WO2008030648A1 - Stable suspensions containing microcapsules and methods for the preparation thereof - Google Patents
Stable suspensions containing microcapsules and methods for the preparation thereof Download PDFInfo
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- WO2008030648A1 WO2008030648A1 PCT/US2007/071373 US2007071373W WO2008030648A1 WO 2008030648 A1 WO2008030648 A1 WO 2008030648A1 US 2007071373 W US2007071373 W US 2007071373W WO 2008030648 A1 WO2008030648 A1 WO 2008030648A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/12—Processes in which the treating agent is incorporated in microcapsules
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/345—Nitriles
- D06M13/348—Nitriles unsaturated, e.g. acrylonitrile
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
Definitions
- This invention relates generally to temperature regulating fabrics. More particularly, the present invention relates to a stable suspension used for the production of such fabric, which suspension comprises microcapsules comprising at least one phase-change material.
- the human body maintains its temperature at a constant level, by use of the sweating process for cooling and body hair as an isolation medium.
- Temperature-regulating material such as phase-change material
- phase-change material when placed near the body can help regulate skin and microclimate temperatures.
- Phase-change material with a phase- changing temperature in a desired range absorbs energy from the skin as the body temperature rises, and releases heat to the body as the body cools down. This results in less fluctuation in the human skin and microclimate temperatures, a greater feeling of comfort, less sweating, and lower microclimate relative humidity.
- Phase-change material can also function as an energy saver, e.g., if a room is furnished with an element containing phase-change material, such as paints, carpets, furniture finish, furniture fabrics or furniture coating, the element absorbs excessive heat during the warmer hours, and releases it during cooler hours.
- an element containing phase-change material such as paints, carpets, furniture finish, furniture fabrics or furniture coating
- the element absorbs excessive heat during the warmer hours, and releases it during cooler hours.
- it may also be used in building and construction materials such as insulation, roofing, wallboards, wallcoverings, ceiling materials, floor and floor covering materials, etc.
- phase-change materials may also be used in numerous other markets where temperature regulation, or temperature buffering, may have a benefit, such as: healthcare, apparel, electronics, transportation, shipping, cosmetics/personal care, food and beverage packaging, appliances, disposables and more.
- a temperature-regulating material may comprise any substance (or mixture of substances) that has the capability of absorbing or releasing thermal energy to reduce or eliminate heat flow at or within a temperature stabilizing range.
- the temperature stabilizing range may comprise a particular transition temperature or range of transition temperatures.
- a phase-change material if properly located in the final product, is capable of inhibiting a flow of thermal energy during a time when the phase-change material is absorbing or releasing heat, typically as the phase-change material undergoes a transition between two states (e.g., liquid and solid states, liquid and gaseous states, solid and gaseous states, or two solid states).
- This action is typically transient, e.g., occurs until a latent heat of the phase-change material is absorbed or released during a heating or cooling process.
- Thermal energy may be stored or removed from the phase-change material, and the phase-change material typically can be effectively recharged by a hot or cold source.
- Phase-change material normally is encapsulated. Encapsulation is desired for some of the following reasons: protection against leakage of the phase-change material after the phase- change to a liquid state; and protection of phase-change material from contamination, increased durability; product feel, etc.
- the capsules be in the micrometer / nanometer size range.
- the phase-change material capsules can be incorporated into a product without change in the appearance, texture or production process of the product.
- Capsules in the micrometer / nanometer size range are referred to here as microcapsules.
- Phase-change material encapsulated with microcapsules is referred to as microencapsulated phase-change material (mPCM)
- Microencapsulated phase-change material can be introduced into commercial products in various ways. According to some industrial practices, mPCM, typically in combination with binders, and possibly other components, is coated on commercial products. Coating may use known methods, such as knife -over-roll coating, roll coating, slot coating, screenprinting, foam coating, laminating, exhausting, spraying, padding, extrusions, embossing or flocking e.g. as described in U.S patents; 5,366,801; 6,207,738; 6,217,993; 6,503,976; 6,514,362; and 6,660,667, the relevant teachings of which are incorporated here by reference.
- Microencapsulated phase-change material can be coated on fibers prior to conversion to the final commercial product or after it.
- mPCM may be incorporated into the fibers in the process of their manufacture.
- the solution spinning process is generally used to form acrylic or regenerated cellulosic fibers
- the melt spinning process is generally used to form nylon fibers, polyester fibers, polypropylene fibers, and other similar type fibers.
- the solution spinning process is divided into two main spinning techniques; dry spinning and wet spinning. In the wet spinning process the spinnerets are submerged in or held very close to a chemical bath and as the filaments emerge they contact the chemical bath and precipitate from solution and solidify. In the dry spinning process instead of precipitating the polymer by dilution or chemical reaction, solidification is achieved by evaporating the solvent in a stream of air or inert gas which can be heated or cooled.
