotion composition, and even more desirably from about 0.1% by weight of the hydrophilic lotion composition to about 40% by weight of the hydrophilic lotion composition.
[0066] The hydrophilic lotion composition may include one or more viscosity enhancers in an amount from about 0.01% by weight of the hydrophilic lotion composition to about 25% by weight of the hydrophilic lotion composition, more desirably, of from about 0.05% by weight of the hydrophilic lotion composition to about 10% by weight of the hydrophilic lotion composition, and even more desirably from about 0.1% by weight of the hydrophilic lotion composition to about 5 % by weight of the hydrophilic lotion composition.
[0067] The hydrophilic lotion composition optionally may additionally contain humectants. Examples of suitable humectants include glycerin, glycerin derivatives, sodium hyaluronate, betaine, amino acids, glycosaminoglycans, honey, sorbitol, glycols, polyols, sugars, polyol, hydrogenated starch hydrolysates, PCA salts, lactic acid, lactates and urea. A particularly preferred humectant is glycerin. The hydrophilic lotion composition may suitably include one or more humectants in an amount from about 0.05% by weight of the hydrophilic lotion composition to about 25% by weight of the hydrophilic lotion composition.
[0068] The hydrophilic lotion composition optionally may additionally contain film formers. Examples of suitable film formers include lanolin derivatives (eg acetylated lanolins), superfatty oils, cyclomethicone, cyclopentasiloxane, dimethicone, synthetic and biological polymers, proteins, quaternary ammonium materials, starches, gums, cellulosic products, polysaccharides, albumin, acrylate derivatives, IPDI derivatives, and the like. The composition of the present invention may suitably include one or more film formers in an amount of from about 0.01% by weight of the hydrophilic lotion composition to about 20% by weight of the hydrophilic lotion composition.
[0069] The hydrophilic lotion composition optionally may additionally contain slip modifiers. Examples of suitable slip modifiers include bismuth oxychloride, iron oxide, mica, surface treated mica, ZnO, Zr02, silica, silica silylate, colloidal silica, attapulgite, sepiolite, starches (i.e. corn, tapioca, rice) , cellulosic products, nylon-12, nylon-6, polyethylene, talc, styrene, polystyrene, polypropylene, ethylene/acrylic acid copolymer, acrylates, acrylate copolymers (crosslinked methyl methacrylate polymer), sericite, titanium dioxide, oxide of aluminum, silicone resin, barium sulfate, calcium carbonate, cellulose acetate, poly(methyl methacrylate), poly(methylsilsequioxane), talc, tetrafluoroethylene, silk powder, boron nitride, lauroyllysine , synthetic oils, natural oils, esters, silicones, glycols and the like. The hydrophilic lotion composition may suitably include one or more slip modifiers in an amount from about 0.01% by weight of the hydrophilic lotion composition to about 20% by weight of the hydrophilic lotion composition.
[0070] The hydrophilic lotion composition may also additionally contain surface modifiers. Examples of suitable surface modifiers include silicones, quaternary materials, powders, salts, peptides, polymers, clays and glyceryl esters. The hydrophilic lotion composition may suitably include one or more surface modifiers in an amount from about 0.01% by weight of the hydrophilic lotion composition to about 20% by weight of the hydrophilic lotion composition.
[0071] The hydrophilic lotion composition may also additionally contain skin protectants. Examples of suitable skin protectants include ingredients referenced in the SP Monograph (21 CFR part 347). Suitable skin protectants and amounts include those shown in the SP Monograph, Subpart B Active Ingredients Sec 347.10: (a) Allantoin, 0.5 to 2%, (b) Aluminum hydroxide gel, 0.15 to 5%, (c) ) Calamine, 1 to 25%, (d) Cocoa butter, 50 to 100%, (e) Cod liver oil, 5 to 13.56%, according to 347.20(a)(1) or (a) (2), provided the product is labeled such that the quantity used in a 24-hour period does not exceed 10,000 USP Units of vitamin A and 400 Units U.S.P. of cholecalciferol, (f) Colloidal oatmeal, 0.007% minimum; 0.003% minimum in combination with mineral oil in accordance with §347.20(a)(4), (g) Dimethicone, 1 to 30%, (h) Glycerin, 20 to 45%, (i) Hard fat, 50 to 100% , (j) Kaolin, 4 to 20%, (k) Lanolin, 12.5 to 50%, (1) Mineral oil, 50 to 100%; 30 to 35% in combination with colloidal oatmeal according to §347.20(a)(4), (m) Petrolatum, 30 to 100%, (n) Sodium bicarbonate, (o) Topical starch, 10 to 98% , (p) White petroleum, 30 to 100%, (q) Zinc acetate, 0.1 to 2%, (r) Zinc carbonate, 0.2 to 2%, (s) Zinc oxide, 1 to 25 %.
[0072] The hydrophilic lotion composition may also additionally contain quaternary ammonium materials. Examples of suitable quaternary ammonium materials include polyquaternium-7, polyquaternium-10, benzalkonium chloride, berrentrimonium methosulfate, cetrimonium chloride, cocamidopropyl pg-dimonium chloride, guar hydroxy-propyl-trimonium chloride, isostearamido-propyl-lactate. morpholine, polyquaternium-33, polyquaternium-60, polyquaternium-79, quaternium-18 hectorite, hydrolyzed quaternium-79 silk, hydrolyzed quaternium-79 soy protein, starch-propyl-ethyl-dimonium ethosulfate of rapeseed, silicone quaternium-7, stearalkonium chloride, palmitamido-propyl-trimonium chloride, butyl-glycosides, hydroxy-propyl-trimonium chloride, laurdimonium chloride-hydroxy-propyl-decyl-glycosides, and the like. The hydrophilic lotion composition may suitably include one or more quaternary materials, in an amount from about 0.01% by weight of the hydrophilic lotion composition to about 20% by weight of the hydrophilic lotion composition.
[0073] The hydrophilic lotion composition optionally may additionally contain surfactants. Examples of suitable additional surfactants include, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, nonionic surfactants and combinations thereof. Specific examples of suitable surfactants are known in the art and include those suitable for incorporation into hydrophilic lotion compositions and cleaning cloths. The hydrophilic lotion composition may suitably include one or more surfactants in an amount of from about 0.01% by weight of the hydrophilic lotion composition to about 20% by weight of the hydrophilic lotion composition.
[0074] The hydrophilic lotion composition may also additionally contain additional emulsifiers. As mentioned above, natural fatty acids, esters and alcohols and their derivatives, and combinations thereof, can act as emulsifiers in the composition. Optionally, the composition may contain an additional emulsifier other than natural fatty acids, esters and alcohols and their derivatives, and combinations thereof. Examples of suitable emulsifiers include nonionic ones such as polysorbate 20, polysorbate 80, anionic ones such as DEA phosphate, cationic ones such as berentrimonium methosulfate, and the like. The hydrophilic lotion composition may suitably include one or more additional emulsifiers in an amount from about 0.01% by weight of the hydrophilic lotion composition to about 20% by weight of the hydrophilic lotion composition.
[0075] The hydrophilic lotion composition may additionally include adjuvant components conventionally found in pharmaceutical compositions in their art-established manner and at their art-established levels. For example, the compositions may contain additional compatible pharmaceutically active materials for combination therapy, such as antimicrobial agents, antioxidants, antiparasitic agents, antipruritic agents, antifungal agents, antiseptic actives, biological actives, astringents, keratolytic actives, local anesthetics, antisting agents, anti-redness agents , skin softening agents, and combinations thereof. Other suitable additives that may be included in hydrophilic lotion compositions include dyes, deodorants, fragrances, perfumes, emulsifiers, defoaming agents or defoaming agents, lubricants, natural moisturizing agents, skin conditioning agents, skin protectants and other beneficial agents of the skin (eg extracts such as aloe vera and antiaging agents such as peptides), solvents, solubilizing agents, suspending agents, wetting agents, humectants, preservatives, pH adjusters, buffering agents, dyes and/ or pigments, and combinations thereof.
[0076] In addition to a product having two webs, as shown in Figure 2, other tissue paper products, which can be prepared in accordance with the present invention, may include more than two webs. For example, a tissue paper product with 3 webs 30 is illustrated in Figure 3. As shown, the tissue paper product 30 includes a tissue paper web of medium 34 laminated or bonded or combined by any other means to the tissue paper webs. external 32 and 36. A temperature change composition is positioned between the first tissue paper web 32 and the medium tissue paper web 34. A temperature change composition 40 is also positioned between the medium tissue paper web 34 and the second outer tissue paper web 36.
[0077] Furthermore, each of the tissue paper webs can be single-ply or multi-ply. In a desirable embodiment, each of the tissue paper webs contains two layers.
Referring now to Figure 3, a converting line 50 is schematically illustrated. Two rolls 52 of tissue paper web are provided. Tissue paper webs have a first side 64 and a second side 66.
[0079] Prior to conversion, each of the tissue paper webs is passed through an gravure coater 70, as illustrated in Figure 4. Each gravure coater 70 has two gravure rollers 72, 74. The first gravure roller 72 contains the temperature change composition including the phase change material, while the second gravure roller 74 contains the hydrophilic lotion composition. The first gravure roller 72 applies the temperature change composition to a first side 64 of both rolls of tissue paper web. Second gravure roller 74 applies the hydrophilic lotion composition to a second side 66 of both rolls of tissue paper web.
[0080] The rewinding machine joins the two rolls 52 of the tissue paper web into a combined web. The two rolls of tissue paper 52 are wound together such that the first side 64 of the first web and the first side 64 of the second web face each other. Therefore, the temperature shift composition is between the first web and the second web, and the hydrophilic lotion composition is present on the outer surfaces of the combined web.
[0081] If a web with the temperature change composition is provided on both sides of the web, blocking may occur during the production process. By providing two webs with the temperature change composition on a first side, and a hydrophilic lotion composition on a second side, blocking issues can be reduced. Therefore, the method described is a more efficient process to produce the tissue paper product.
[0082] The combined web then optionally can be passed through a 52 calender or multiple calenders. The calender can use non-compressive metallic rollers; compression rollers such as urethane, paper, rubber or composite; or using a combination of a non-compression roller and a compression roller. The calender can be operated in a nip condition for a fixed load, or in an interval mode for a fixed interval, or in an interval mode with one of the rollers transitioning at a speed faster than the speed of the webs.
[0083] After calendering, the combined web can then optionally be passed through a crimp station 54. The crimp station includes an anvil roller and a plurality of crimp wheels. The crimp wheels emboss the combined weft such that the two wefts become connected to each other.
[0084] The combined web then passes through a rolling mill 58 and is wound onto a hard roll 60 by a winder 62. Subsequent converting equipment, known to those skilled in the art, can unwind the two-layer hard roll, cut, fold and wrap the stiff roll into the shape of a box of facial tissue papers. EXAMPLES
[0085] The present invention can be better understood with reference to the following examples. Comparative Example 1
[0086] Comparative Example 1 represents a facial tissue paper treated with commercial lotion for a control product. A three-layer creped tissue paper sheet having a finished weight of 44 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers was used. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. A hydrophobic lotion treatment composition was heated to a temperature of 63°C and printed on both outer sides of the three-layer tissue paper product via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 63°C to ensure that the hydrophobic lotion treatment composition remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The three-layer facial tissue paper is treated with the hydrophobic lotion treatment composition to a final treatment level of 7.8 g/m2. The composition of the hydrophobic lotion treatment is shown below in Table 1. Table 1: Hydrophobic lotion treatment composition
Comparative Example 2
[0087] Comparative Example 2 represents a facial tissue paper treated with hydrophilic lotion without any phase change material. A three-layer creped tissue paper sheet having a finished weight of 44 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers was used. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. A hydrophilic lotion treatment composition was heated to a temperature of 63°C and printed on both outer sides of the three-layer tissue paper product via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 63°C to ensure that the hydrophilic lotion treatment composition remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The three-layer facial tissue paper is treated with the single pass hydrophilic lotion treatment composition to a final treatment level of 12.5 g/m2. The composition of hydrophilic lotion treatment composition 1 is shown below in Table 2. Table 2: Hydrophilic lotion treatment composition 1
Comparative Example 3
[0088] Comparative Example 3 represents a facial tissue paper with an inner phase change material but without any outer treatment layer. A two-layer creped tissue paper sheet having a finished basis weight of 30 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers was used. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. A temperature shift composition of n-octadecane (commercially available from Chevron-Philips) was heated to a temperature of 40°C and printed on both outer sides of the two-layer tissue paper product via a gravure printing process on simultaneous offset. The printer's fluid reservoirs were heated to 40°C to ensure the phase change material remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layer facial tissue paper was treated with molten n-octadecane and printed onto both sides of the two-layer tissue paper substrate. The tissue paper substrate was treated twice to a final treatment level of 11.1 g/m2. In addition, an untreated two-layer tissue paper web was prepared for an outer layer.
[0089] The rolls were positioned on two unwinders such that the roll of treated phase change material was situated in front of the roll for the outer layer. The layers on the roll for the outer layers were separated to sandwich the two-layer sheet from the roll treated with the phase change material. The resulting four layer structure was calendered, crimped and cut to standard facial tissue paper width. The four-layer finished product consisted of two inner layers treated with a phase change material and two outer layers without any treatment. The untreated outer layers would come into direct contact with the skin during use. Comparative Example 4
[0090] Comparative Example 4 represents a facial tissue paper with an internal phase change material with a hydrophobic lotion treatment layer. A two-layer creped tissue paper sheet having a finished basis weight of 30 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers was used. Each layer was made up of a supply of laminated fibers including two outer layers and a middle layer. A temperature shift composition of stearyl heptanoate (Tegasoft SH commercially available from Evonik, Inc.) was heated to a temperature of 40°C and printed on both outer sides of the two-layer tissue paper product via a printing process by simultaneous offset gravure printing. The printer's fluid reservoirs were heated to 40°C to ensure the phase change material remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layer facial tissue paper was treated with molten stearyl heptanoate and printed onto both sides of the two-layer tissue paper substrate. The tissue paper substrate was treated with two passes to a final treatment level of 13.7 g/m2.
[0091] In addition, a two-layer creped tissue paper sheet was used, having a finished basis weight of 30 g/m2, consisting of 70 percent hardwood fibers and 30 percent softwood fibers. Each layer was made up of a supply of laminated fibers including two outer layers and a middle layer. A hydrophobic lotion treatment composition was heated to a temperature of 63°C and printed on both outer sides of the two-layer tissue paper product via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 63°C to ensure that the hydrophobic lotion treatment composition remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, W1). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layered facial tissue paper is treated with the hydrophilic lotion treatment composition of Comparative Example 1 to a final treatment level of 7.8 g/m2.
[0092] The two rollers were then positioned on two unwinders such that the treated phase change material was situated in front of the roller to the outer layer featuring the hydrophobic lotion composition. The layers on the roll for the outer layers were separated to sandwich the two-layer sheet from the roll treated with the phase change material. The resulting four layer structure was calendered, crimped and cut to standard facial tissue paper width. The four-layer finished product consisted of two inner layers treated with a phase change material and two outer layers with a hydrophobic lotion treatment. The outer layers with the hydrophobic lotion treatment would come into direct contact with the skin during use. Comparative Example 5
[0093] Comparative Example 5 represents another facial tissue paper with an internal phase change material with a hydrophobic lotion treatment layer. A two-layer creped tissue paper sheet having a finished basis weight of 30 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers was used. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. A temperature shift composition of n-octadecane (commercially available from Chevron-Philips) was heated to a temperature of 40°C and printed on both outer sides of the two-layer tissue paper product via a gravure printing process on simultaneous offset. The printer's fluid reservoirs were heated to 40°C to ensure the phase change material remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layer facial tissue paper was treated with molten n-octadecane and printed onto both sides of the two-layer tissue paper substrate. The tissue paper substrate was treated twice to a final treatment level of 11.1 g/m2.
[0094] In addition, a two-layer creped tissue paper sheet was used, having a finished basis weight of 30 g/m2, consisting of 70 percent hardwood fibers and 30 percent softwood fibers. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. A hydrophobic lotion treatment composition was heated to a temperature of 63°C and printed on both outer sides of the two-layer tissue paper product via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 63°C to ensure that the hydrophobic lotion treatment composition remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layer facial tissue paper is treated with the hydrophobic lotion treatment composition from Comparative Example 1 for a final treatment level of 7.8 g/m2.
[0095] The two rolls were then positioned on two unwinders such that the roll of treated phase change material was situated in front of the roll for the outer layer featuring the hydrophobic lotion composition. The layers on the roll for the outer layers were separated to sandwich the two-layer sheet from the roll treated with the phase change material. The resulting four layer structure was calendered, crimped and cut to standard facial tissue paper width. The four-layer finished product consisted of two inner layers treated with a phase change material and two outer layers with a hydrophobic lotion treatment. The outer layers with the hydrophobic lotion treatment would come into direct contact with the skin during use. Example 1
[0096] Example 1 represents a facial tissue paper with an inner phase change material layer and a hydrophilic lotion treatment layer. A two-layer creped tissue paper sheet having a finished basis weight of 30 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers was used. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. A material (from Chevron-Philips) was heated to a temperature of 40°C and printed on both outer sides of the two-layer tissue paper product via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 40°C to ensure the phase change material remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Rolier Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layer facial tissue paper was treated with molten n-octadecane and printed onto both sides of the two-layer tissue paper substrate. The tissue paper substrate was treated twice to a final treatment level of 11.1 g/m2.
[0097] In addition, a two-layer creped tissue paper sheet was used, having a finished weight of 30 g/m2, consisting of 70 percent hardwood fibers and 30 percent softwood fibers. Each layer was made up of a supply of laminated fibers including two outer layers and a middle layer. A hydrophilic lotion treatment composition was heated to a temperature of 63°C and printed on both outer sides of the two-layer tissue paper product via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 63°C to ensure that the hydrophilic lotion treatment composition remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a line screen of 360 cells per linear inch and a volume of 8 billion cubic micrometers (BCM) per square inch of roller surface. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Roller Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute). The two-layered facial tissue paper is treated with the hydrophilic treatment composition of Comparative Example 2 to a final treatment level of 11.8 g/m2.
[0098] The rollers were positioned on two unwinders, such that the treated phase change material was situated in front of the roller to the outer layer featuring the hydrophilic lotion composition. The layers on the roll for the outer layers were separated to sandwich the two-layer sheet from the roll treated with the phase change material. The resulting four layer structure was calendered, crimped and cut to standard facial tissue paper width. The four-layer finished product consisted of two inner layers treated with a phase change material and two outer layers with a hydrophilic lotion treatment. The outer layers with the hydrophilic lotion treatment would come into direct contact with the skin during use. Experiment 1
[0099] Comparative Examples 1-5 and Example 1 were evaluated in clinical and sensory tests. A Nostril Irritation Study evaluated the skin beside the nasal region after frequent repeated cleaning with tissue paper substrate. The Adaptive Methodology Panel (AMP) assessed the characteristics of tissue paper, including those associated with cooling and residue (as measured by auditory intensity). The results from these studies are illustrated in Table 3 and summarized below. For characteristics, examples with the same letter are similar in that attribute, and examples with the letter "A" are considered to have the maximum of that characteristic. Treatment levels are the total treatment applied to 2 sides of the treated tissue paper. Table 3: Clinical/Sensory Study Results