- This agglomeration may lead to manufacturing and yield problems and to the production of unattractive mPCM-containing fibers. Particularly affected are the physical properties of the fiber such as strength, denier variation, thick and thin spots, etc. If microcapsules agglomerate, production problems such as filter blockage, deposition on pipe walls, pressure and flow variations and spinneret hole blockage may occur. This further causes changes in fiber denier and or production line stoppage.
- a suspension of mPCM in a solution is produced and then mixed with a solution of a polymer or of a polymer-precursor (e.g. monomer) for spinning.
- the manufacturing process is simplified if a suspension of mPCM is formed in a way that is stable enough to enable storage prior to mixing with the polymer (or precursor) for a prolonged period with no substantial agglomeration or phase separation.
- the mPCM should be evenly dispersed in the mixture to enable the production of fibers with desired distribution of mPCM. Achieving such desired stable suspensions and even dispersion is difficult in many cases, e.g. due to the high ionic strength of the solution.
- creaming is observed. This term is used to describe the formation of two layers, with the microcapsules presiding in the top layer. If creaming occurs in pipe work, it forms a skin or coating on the pipe work which is very difficult to remove.
- a stable first suspension for the production of a temperature-regulating, polymer-containing fabric comprising a solvent and a plurality of microcapsules containing at least one phase- change material, wherein said microcapsules are to be incorporated in said polymer-containing fabric, and wherein said stable first suspension is characterized in that said solvent is capable of dissolving a fabric-forming component selected from the group consisting of at least one of said polymer and precursors thereof; and said suspension is stable for at least about 20 hours.
- the suspension stable for at least about 20 hours, meaning that no significant aggregation is noted, but the microcapsules in the suspension are also stable to degradation. Such degradation may lead to undesired leakage of phase-change material, if in liquid form.
- At least about 95% of the microcapsules in the suspension stay intact in the suspension for at least about 20 hours. According to an especially preferred embodiment, at least about 98% of the microcapsules in the suspension stay intact in the suspension for at least about 20 hours. In the most preferred embodiments, at least about 98% of the microcapsules in the suspension stay intact in the suspension for at least about 40 hours.
- said fabric is formed from at least one type of polymeric fiber.
- said polymer is selected from the group consisting of acrylonitrile-based polymers, cellulose-based polymers, polyester-based polymers, polyamide-based polymers and polyolefm based polymers.
- said solvent is an aqueous solution.
- said aqueous solution comprises at least one further component selected from the group consisting of sodium bases, sodium thiocyanate, zinc chloride, n-methyl morpholine oxide, ammonia, copper sulfate nitric acid, acetone, dimethyl formamide (DMF) and n-methyl pyrrolidone (NMP).
- at least one further component selected from the group consisting of sodium bases, sodium thiocyanate, zinc chloride, n-methyl morpholine oxide, ammonia, copper sulfate nitric acid, acetone, dimethyl formamide (DMF) and n-methyl pyrrolidone (NMP).
- said first suspension further comprises at least one further component selected from the group consisting of a defoaming agent, a flow-control agent, a wetting agent, a dispersing agent and surfactant.
- said aqueous solutions comprise at least one further component selected from the group consisting of sodium bases, sodium thiocyanate, zinc chloride, n-methyl morpholine oxide, ammonia, copper sulfate, nitric acid, acetone, DMF and NMP.
- microcapsules comprise a shell and a core and said shell is formed from at least one component selected from the group consisting of acrylic acid and derivatives thereof, methacrylic acid and derivatives thereof, formaldehyde, isocyanate, urea, carboxylic acid derivatives , silica precursor and gelatin.
- the microcapsules may comprise a shell and a core, wherein said core comprises a phase-change material selected from the group consisting of octadecane, straight-chain hydrocarbons with 15 to 25 carbon atoms, branched-chain hydrocarbons with 15 to 25 carbon atoms.
- the at least one phase-change material has a melting point in a range between about 2O°C and about 5O°C. According to still another embodiment of the invention the at least one phase-change material has a melting enthalpy in a range between about 80 J/g and about 400 J/g.
- microcapsules comprise a shell and a core and the weight ratio between said shell and core is in the range between about 0.5:9.5 and about 4:6.
- the weight ratio may also be in a range between about 1 :9 to about 3:7.
- microcapsules may form between about 5 and about 40 percent by weight of said suspension.
- microcapsules may form between about 10 and about 30 percent by weight of said suspension.
- the microcapsules may have a variety of regular or irregular shapes (e.g., spherical, ellipsoidal, and so forth) and variety of sizes.
- the individual microcapsules may have the same or different shapes or sizes.
- the microcapsules have a maximum linear dimension ranging between about 0.1 and about 20 micron.
- the microcapsules Preferably have a maximum linear dimension ranging between about 0.3 and about 2 micron.
- the polymer is acrylonitrile-based
- the solvent of the stable suspension comprises water and sodium thiocyanate
- the concentration of the sodium thiocaynate ranges between about 40 and about 60 percent by weight of the solvent and the microcapsules form between about 5 and about 30 percent by weight of said suspension.
- the polymer is acrylonitrile-based
- the solvent of the stable suspension comprises water and sodium thiocaynate
- the concentration of the sodium thiocyanate ranges between about 45 and about 55 percent by weight of the solution
- the microcapsules form between about 8 and about 20 percent by weight of said suspension and the suspension is kept at an ambient temperature.
- said polymer is cellulose-based, wherein said solvent comprises water and sodium hydroxide, wherein the concentration of the sodium hydroxide ranges between about 1 percent and about 5 percent and wherein said microcapsules form between about 5 and about 30 percent of said suspension.
- a second suspension formed from the first suspension as defined above, in combination with at least one polymeric fiber forming component selected from the group consisting of a polymer and a precursor thereof.
- Said microcapsules may be evenly dispersed throughout said second suspension.
- the second suspension contains microcapsules incorporating at least one functional compound, said functionality being selected from the group consisting of fire retardation, bioactivity, antimicrobial activity, odor resistance, UV absorption, moisture management and resistance to water, grease, dirt and/or stain.
- microcapsules are present in said stable suspension prior to said combining, introduced with the combined polymer or precursor, introduced after said combining or any combination of those options.
- all types of microcapsules are evenly dispersed in the second suspension.
- the solvent is preferably selected so that it is capable of dissolving the polymer and/or a precursor for its formation.
- the solvent is an aqueous solution.
- an aqueous solution of sodium thiocyanate is a suitable solution in case the polymer is acrylonitrile based while an aqueous solution of sodium hydroxide is a suitable solution if the polymer is cellulose based.
- the solvent is provided at an ambient temperature.
- the solvent and a plurality of microcapsules are mixed to form the stable suspension.
- the solvent is added to the microcapsules while being mixed with a low-shear mixer.
- a method for manufacturing of said first suspension comprising the steps of providing microcapsules containing a phase-change material; providing a solvent capable of dissolving a fabric-forming component selected from the group consisting of at least one of said polymer and precursors thereof; and mixing said solvent and said microcapsules to form said first suspension.
- said solvent is provided at a temperature in the range of between about ambient and 120 °C.
- said first suspension is kept at a temperature in the range of between about ambient and 120 °C.
- said first suspension is kept under low-shear mixing.
- Said microcapsules may be provided in a vessel and said solvent is added to said microcapsules in said vessel to form said first suspension.
- Said solvent may be an aqueous solvent.
- Said microcapsules may be provided as a third suspension of microcapsules in a fluid and said third suspension may be in an aqueous medium.
- the weight ratio between the microcapsules and the water in the third suspension may be in a range between about 30 and 80 percent.
- That third suspension is generated in any known way, e.g. by mixing microcapsules with water or with an aqueous solution.
- a suspension is generated in the process of manufacturing the phase-change material-comprising microcapsules. In such cases, that suspension is used as the third suspension, as such, or after some modification.
- the viscosity of said third suspension is in the range of between about 100 and about 3000 cps.
- the viscosity of said third suspension is in the range of between about 1000 and about 2000 cps.
- said third suspension is provided at a temperature in the range of between about ambient and 120 °C.
- said method further comprises the step of adding at least one further component selected from the group consisting of a defoaming agent, wetting agent a flow-control agent, a dispersing agent and a surfactant to said first suspension.
- the polymer and/or precursor is provided in any form, for example in a solution.
- Any solvent capable of dissolving the polymer and/or precursor is suitable for such polymer and/or precursor solution.
- that solvent is composed of components used as solvent in the formation of the first suspension.
- the solvent of the polymer and/or precursor solution is similar in composition to the solvent in the first suspension, e.g. both are aqueous solutions of sodium thiocyanate when the polymer is acrylonitrile based and aqueous solutions or sodium hydroxide, when the polymer is cellulose based. Combining could use known method, such as mixing.
- the microcapsules are evenly dispersed in the second suspension. [0052] In this aspect of the present invention said method further comprises wet spinning or dry spinning of said second suspension.
- the invention is also directed to a fiber whenever manufactured according to one of said spinning steps.
- microcapsules are evenly dispersed throughout said fiber.
- said fiber is preferably combined with other fibers to form a fabric.
- FIG. 1 is a graphic representation of particle size distribution of a freshly formed stable suspension of microcapsules produced according to Example 3.
- FIG. 2 is a graphic representation of particle size distribution of a stable suspension of microcapsules produced according to Example 3 after 24 hours.
- stable suspension can refer, for example, to a suspension wherein a plurality of microcapsules comprising phase-change material is suspended in a solvent and wherein the majority of said microcapsules are evenly dispersed.
- the term can also refer to that suspension, wherein the majority of the microcapsules are not substantially agglomerated.
- the term can also refer to that suspension, wherein the majority of the microcapsules do not float on top of the solvent nor sink to its bottom.
- the term can also refer to that suspension, wherein no creaming takes place.
- polymer precursor refers, for example, to compounds that are converted to a polymer by polymerization, optionally with other compounds. Monomers are examples of polymer precursors.
- the term “evenly dispersed” refers, for example, to a state where the majority of the microcapsules are not agglomerated.