[00100] Comparative Example 1 serves as the performance benchmark for cooling tissue paper in terms of auditory intensity and low skin damage and redness. The control product of Comparative Example 1 is not perceived to be cooling.
[00101] Comparative Example 2 is also not perceived to be cooling. Comparative Example 2 is comparable in terms of hearing intensity, skin damage and redness to Comparative Example 1.
[00102] Comparative Example 3 provides a feeling of cooling, but has high residue, or higher hearing intensity, and causes skin irritation. The phase change material in Comparative Example 3 has likely migrated by capillarity to the surface of the tissue paper and becomes available for direct contact with the skin, without the use of a hydrophilic lotion composition.
[00103] Comparative Example 4 is cooling, has acceptable hearing intensity, but is more damaging to the skin than Comparative Examples 1 and 2. Since the outer lotion is hydrophobic, some of the phase change material may have migrated to the surface of the tissue paper or migrated by capillary to the surface upon fusion and made available for direct contact with the skin.
[00104] tissue paper from Comparative Example 5 has acceptable residue (hearing intensity), but is only slightly cooling and is more harmful to the skin than Comparative Examples 1 and 2. Treatment with hydrophobic outer layer reduced the residue, a skin injury and redness, when compared to Comparative Example 3, but reduces the sensation of cooling. It appears that the hydrophobic treatment components may have mixed with the n-octadecane to disturb its crystallinity and cooling. It is also likely that some of the n-octadecane has migrated or capillary-migrated to the tissue paper surface upon fusion and has become available for direct contact with the skin.
[00105] Example 1 has excellent cooling characteristics and compares favorably with acceptable residue (hearing intensity), skin damage and redness, when compared to Comparative Examples 1 and 2. In addition, Example 1 is of greater cooling than Comparative Examples 4 and 5, but lacks the skin damage and redness deficiencies. Finally, Example 1 is just as cool as Comparative Example 3, without showing the residual deficiencies (hearing intensity), skin damage and redness. The use of an external hydrophilic lotion treatment with the phase change material provides a combination of the best attributes. Experiment 2
[00106] Piles comprising 50-90 treated tissue papers from Comparative Examples 2-5 and Example 1 were placed in boxes and evaluated in a one month aging study. The stack size varied in the number of layers on each sheet. Boxes containing sheets with four layers typically had stacks with a count of 50-60, while boxes containing sheets with three layers typically had stacks with a count of 90. All boxes were filled such that the top sheet was in contact with the top inner surface of the box. The boxes were inspected after storage for one month at both 25°C and 55°C. Packaging notes are indicated as light with grease-like buildup and/or staining at the bottom of the box; moderate with grease-like buildup and/or staining on the bottom and sides of the box; and severe with grease-like build-up and/or staining on the bottom, sides and top of the case. The results are shown in Table 4, below. Table 4: Results of Aging Study by Packaging