- solvent capable of dissolving refers, for example, to a solvent wherein the polymer or its precursor is soluble to the extent that a solution containing at least 1 weight percent of the solute can be prepared.
- the term “latent heat” refers, for example, to the quantity of energy absorbed or released by a substance undergoing a change of state.
- phase-change material refers, for example, to a material that has the capability of absorbing or releasing energy to adjust heat transfer at or within a temperature stabilizing range.
- a temperature stabilizing range can include a specific transition temperature or a range of transition temperatures.
- a phase-change material can be capable of inhibiting heat transfer during a period of time when the phase-change material is absorbing or releasing heat, typically as the phase-change material undergoes a transition between two states. This action is typically transient and will occur until a latent heat of the phase-change material is absorbed or released during a heating or cooling process.
- a phase-change material can be a mixture of two or more materials. By selecting two or more different materials and forming a mixture, a temperature stabilizing range can be adjusted for any desired application. The resulting mixture can exhibit two or more different transition temperatures or a single modified transition temperature when incorporated in accordance with the following articles. "A Review on Phase-change Energy Storage: Materials and Applications” by Farid, M. M., et. al in Energy Conversion and Management 45, (2004) 1597-1615.
- Phase-change materials that can benefit from stabilization in accordance with various embodiments of the invention include a variety of organic substances.
- Exemplary phase-change materials include, by way of example and not by limitation, hydrocarbons (e.g., straight chain alkanes or paraffinic hydrocarbons, branched-chain alkanes, unsaturated hydrocarbons, halogenated hydrocarbons, and alicyclic hydrocarbons), fatty acids, fatty acid esters, dibasic acids, dibasic esters, 1-halides, primary alcohols, aromatic compounds, anhydrides (e.g., stearic anhydride), ethylene carbonate, glycols, polyhydric alcohols (e.g., 2,2-dimethyl-l, 3- propanediol, 2-hydroxymethyl-2-methyl-l, 3 -propanediol, polyethylene gylcol, pentaerythritol, dipentaerythrital, pentaglycerine), polymers, polyglycols ,metals,
- phase-change material can be dependent upon a latent heat and a transition temperature of the phase-change material.
- a latent heat of the phase-change material typically correlates with its ability to reduce or eliminate heat transfer.
- the phase-change material can have a latent heat that is at least about 40 J/g, such as at least about 50 J/g, at least about 60 J/g, at least about 70 J/g, preferably at least about 80 J/g, especially preferred at least about 90 J/g, and most preferred at least about 100 J/g.
- the phase-change material can have a latent heat ranging from about 40 J/g to about 400 J/g, preferably from about 60 J/g to about 400 J/g, especially preferred from about 80 J/g to about 400 J/g, and most preferred from about 100 J/g to about 400 J/g.
- a transition temperature of the phase-change material typically correlates with a desired temperature or a desired range of temperatures that can be maintained by the phase-change material.
- the phase- change material can have a transition temperature ranging from about -10 °C to about 110 °C, such as from about 0 °C to about 100 °C, from about 0 °C to about 50 °C, from about 10 °C to about 50 °C, preferably from about 15 °C to about 45 °C, especially preferred from about 22 °C to about 40 °C, and most preferred from 22 °C to about 28 °C.
- the selection of the phase- change material can be dependent upon other considerations, such as its reactivity or lack of reactivity with a material forming the shells, its resistance to degradation under ambient or processing conditions, its biodegradability, and its toxicity.
- Table 1 provides a list of exemplary paraffinic hydrocarbons that may be used as the phase-change material stabilized in the accordance with various embodiments of the invention.
- a phase-change material can be a mixture of two or more substances (e.g., two or more of the exemplary phase-change materials discussed above). By selecting two or more different substances (e.g., two different paraffinic hydrocarbons) and forming a mixture thereof, a temperature stabilizing range can be adjusted over a wide range for any desired application.
- a phase-change material may comprise a copolymer of two or more substances (e.g., two or more of the exemplary phase-change materials discussed above).
- phase-change material will typically be dependent upon a desired transition temperature or a desired application of a resulting multi-component fiber.
- a phase-change material having a transition temperature near room temperature may be desirable for applications in which the resulting multi-component fiber is incorporated into apparel designed to maintain a comfortable temperature for a user.
- phase-change materials include paraffmic hydrocarbons having between 10 to 44 carbon atoms (i.e., C 10 -C 44 paraffmic hydrocarbons).
- Table 1 provides a list of exemplary C 13 -C 28 paraffmic hydrocarbons that may be used as the phase-change material in the silica capsules described herein.
- the number of carbon atoms of a paraff ⁇ nic hydrocarbon typically correlates with its melting point. For example, n-Octacosane, which contains twenty-eight straight chain carbon atoms per molecule, has a melting point of 61.4°C.
- n-Tridecane which contains thirteen straight chain carbon atoms per molecule, has a melting point of -5.5°C.
- n-Octadecane which contains eighteen straight chain carbon atoms per molecule and has a melting point of 28.2°C, is particularly desirable for clothing applications.