[00107] Buildup and staining of the boxes were observed for Comparative Examples 4 and 5, but not for Comparative Examples 2 and 3 or Example 1. Buildup is clearly a problem for comparative examples with outer layers containing hydrophobic lotion treatments . This can be the result of the direct interaction of the treatment with the box or the interaction of the phase change material with the hydrophobic treatment and the box. At 55°C, the phase change material is melted and free to mix with the softened hydrophobic treatment composition. In the case of the hydrophilic lotion treated outer layer (Example 1), the phase change material and treatment are immiscible, thus the phase change material is presumably contained within the structure. Neither the hydrophilic treatment (Comparative Example 2) nor the phase change materials alone (Comparative Example 3) caused accumulation in the boxes. Example 2
[00108] An alternative four-layer structure can be created by applying a different treatment to each side of a two-layer web and then combining these webs. The resulting four-layer structure would then feature hydrophilic lotion-treated outer layers with an inner core treated with phase change material.
[00109] Unlike Example 1, the hydrophilic treatment is separated from the phase change material, on both sides, by two layers of tissue paper instead of one. In this structure, the hydrophilic treatment and two layers of tissue paper would serve as a potential barrier between the phase change material and human skin during use.
[00110] Two-layer creped tissue paper sheets having a finished basis weight of 30 g/m2 consisting of 70 percent hardwood fibers and 30 percent softwood fibers were used. Each layer was made from a supply of laminated fibers including two outer layers and a middle layer. Stearyl heptanoate was melted and placed in a cavity of a heated double offset gravure printing process equipped with an 8 BCM gravure roller. The hydrophilic treatment composition from Comparative Example 2 was prepared and placed in the other cavity of the printing process equipped with a 4 BCM gravure roller. Both compositions were heated to a temperature of 63°C and printed on both outer sides of each of the two-layer tissue paper products via a simultaneous offset gravure printing process. The printer's fluid reservoirs were heated to 63°C to ensure that the hydrophilic lotion treatment composition remained molten throughout the entire application process. The engraving rollers were electronically engraved chrome-on-copper rollers supplied by Southern Graphics Systems (Louisville, KY). The rollers featured a 360 cells per linear inch line screen. The rubber coated offset applicator rolls featured a 75 Shore A durometer hollow polyurethane surface and were supplied by the American Rolier Company (Union Grove, WI). The process was adjusted to a condition having 0.7938 cm (0.3125 inches) of interference between the gravure rollers and the rubber-lined rollers and 0.007 cm (0.003 inches) of clearance between the facing rubber-lined rollers. The simultaneous offset/offset gravure press was operated at 45.7 m/min (150 ft/minute).
[00111] The treated wefts were cooled to 25°C to solidify the treatments before winding. The treated rolls were immediately treated a second time. Care was taken to ensure that the second print run applied the same treatment to a given side as was applied in the first print run.
[00112] Rolls treated with two layers were combined and converted into finished product with four layers. The rolls were positioned on two unwinders so that the stearyl heptanoate treated layers of each roll were in the center of the four ply sheet, and the hydrophilic treated plies of each roll were the outer layers of the four ply sheet. The combined four layer structure was calendered, crimped and cut to standard facial tissue paper width. Example 2 was found to be cooling, although causing little redness or damage to the skin. Example 3
[00113] Example 3 was produced in the same manner as described in Example 2, but with a different hydrophilic lotion composition. The composition of hydrophilic lotion treatment composition 2 is shown below in Table 5. Table 5: Hydrophilic lotion treatment composition 2