- phase-change materials include polymeric phase-change materials having transition temperatures suitable for a desired application of the multi-component fiber (e.g., from about 22°C to about 4O°C for clothing applications).
- a polymeric phase-change material may comprise a polymer (or mixture of polymers) having a variety of chain structures that include one or more types of monomer units.
- polymeric phase-change materials may include linear polymers, branched polymers (e.g., star branched polymers, comb branched polymers, or dendritic branched polymers), or mixtures thereof.
- a polymeric phase-change material may comprise a homopolymer, a copolymer (e.g., terpolymer, statistical copolymer, random copolymer, alternating copolymer, periodic copolymer, block copolymer, radial copolymer, or graft copolymer), or a mixture thereof.
- a copolymer e.g., terpolymer, statistical copolymer, random copolymer, alternating copolymer, periodic copolymer, block copolymer, radial copolymer, or graft copolymer
- the reactivity and functionality of a polymer may be altered by addition of a functional group such as, for example, amine, amide, carboxyl, hydroxyl, ester, ether, epoxide, anhydride, isocyanate, silane, ketone, and aldehyde.
- a polymer comprising a polymeric phase-change material may be capable of cross
- a polymeric phase-change material may be desired which has a higher molecular weight, larger molecular size, or higher viscosity relative to a non-polymeric phase-change material (e.g., paraffinic hydrocarbons).
- a polymeric phase-change material may exhibit a lesser tendency to leak from its shell, for example, the larger molecular size or higher viscosity may prevent the polymeric phase-change material from flowing through a sheath member or seal member forming the exterior of the shell.
- polyethylene glycols may be used as the phase-change material in some embodiments of the invention.
- the average molecular weight of a polyethylene glycol typically correlates with its melting point.
- a polyethylene glycol having an average molecular weight range of 570 to 630 e.g., Carbowax 600
- Carbowax 600 will have a melting point of 2O°C to 25°C.
- Other polyethylene glycols that may be useful at other temperature stabilizing ranges include Carbowax 400 (melting point of 4°C to 8°C ), Carbowax 1500 (melting point of 44°C. to 48°C), and Carbowax 6000 (melting point of 56 °C to 63 °C).
- phase-change materials having a melting point in the range of 6O°C to 65°C may also be used as phase-change materials in some embodiments of the invention.
- Further desirable phase-change materials include polyesters having a melting point in the range of 0°C to 40 °C, that may be formed, for example, by polycondensation of glycols (or their derivatives) with diacids (or their derivatives).
- Table 2 sets forth melting points of exemplary polyesters that may be formed with various combinations of glycols and diacids.
- a polymeric phase-change material having a desired transition temperature may be formed by reacting a phase-change material (e.g., an exemplary phase-change material discussed above) with a polymer (or mixture of polymers).
- a phase-change material e.g., an exemplary phase-change material discussed above
- a polymer or mixture of polymers.
- n-octadecylic acid i.e., stearic acid
- dodecanoic acid i.e., lauric acid
- phase-change materials e.g., phase-change materials with one or more functional groups such as amine, carboxyl, hydroxyl, epoxy, silane, sulfuric, and so forth
- polymers may be reacted to yield polymeric phase-change materials having desired transition temperatures.
- a phase-change material can comprise a mixture of two or more substances (e.g., two or more of the exemplary phase-change materials discussed above).
- a temperature stabilizing range can be adjusted over a wide range for any particular application.
- the mixture of two or more different substances may exhibit two or more distinct transition temperatures or a single modified transition temperature.
- the microcapsules comprise a shell and a core.
- the core comprises phase-change material.
- the shell provides at least one of encapsulating, containing, surrounding and absorbing the phase- change material. This shell may facilitate handling of the phase-change material while offering a degree of protection to the phase-change material during manufacture of the fibers (e.g., protection from high temperatures or shear forces).
- Various materials are suitable for the microcapsules shells, including synthetic polymers, such as formaldehyde-based ones, isocyanate, amines, carboxylic acid derivatives, natural materials such as gelatin or cellulose and acrylic polymers, and others such as silica.
- the shell polymers can be thermoplastic or thermoset, crosslinked or uncrosslinked, soft or hard, flexible or rigid.
- the shell is formed from formaldehyde-based polymers, silica particles, or acrylic polymers precursors such as acrylic acid, methacrylic acid, formaldehyde and a silica precursor, such as described in patents EP 1321182 and US6716526 and patent applications WO2004092299 and WO2005105291, the details of which are incorporated by reference in their entirety into the present disclosure.
- the stable suspension of the present invention comprises a solvent capable of dissolving a polymer to be included in a temperature-regulating fabric, or capable of dissolving a precursor of such polymer.
- a solvent capable of dissolving a polymer to be included in a temperature-regulating fabric or capable of dissolving a precursor of such polymer.
- Any polymer is suitable for the present invention, if it is incorporated in such temperature-regulating fabric.
- the polymer is at least one of acrylonitrile-based polymers and cellulose-based polymer.