[00114] Example 3 was found to be cooling, although causing little redness or damage to the skin.
[00115] These and other modifications and variations, in relation to the appended claims, may be practiced by those skilled in the art, without departing from the spirit and scope of the appended claims. In addition, it should be understood that aspects of the various modalities can be interchanged, both in whole and in part. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the appended claims.

权利要求:
Claims (11)
[0001]
1. Dry substrate, characterized in that it comprises: a first web (22, 32), comprising fibers, and a second web (24), comprising fibers; a temperature change composition (26) located between the first web (22, 32) and the second web (24), the temperature change composition (26) containing a phase change agent which undergoes a phase change at a temperature of 20°C to 35°C, the phase change agent having a heat of fusion of at least 100 J/g and being present in the dry substrate such that the dry substrate has a heat absorption factor of at least 100 J/g. minus 500 J/m2; and a hydrophilic lotion on an outer surface of the dry substrate comprising a carrier present in an amount of between 1% by weight of the hydrophilic lotion composition (28) and 99.9% by weight of the hydrophilic lotion composition (28) and a conditioning agent. thermo-reversible gelation present in an amount between 0.1% by weight of the hydrophilic lotion composition (28) and 50% by weight of the hydrophilic lotion composition (28).
[0002]
2. Dry substrate according to claim 1, characterized by the fact that the phase change agent is oil soluble and hydrophobic.
[0003]
3. Dry substrate according to claim 1, characterized in that the phase change agent is selected from tricaprin, paraffin, nonadecane, octadecane, stearyl heptanoate, lauryl lactate, lauryl alcohol, capric acid, babassuate of cetyl, dipropylene glycol isocetet-20 acetate, PEG-12, bis-PEG-15 methyl ether dimethicone, Butyrospermum parkii butter, di-C12-C15-alkyl fumarate, stearyl caprylate, cetyl lactate, acetate cetyl, C24-C28-alkylmethicone, glyceryl dilaurate, cocet-10, PG-dimonium stearamidopropyl chloride-phosphate, cetyl alcohol, jojoba esters and combinations thereof.
[0004]
4. Dry substrate according to claim 1, characterized in that the vehicle is selected from water, glycerin, diglycerin, glycerin derivatives, glycols, glycol derivatives, sugars, ethoxylated and/or propoxylated ethers and esters , urea, sodium PCA, alcohols, ethanol, isopropyl alcohol, and combinations thereof.
[0005]
5. Dry substrate according to claim 1, characterized in that the thermo-reversible gelling agent is selected from poly(ethylene glycols) and derivatives thereof, PEG-150 pentaerythryl tetrastearate, distearet- 75 IPDI, distearet-100 IPDI, fatty alcohols, fatty acids, fatty acid salts and combinations thereof.
[0006]
6. Dry substrate according to claim 1, characterized in that the temperature change composition (26) is present in the web in an amount from 4 g/m2 to 40 g/m2.
[0007]
7. Dry substrate according to claim 1, characterized in that the substrate includes a third web (34).
[0008]
8. Dry substrate according to claim 1, characterized in that the phase change agent comprises a hydrocarbon, a wax, an oil, a fatty acid, a fatty acid ester, a dibasic acid, a dibasic ester , a 1-halide, a primary alcohol, an aromatic compound, an anhydride, an ethylene carbonate, a polyhydric alcohol, or mixtures thereof.
[0009]
9. Dry substrate, according to claim 1, characterized in that the substrate comprises a tissue paper (10) facial.
[0010]
10. Dry substrate according to claim 1, characterized in that each of the first web (22, 32) and second web (24) comprises two layers.
[0011]
11. Method of preparing the dry substrate as defined in claim 1, characterized in that it comprises: providing a first web (22, 32) comprising fibers, the first web (22, 32) having a first side (64) and a second side (66); providing a second web (24) comprising fibers, the second web (24) having a first side (64) and a second side (66); applying a temperature change composition (26) onto the first side (64) of the first web (22, 32) and the first side (64) of the second web (24); applying a hydrophilic lotion composition (28) onto the second side (66) of the first web (22, 32) and the second side (66) of the second web (24); winding the first weft (22, 32) and the second weft (24) together to form a combined weft so that the first side (64) of the first weft (22, 32) faces the first side (64 ) of the second web (24) and that the temperature change composition (26) is between the first web (22, 32) and the second web (24); combined weft calendering; and crimping the first frame (22, 32) to the second frame (24).

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012011937B1|2021-06-22|DRY SUBSTRATE, E, METHOD OF PREPARATION OF THE DRY SUBSTRATE

---

US9545365B2|2017-01-17|Temperature change compositions and tissue products providing a cooling sensation

---

BR112012011934B1|2021-07-20|DRY SUBSTRATE

---

US8940323B2|2015-01-27|Tissue products having a cooling sensation when contacted with skin

同族专利:

---

公开号 | 公开日

---

IL219228A|2014-03-31|

---

AU2010320532B2|2016-03-24|

---

US20130292044A1|2013-11-07|

---

US20110123578A1|2011-05-26|

---

EP2501265B1|2016-01-13|

---

US8480852B2|2013-07-09|

---

KR20120107073A|2012-09-28|

---

MX343237B|2016-10-27|

---

WO2011061641A3|2011-10-27|

---

JP5731527B2|2015-06-10|

---

EP2501265A2|2012-09-26|

---

AU2010320532A1|2012-05-17|

---

EP2501265A4|2015-05-06|

---

IL219228D0|2012-06-28|

---

CA2777842C|2017-10-24|

---

JP2013511508A|2013-04-04|

---

BR112012011937A2|2020-09-08|

---

MX2012005788A|2012-06-19|

---

CA2777842A1|2011-05-26|

---

ZA201202789B|2013-06-26|

---

WO2011061641A2|2011-05-26|

---

KR101783492B1|2017-09-29|

---

US8894814B2|2014-11-25|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US1253603A|1916-11-13|1918-01-15|Clinton D Keagy|Disinfecting device.|

---

GB107922A|1916-12-08|1917-07-19|John Harwood|Improvements in Cases for Treasury Notes, Cheques, Bills or the like.|

---

US1579124A|1923-09-27|1926-03-30|Macgrath Harold Faulder|Disinfecting attachment for money drawers|

---

US1885278A|1931-10-24|1932-11-01|Chauncey D Monett|Money sterilizer|

---

US2721554A|1954-08-02|1955-10-25|Joa Curt George|Sanitary napkin and absorbent pad which comprises a part thereof|

---

US3301746A|1964-04-13|1967-01-31|Procter & Gamble|Process for forming absorbent paper by imprinting a fabric knuckle pattern thereon prior to drying and paper thereof|

---

US3264172A|1965-04-24|1966-08-02|Calgon Corp|Bacteriostatic paper containing a guanidine salt and method of making the same|

---

US3516941A|1966-07-25|1970-06-23|Minnesota Mining & Mfg|Microcapsules and process of making|

---

US3607348A|1968-05-14|1971-09-21|Little Rapids Pulp Co|Twice-coated cellulosic-fiber structure and its manufacture|

---

US3585104A|1968-07-29|1971-06-15|Theodor N Kleinert|Organosolv pulping and recovery process|

---

US4208459A|1970-04-13|1980-06-17|Becker Henry E|Bonded, differentially creped, fibrous webs and method and apparatus for making same|

---

US3812000A|1971-06-24|1974-05-21|Scott Paper Co|Soft,absorbent,fibrous,sheet material formed by avoiding mechanical compression of the elastomer containing fiber furnished until the sheet is at least 80%dry|

---

US3974025A|1974-04-01|1976-08-10|The Procter & Gamble Company|Absorbent paper having imprinted thereon a semi-twill, fabric knuckle pattern prior to final drying|

---

US4100324A|1974-03-26|1978-07-11|Kimberly-Clark Corporation|Nonwoven fabric and method of producing same|

---

US4594130A|1978-11-27|1986-06-10|Chang Pei Ching|Pulping of lignocellulose with aqueous alcohol and alkaline earth metal salt catalyst|

---

US4191609A|1979-03-09|1980-03-04|The Procter & Gamble Company|Soft absorbent imprinted paper sheet and method of manufacture thereof|

---

US4504442A|1982-10-19|1985-03-12|Scopas Technology Corporation|Use of chlorine dioxide gas as a chemosterilizing agent|

---

US4637859A|1983-08-23|1987-01-20|The Procter & Gamble Company|Tissue paper|

---

US4528239A|1983-08-23|1985-07-09|The Procter & Gamble Company|Deflection member|

---

US4514345A|1983-08-23|1985-04-30|The Procter & Gamble Company|Method of making a foraminous member|

---

US4604313A|1984-04-23|1986-08-05|Kimberly-Clark Corporation|Selective layering of superabsorbents in meltblown substrates|

---

US4585482A|1984-05-25|1986-04-29|Southern Research Institute|Long-acting biocidal compositions and method therefor|

---

US4738847A|1985-01-14|1988-04-19|Kimberly-Clark Corporation|Multi-ply virucidal product|

---

US4793898A|1985-02-22|1988-12-27|Oy Keskuslaboratorio - Centrallaboratorium Ab|Process for bleaching organic peroxyacid cooked material with an alkaline solution of hydrogen peroxide|

---

US4677003A|1985-04-30|1987-06-30|Rohm And Haas Company|Microsuspension process for preparing solvent core sequential polymer dispersion|

---

BE905997A|1986-12-19|1987-04-16|Damman Max Willem|Disinfecting anti-contagion elements - for affixing to every-day objects e.g. telephone receiver, vacuum cleaner, ventilation duct, money etc.|

---

JPH0675589B2|1987-05-29|1994-09-28|エヌオーケー株式会社|Sterilizer / deodorant|

---

JP2747496B2|1988-11-04|1998-05-06|キンバリー―クラーク・テイシュー・カンパニー|Chemically treated paper products-towels and tissues|

---

US5126070A|1989-10-20|1992-06-30|The Drackett Company|Chlorine dioxide generator|

---

US5260171A|1990-06-29|1993-11-09|The Procter & Gamble Company|Papermaking belt and method of making the same using a textured casting surface|

---

DK0536320T3|1990-06-29|1995-02-20|Procter & Gamble|Paper making tape and method for making same using different lighting transmission technique|

---

US5098522A|1990-06-29|1992-03-24|The Procter & Gamble Company|Papermaking belt and method of making the same using a textured casting surface|

---

US5275700A|1990-06-29|1994-01-04|The Procter & Gamble Company|Papermaking belt and method of making the same using a deformable casting surface|

---

CA2069193C|1991-06-19|1996-01-09|David M. Rasch|Tissue paper having large scale aesthetically discernible patterns and apparatus for making the same|

---

CH686682A5|1992-05-05|1996-05-31|Granit Sa|Production of pulp according to the SAP procedure.|

---

US6319599B1|1992-07-14|2001-11-20|Theresa M. Buckley|Phase change thermal control materials, method and apparatus|

---

HU218422B|1992-08-26|2000-08-28|The Procter & Gamble Co.|Apparatus used in manufacturing a cellulosie fibrous structure and cellulosic fibrous structure made thereon|

---

US5350624A|1992-10-05|1994-09-27|Kimberly-Clark Corporation|Abrasion resistant fibrous nonwoven composite structure|

---

US6238682B1|1993-12-13|2001-05-29|The Procter & Gamble Company|Anhydrous skin lotions having antimicrobial components for application to tissue paper products which mitigate the potential for skin irritation|

---

WO1995016824A1|1993-12-13|1995-06-22|The Procter & Gamble Company|Lotion composition for imparting soft, lubricious feel to tissue paper|

---

US5500277A|1994-06-02|1996-03-19|The Procter & Gamble Company|Multiple layer, multiple opacity backside textured belt|

---

US5496624A|1994-06-02|1996-03-05|The Procter & Gamble Company|Multiple layer papermaking belt providing improved fiber support for cellulosic fibrous structures, and cellulosic fibrous structures produced thereby|

---

AT192519T|1994-06-17|2000-05-15|Procter & Gamble|LIQUID COMPOSITION FOR TREATING TISSUE PAPER|

---

BR9507940A|1994-06-17|1997-11-18|Procter & Gamble|Tissue paper with lotion|

---

US5529665A|1994-08-08|1996-06-25|Kimberly-Clark Corporation|Method for making soft tissue using cationic silicones|

---

US5643588A|1994-11-28|1997-07-01|The Procter & Gamble Company|Diaper having a lotioned topsheet|

---

JP3420647B2|1994-12-15|2003-06-30|株式会社トーメー|Cleaning agent for contact lenses|

---

US5665426A|1995-02-06|1997-09-09|Kimberly-Clark Corporation|Soft treated tissue|

---

US5705164A|1995-08-03|1998-01-06|The Procter & Gamble Company|Lotioned tissue paper containing a liquid polyol polyester emollient and an immobilizing agent|

---

US5624676A|1995-08-03|1997-04-29|The Procter & Gamble Company|Lotioned tissue paper containing an emollient and a polyol polyester immobilizing agent|

---

JPH09276027A|1996-04-17|1997-10-28|Kyodo Printing Co Ltd|Antibacterial small article|

---

US5830487A|1996-06-05|1998-11-03|The Procter & Gamble Company|Anti-viral, anhydrous, and mild skin lotions for application to tissue paper products|

---

US6028018A|1996-07-24|2000-02-22|Kimberly-Clark Worldwide, Inc.|Wet wipes with improved softness|

---

US5968853A|1997-03-10|1999-10-19|The Procter & Gamble Company|Tissue with a moisture barrier|

---

US5990377A|1997-03-21|1999-11-23|Kimberly-Clark Worldwide, Inc.|Dual-zoned absorbent webs|

---

US5869075A|1997-08-15|1999-02-09|Kimberly-Clark Worldwide, Inc.|Soft tissue achieved by applying a solid hydrophilic lotion|

---

US6423183B1|1997-12-24|2002-07-23|Kimberly-Clark Worldwide, Inc.|Paper products and a method for applying a dye to cellulosic fibers|

---

TW440641B|1997-12-24|2001-06-16|Kimberly Clark Co|Paper products and methods for applying chemical additives to cellulosic fibers|

---

WO1999042658A1|1998-02-20|1999-08-26|Textile Biocides, Inc.|Antimicrobial treatment of currency paper|

---

JP2000163629A|1998-11-30|2000-06-16|Hitachi Asahi Electronics Co Ltd|Paper money cleaning mechanism|