- Any solvent capable of dissolving the polymer to be incorporated or its precursor is suitable.
- the solvent is an aqueous solution.
- the aqueous solution comprises at least one solute, such as sodium base, sodium thiocyanate, zinc chloride, acetone, DMF, NMP and nitric acid.
- solute concentration in the solvent on microcapsules- free basis is in a range of between about 0.5 percent and about 90 percent by weight.
- solute concentration in the solvent on microcapsules- free basis is in a range of between about 1 percent and about 70 percent by weight.
- the stable suspension of the present invention comprises said solvent and said phase- change material-comprising microcapsules.
- the microcapsules form between about 5 and about 50 percent by weight of the suspension.
- the microcapsules form between about 10 and about 30 percent by weight of the suspension.
- a characteristic of the stable suspension of the present invention, comprising said solvent and said microcapsules is that it is stable for at least 20 hours. According to an embodiment of the invention, the stable suspension is stable for at least 40 hours.
- the term “stable suspension” can refer to a suspension wherein the majority of the microcapsules are evenly dispersed. As used herein the term “evenly dispersed” refers to a state where the majority of the microcapsules are not agglomerated.
- the term “stable suspension” can also refer to that suspension, wherein the majority of the microcapsules are not agglomerated.
- the term can also refer to that suspension, wherein the majority of the microcapsules do not float on top of the solvent nor sink to its bottom. The term can also refer to that suspension, wherein no creaming is observed.
- the stable suspension comprises an additive selected from a group consisting of defoaming agents, wetting agents, flow-control agents, dispersing agents and surfactants.
- Suitable additives include:
- Flow control and rheological agents such as water soluble polymers, water insoluble polymers, clays, microcrystalline cellulose aerosols
- Dispersing agents such as anionic, cationic, amphoteric and nonionic surfactants, derivatives of polyacryllic acids , low or high molecular weight unsaturated acidic polycarboxylic acid polyester , polyquaternary ammonium compounds, polycarboxylic acids , salts of long chain polyamine amides, and alkylolammonium salt of a block copolymer with acidic groups
- Wetting agents such as polyether modified poly-dimethyl-siloxane (such as BYK-348, BYK-346 ,BYK-333 from Byk Chemie) .
- the wetting agents may be selected from a group consisting of silicon compounds, fluorine compounds, polyglycols, fatty acids, fatty amides, fatty alcohols and their esters and ethers. Suitable agents can also comprises various mixtures, blends and copolymers from the above list.
- said first suspension further comprises at least one compound with some functional aspect
- said functionality may include, for example, fire retardation, bioactivity, antimicrobial activity, odor resistance, UV absorption, moisture management and resistance to water, grease, dirt and/or stain.
- functional compounds and functionality are selected from a group consisting of those set forth in Table 3 as well as any similar or related functions.
- the functional compound is dissolved in the stable suspension.
- the functional compound is encapsulated in shells.
- the shell is similar in properties to the shells of the phase-change material microcapsules.
- the shell of the functional-compound microcapsules is made of the same material as the shell of phase- change material microcapsules.
- the functional compound is encapsulated and the microcapsules are evenly dispersed in the stable suspension of the invention.
- the stable suspension is kept at a controlled temperature. According to a related embodiment, that temperature is in the range between about 15°C and about 12O°C. According to another embodiment, the temperature is kept at a temperature between about 2O°C and about 5O°C. According to another embodiment, the stable suspension is kept under low-shear mixing. According to an embodiment of the solution, low-shear mixing is mixing or agitation with paddles or propellers at shear rates of 1-100 sec "1 , preferably 1-10 sec "1 .
- the stable suspension which comprises the solvent and the plurality of the microcapsules, is used for the production of temperature-regulating, polymer comprising fabric.
- the solvent of the stable suspension comprises water and sodium hydroxide
- the concentration of the sodium hydroxide ranges between about one percent and about 8 percent by weight of the solvent and the microcapsules form between about 15 percent and about 50 percent by weight of said suspension.
- the polymer is cellulose- based
- the solvent of the stable suspension comprises water and sodium hydroxide
- the concentration of the sodium hydroxide ranges between about 1.5 percent and about 3 percent by weight of the solvent and the microcapsules form between about 15 percent and about 30 percent by weight of said suspension and the suspension is kept at an ambient temperature.
- aspects of the present invention also provides a fabric produced by a method using the stable suspension. More specifically, the provided fabric is a commercial product. According to an embodiment of the invention the fabric or commercial product comprises a fiber or plurality of fibers.
- the stable suspension comprises at least one additive selected from a group consisting of defoaming agents, flow-control agents, wetting and dispersing agents and surfactants, e.g. the ones listed above.
- a suitable additive is present in the third suspension, when used to provide the microcapsules.
- the additive is used in the process of producing the microcapsules and remain in a suspension generated during that production, which suspension is used as the third suspension, as such or after some modification.
- the additive is added as such or in any combination, e.g. solution, to the provided components, e.g. the third suspension or the solvent prior to mixing, and/or added after mixing.
- the stable (first) suspension is kept at a temperature in the range between about ambient and about 12O°C.
- the stable suspension is kept under low-shear mixing.
- a method of manufacturing polymer-containing temperature-regulating fabric comprising providing and incorporating at least one functional compound with functionality selected from a group consisting of fire retardation, bioactivity, antimicrobial, odor resistance and UV absorption as described hereinafter.
- functional compounds and functionality are selected from the group consisting of those set forth in Table 3.
- the functional compound is provided in a dissolved form.
- the functional compound is encapsulated in shells.
- the shell is similar in properties to the shells of the phase-change material microcapsules.
- the shell of the functional-compound microcapsules is made of the same material as the shell of phase-change material microcapsules. Any form of provided the functional material and/or its microcapsules is suitable, e.g. in the stable first solution or with the polymer and/or precursor prior to combining those or after such combining. Incorporating the functional compound and/or its microcapsules may use any known method, e.g. mixing.
- the functional compound is encapsulated and its microcapsules are evenly dispersed in the second suspension.
- the formed second suspension comprises microcapsules of both phase-change material and functional compounds and both microcapsules are evenly dispersed in the second suspension.
- the functional material is provided in the phase-change material-comprising microcapsules.
- the method for manufacturing of polymer-containing temperature -regulating fabric comprises the step of converting the second suspension, as such, or with additional components to said fabric.
- the second suspension is coated by known methods on surfaces, where they is further treated, e.g. evaporation of solvent, precipitation and/or polymerization of components included therein.
- converting the second suspension into polymer pellets, wherein the microcapsules are evenly dispersed, which pellets is then converted to commercial products.
- the method for manufacturing of polymer-containing temperature-regulating fabric may also comprise the step of converting the second suspension into fiber.
- the microcapsule-containing, phase-change material is evenly dispersed in said manufactured fiber.
- the microcapsules-comprising fiber is produced by the melt spinning process, wherein a molten polymer and microcapsules are provided, spun and cooled for solidification. Polymer pellets, wherein the microcapsules are evenly dispersed, are useful for such fiber production via melt spinning.
- the shell of the microcapsules used for such melt spinning is made out of silica.
- the fiber is manufactured by means of solution spinning involving spinning a feed solution comprising polymer and/or polymer precursor, phase-change material-microcapsules and optionally also at least one agent, surfactant or functional compound, as described above.
- the feed solution may comprises the above-described second solution.
- a stable suspension is manufactured, as described above, and stored in a suitable first vessel at the above-specified temperature range and under the above- specified mixing. The amount of produced stable suspension is suitable for at least 20 hours of fiber production, preferably for at least 40 hours. A solution of the polymer and/or precursor is also produced and kept in a second vessel.
- a feed solution is generated by mixing a suspension from said first vessel with solution from said second vessel, which is then spun through at least one spinneret and further treated, e.g. via, optionally polymerization, dry spinning or wet spinning.
- the spinnerets are submerged in or held very close to a chemical bath and as the filaments emerge, they contact the chemical bath, and they precipitate from solution and solidify.
- solidification is achieved by evaporating the solvent in a stream of air or inert gas. For more details, see Acrylic Fibers by R.
- the fiber is acrylonitrile-based.
- the solution in the second vessel is preferably comprised of between about 5 and about 20 percent by weight solute in a solvent.
- the solution in the vessel comprises between about 10 and about 15 percent by weight solute in solvent.
- the solute on a dry basis, is preferably made from between about 80 and about 100 percent by weight of acrylonitrile monomer; between about 0 and about 20 percent by weight of neutral monomer, e.g. at least one of methyl acrylate, vinyl acetate, methyl methacrylate and acrylamide, and between about 0 and about 2 percent by weight of acid comonomer, e.g. sodium styrene sulphonate, sodium methallyl sulphonate, sodium 2-methyl- 2acrylamidopropane sulphonate and itaconic acid.
- acid comonomer e.g. sodium styrene sulphonate, sodium methallyl sulphonate, sodium 2-
- the solute on a dry basis, is made from between about 90 and about 95 percent by weight of acrylonitrile monomer and between about 0 and about 14 percent by weight of said neutral monomer.
- the fiber is a modacrylic fiber
- the proportion is acrylonitrile in the solute is smaller and the solute contains also another comonomer, typically halogenated ethylenically unsaturated molecules.
- the solvent of the solution in the second vessel is an aqueous solution of sodium thiocyanate, e.g. with sodium thiocyanate concentration in a range between about 40 and about 60 percent by weight.
- the solvent is a solution of acetone. That solution is prepared by known methods, such as dissolving the polymer by adding it slowly, with stirring, to cold solvent and then raising the temperature to complete dissolution
- the solution in the second vessel is kept at a temperature of about ambient.
- the stable suspension in the first vessel comprises an aqueous solution of sodium thiocyanate as a solvent.
- concentration of the sodium thiocyanate in that solution is between about 40 and about 60 percent by weight.
- the stable suspension comprises microcapsules with a shell and a core, the shell forming between about 5 and about 40 percent by weight of the microcapsules.