---

US6187695B1|1998-12-08|2001-02-13|Kimberly-Clark Worldwide, Inc.|Cool feeling tissue product and method|

---

EP1078980A1|1999-07-12|2001-02-28|The Procter & Gamble Company|A method of stain removal from garments worn on the body|

---

JP2001043447A|1999-07-29|2001-02-16|Toshiba Tec Corp|Cash box|

---

US20030077962A1|1999-08-24|2003-04-24|Krzysik Duane Gerard|Absorbent tissues providing skin barrier enhancement|

---

US6258249B1|1999-11-10|2001-07-10|Sulzer Carbomedics Inc.|Sterilization of surgical sites|

---

CN1088557C|1999-12-30|2002-08-07|王雪平|Persistent disinfectant and preparation process thereof|

---

MXPA02006539A|1999-12-30|2002-12-09|Kimberly Clark Co|Antiviral lotion tissue, and methods for making and using the same.|

---

GB0004796D0|2000-03-01|2000-04-19|Flux Peter J|Dispenser|

---

CN100488517C|2000-03-07|2009-05-20|拉什-长老会-圣路加医学中心|Composition for trapping and inactivating pathogenic microbes and spermatozoa and its pharmaceutical uses|

---

GB0016501D0|2000-07-06|2000-08-23|North John H|Improved dust/particle collecting bin for cyclone separators|

---

US6379712B1|2000-09-13|2002-04-30|Globoasia, L.L.C.|Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same|

---

US6756520B1|2000-10-20|2004-06-29|Kimberly-Clark Worldwide, Inc.|Hydrophilic compositions for use on absorbent articles to enhance skin barrier|

---

US6733773B1|2000-11-21|2004-05-11|Kimberly-Clark Worldwide, Inc.|Paper products treated with oil-in-water emulsions|

---

US6749860B2|2000-12-22|2004-06-15|Kimberly-Clark Worldwide, Inc.|Absorbent articles with non-aqueous compositions containing botanicals|

---

US6860967B2|2001-01-19|2005-03-01|Sca Hygiene Products Gmbh|Tissue paper penetrated with softening lotion|

---

US6905697B2|2001-01-19|2005-06-14|Sca Hygiene Products Gmbh|Lotioned fibrous web having a short water absorption time|

---

US6432270B1|2001-02-20|2002-08-13|Kimberly-Clark Worldwide, Inc.|Soft absorbent tissue|

---

GB0107922D0|2001-03-30|2001-05-23|Hansen Transmissions Int|Gear shaft bearing assembly|

---

GB2390609B|2001-04-09|2005-11-09|Scott Paper Ltd|Tissue products containing softness|

---

US6921609B2|2001-06-15|2005-07-26|Kureha Chemical Industry Co., Ltd.|Gradient cathode material for lithium rechargeable batteries|

---

US7005557B2|2001-07-03|2006-02-28|The Procter & Gamble Company|Film-forming compositions for protecting skin from body fluids and articles made therefrom|

---

DE10133399A1|2001-07-13|2003-01-23|Cognis Deutschland Gmbh|Low water-content wax-based composition for impregnating tissue paper or wet wipes to give body-care material contains dialkyl ether, dialkyl carbonate, dicarboxylic acid and/or hydroxyfatty alcohol|

---

US20030108761A1|2001-09-12|2003-06-12|Tammy Eddlemon|Anti-bacterial paper products|

---

WO2003035238A2|2001-10-19|2003-05-01|Clearant, Inc.|Methods for combating bio-terrorism|

---

US6582558B1|2001-11-15|2003-06-24|Kimberly-Clark Worldwide, Inc.|Soft absorbent tissue containing hydrophilic polysiloxanes|

---

US7045096B2|2001-12-31|2006-05-16|Argentara Five, Inc.|Sterilization and detoxification of confined spaces|

---

US20030147773A1|2002-02-01|2003-08-07|Bryner Roger S.|Apparatus and method for paper and dry goods bio-decontamination|

---

US20040140347A1|2002-03-11|2004-07-22|Gueorgui Mihaylov|Sanitizing secure and safe mail box|

---

US20030174810A1|2002-03-12|2003-09-18|Steris Inc.|Method and apparatus for destroying microbial contamination of mail|

---

US7169400B2|2002-05-07|2007-01-30|Fort James Corporation|Waterless lotion and lotion-treated substrate|

---

US8012495B2|2002-05-07|2011-09-06|Georgia-Pacific Consumer Products Lp|Lotion-treated tissue and towel|

---

US6869518B2|2002-06-12|2005-03-22|Ecolab Inc.|Electrochemical generation of chlorine dioxide|

---

US20040076544A1|2002-10-09|2004-04-22|Hung Dao|Method and apparatus for scanning and sterilizing mail received at a drop box|

---

EP1567718B1|2002-11-07|2013-04-17|Georgia-Pacific Consumer Products LP|Absorbent sheet exhibiting resistance to moisture penetration|

---

US6949167B2|2002-12-19|2005-09-27|Kimberly-Clark Worldwide, Inc.|Tissue products having uniformly deposited hydrophobic additives and controlled wettability|

---

US6896766B2|2002-12-20|2005-05-24|Kimberly-Clark Worldwide, Inc.|Paper wiping products treated with a hydrophobic additive|

---

US7008507B2|2002-12-31|2006-03-07|Kimberly-Clark Worldwide, Inc.|Non-impact printing method for applying compositions to webs and products produced therefrom|

---

US20050058674A1|2003-09-11|2005-03-17|Kimberly-Clark Worldwide, Inc.|Moisturizing and lubricating compositions|

---

US20050058693A1|2003-09-11|2005-03-17|Kimberly-Clark Worldwide, Inc.|Tissue products comprising a moisturizing and lubricating composition|

---

US7485373B2|2003-09-11|2009-02-03|Kimberly-Clark Worldwide, Inc.|Lotioned tissue product with improved stability|

---

US20050136765A1|2003-12-23|2005-06-23|Kimberly-Clark Worldwide, Inc.|Fibrous materials exhibiting thermal change during use|

---

CN1946902A|2004-04-23|2007-04-11|宝洁公司|Fibrous structures comprising a surface treating composition and a lotion composition|

---

US20050238701A1|2004-04-23|2005-10-27|Joerg Kleinwaechter|Fibrous structures comprising a transferable agent|

---

US8343534B2|2004-04-23|2013-01-01|The Procter & Gamble Company|Tissue including a volatile rhinological composition|

---

DE102004020083A1|2004-04-24|2005-11-17|Cognis Deutschland Gmbh & Co. Kg|Polyolefin-containing wipes|

---

US20050271710A1|2004-06-04|2005-12-08|Argo Brian P|Antimicrobial tissue products with reduced skin irritation potential|

---

US7381299B2|2004-06-10|2008-06-03|Kimberly-Clark Worldwide, Inc.|Apertured tissue products|

---

US7381693B2|2004-06-14|2008-06-03|Unilever Home & Personal Care Usa, Divison Of Conopco, Inc.|Fibrous elastic gel cleansing article|

---

ES2363688T3|2004-07-01|2011-08-11|E-L Management Corp.|COSMETIC COMPOSITIONS AND PROCEDURE TO PRODUCE A SENSORY REFRESHING SENSATION.|

---

US20060147502A1|2004-12-30|2006-07-06|Kimberly-Clark Worldwide, Inc.|Methods for controlling microbial pathogens on currency and mail|

---

US7582577B2|2005-08-26|2009-09-01|The Procter & Gamble Company|Fibrous structure comprising an oil system|

---

US20070148448A1|2005-12-28|2007-06-28|Kimberly-Clark Worldwide, Inc.|Microencapsulated delivery vehicles including cooling agents|

---

US7914891B2|2005-12-28|2011-03-29|Kimberly-Clark Worldwide, Inc.|Wipes including microencapsulated delivery vehicles and phase change materials|

---

US8319004B2|2006-08-17|2012-11-27|Kimberly-Clark Worldwide, Inc.|Training article for delivering unique sensations|

---

JP4762842B2|2006-09-27|2011-08-31|大王製紙株式会社|Sanitary tissue paper|

---

US8039011B2|2006-10-10|2011-10-18|Kimberly-Clark Worldwide, Inc.|Skin cooling compositions|

---

US20080107698A1|2006-11-08|2008-05-08|Fort James Corporation|Antimicrobial Cellulosic Sheet|

---

US20090110656A1|2007-10-31|2009-04-30|Lemke Sarah A|Skin cooling composition|

---

WO2009076572A2|2007-12-12|2009-06-18|3M Innovative Properties Company|Methods of making an article and articles|

---

US20090157153A1|2007-12-13|2009-06-18|Sarah Anne Lemke|Skin cooling system|

---

US20090155325A1|2007-12-14|2009-06-18|Kimberly-Clark Worldwide, Inc.|Formulation and products for promoting skin cleanliness and health|

---

US7972475B2|2008-01-28|2011-07-05|The Procter & Gamble Company|Soft tissue paper having a polyhydroxy compound and lotion applied onto a surface thereof|

---

US20090191285A1|2008-01-30|2009-07-30|Evonik Degussa Corporation|Moisturizing liquid liner for barrier layer|

---

US8940323B2|2008-05-30|2015-01-27|Kimberly-Clark Worldwide, Inc.|Tissue products having a cooling sensation when contacted with skin|

---

US8551517B2|2008-12-16|2013-10-08|Kimberly-Clark Worldwide, Inc.|Substrates providing multiple releases of active agents|

---

US20110086085A1|2009-10-13|2011-04-14|Wenzel Scott W|Carbohydrate Entrapped Active Agent Delivery Composition and Articles Using the Same|

---

US20110086084A1|2009-10-13|2011-04-14|David William Koenig|Active Agent Containing Polymer Network Delivery Composition and Articles Using the Same|

---

US8795717B2|2009-11-20|2014-08-05|Kimberly-Clark Worldwide, Inc.|Tissue products including a temperature change composition containing phase change components within a non-interfering molecular scaffold|

---

US9181465B2|2009-11-20|2015-11-10|Kimberly-Clark Worldwide, Inc.|Temperature change compositions and tissue products providing a cooling sensation|

---

US8480852B2|2009-11-20|2013-07-09|Kimberly-Clark Worldwide, Inc.|Cooling substrates with hydrophilic containment layer and method of making|

---

US20140054827A1|2012-03-14|2014-02-27|The Procter & Gamble Company|Method of Producing Color Change in a Substrate|US4915930A|1986-07-31|1990-04-10|Aluminum Company Of America|Process for producing aluminum hydroxide of improved whiteness|

---

US8172982B2|2008-12-22|2012-05-08|Kimberly-Clark Worldwide, Inc.|Conductive webs and process for making same|

---

US9181465B2|2009-11-20|2015-11-10|Kimberly-Clark Worldwide, Inc.|Temperature change compositions and tissue products providing a cooling sensation|

---

US8795717B2|2009-11-20|2014-08-05|Kimberly-Clark Worldwide, Inc.|Tissue products including a temperature change composition containing phase change components within a non-interfering molecular scaffold|

---

US8480852B2|2009-11-20|2013-07-09|Kimberly-Clark Worldwide, Inc.|Cooling substrates with hydrophilic containment layer and method of making|

---

JP4676564B1|2009-12-28|2011-04-27|大王製紙株式会社|Manufacturing method and equipment for tissue paper products|

---

US9439549B2|2010-12-08|2016-09-13|Georgia-Pacific Nonwovens LLC|Dispersible nonwoven wipe material|

---

MX353338B|2010-12-08|2018-01-09|Georgia Pacific Nonwovens Llc|Dispersible nonwoven wipe material.|

---

US20130245575A1|2012-03-14|2013-09-19|Sara Jo Griffin|Body product and method of delivery|

---

US20130267915A1|2012-04-09|2013-10-10|David Hoffman|Medical grade cleansing and numbing agent combination pad|

---

US10433700B2|2013-11-27|2019-10-08|Kimberly-Clark Worldwide, Inc.|Multi-purpose tough stain removal articles|

---

WO2015084358A1|2013-12-05|2015-06-11|Empire Technology Development Llc|Thermostatic materials, methods of making, and uses thereof|

---

US10473366B2|2014-09-18|2019-11-12|Carrier Corporation|Heat transfer system with phase change composition|

---

MX2018001611A|2015-08-31|2018-11-09|Kimberly Clark Co|Article of commerce treated with sublimable material.|

---

GB2557810B|2015-11-30|2021-11-24|Kimberly Clark Co|Structures containing thermo-sensitive gels|

---

KR20180035662A|2016-09-29|2018-04-06|엠버 테크놀로지스 인코포레이티드|Heated or cooled drinkware|

---

JP6633564B2|2017-03-31|2020-01-22|大王製紙株式会社|Method for producing tissue paper and tissue paper products|

---

JP6633565B2|2017-03-31|2020-01-22|大王製紙株式会社|Method for producing tissue paper and tissue paper products|

---

WO2021206784A1|2020-04-09|2021-10-14|Dow Global Technologies Llc|Coated sponges|

法律状态:
2020-09-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-02-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

---

2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/10/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, , QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US12/622,581|US8480852B2|2009-11-20|2009-11-20|Cooling substrates with hydrophilic containment layer and method of making|

---

US12/622,581|2009-11-20|

---

PCT/IB2010/054563|WO2011061641A2|2009-11-20|2010-10-08|Cooling substrates with hydrophilic containment layer and method of making|

---