- the shell is made from a compound such as, silica and formaldehyde polymer.
- the core comprises a phase-change material, e.g. a straight-chain or a branched-chain hydrocarbon with 15 to 25 carbon atoms.
- the microcapsules are of a size (largest dimension) of up to about 2 microns.
- the microcapsules form between about 5 and about 30 percent by weight of the suspension, which optionally also contains a viscosity modifier, e.g. as listed above.
- the stable suspension is prepared by gradually adding solvent to microcapsules suspension of about 50% in aqueous medium, while gently mixed. The stable suspension is kept in the first vessel at a temperature of about ambient under gentle low-shear mixing.
- a feed solution is produced by mixing a solution from the second vessel with a suspension from the first vessel (optionally filtered) at a relative rate suitable to yield a concentration of 2-50% mPCM on polymer dry weight basis, more preferably 5-20%. The feed solution is then spun by dry spinning or wet spinning (e.g.
- the spinneret is submerged in or held very close to a relatively dilute aqueous solution) to form acrylic fibers containing microcapsules with phase-change material.
- the fiber contains between about 5 and about 20 percent by weight of evenly dispersed microcapsules.
- Those fibers are then used for the production of various temperature-adaptable commercial products, such as woven fabrics, knit fabrics, and nonwoven fabrics, e.g. ones with enthalpy between about 1 J/g and about 50 J/g.
- the fiber is cellulose-based.
- the solution in the second vessel is composed of between about 5 and about 15 percent by weight solute in a solvent, preferably between about 8 and about 11 percent by weight.
- the composition of the solute, on a dry basis, is between about 5 and about 15 percent of the aqueous sodium hydroxide solution solvent.
- the solvent of the solution in the second vessel is an aqueous solution of sodium hydroxide, e.g. with sodium hydroxide concentration in a range between about 4 and about 10 percent by weight. That solution is prepared by known methods, such as dissolving the sodium hydroxide in water and adding cellulose.
- the dry cellulose is added with stirring, to prevent cellulose powder from sticking and forming clumps, to the correct amount of water and dissolved sodium hydroxide. This is then stirred until the cellulose is dissolved and the solution is clear.
- the solution in the second vessel is kept at a temperature of about ambient
- the stable suspension in the first vessel comprises an aqueous solution of sodium hydroxide as a solvent.
- concentration of the sodium hydroxide in that solution is between about 1 and about 5 percent by weight.
- the pH of the solvent is at least 10, preferably, at least 11.5.
- the stable suspension comprises microcapsules with a shell and a core, the shell forming between about 5 and about 40 percent by weight of the microcapsules.
- the shell is made from at least one compound such as, silica, acrylic acid, its derivative, methacrylic acid and its derivatives.
- the core comprises a phase-change material, e.g. a straight-chain or a branched- chain hydrocarbon with 15 to 25 carbon atoms.
- the microcapsules are of a size (largest dimension) of up to about 2 microns.
- the microcapsules form between about 10 and about 50 percent by weight of the suspension, which optionally also contains a viscosity modifier, e.g. cellulose, cellulose derivatives, acid functional polymers, polyglycols, polysaccharide and polyvinyl alcohol.
- a viscosity modifier e.g. cellulose, cellulose derivatives, acid functional polymers, polyglycols, polysaccharide and polyvinyl alcohol.
- the stable suspension is prepared by gradually adding the solvent to microcapsules suspension of about 50% in an aqueous medium, while gently mixed. The stable suspension is kept in the first vessel at an ambient temperature, under gentle low-shear mixing.
- a feed solution is produced by mixing a solution from the second vessel with a suspension from the first sample (optionally filtered) at a relative rate suitable to yield the desired % of mPCM on cellulose.
- the feed solution is then spun by dry spinning or wet spinning (e.g. by spinnerets submerged in or held very close to a solution of an acid, e.g. sulfuric acid) to form rayon or viscose fiber comprising microcapsules with phase-change material.
- the fiber contains between about 5 and about 40 percent by weight of evenly dispersed microcapsules.
- Those fibers is then used for the production of various temperature-adaptable commercial products -, such as woven fabrics, knit fabrics, and nonwoven fabrics, e.g. ones with enthalpy between about 1 J/g and about 50 J/g.
- Example 2 stable suspension of mPCM for acrylic fibers
- Example 3 stable suspension of mPCM for Rayon , Viscose or Cellulose fibers
- Example 4 Unstable suspension of mPCM for Rayon, Viscose or Cellulose fibers
- Example 5 stable suspension of mPCM for Lyocell fibers
- Example 6 stable suspension of mPCM for Lyocell fibers
- the solids included a 90/10 weight ratio of cellulose/microcapsules containing the phase-change material.
- the vial was placed in a 125°C oven and periodically mixed until its contents were homogenously mixed and melted. This solution can be used immediately or it can be cooled/solidified for storage then reheated. This cycle can be repeated numerous times.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009518448A JP2010509505A (en) | 2006-07-04 | 2007-06-15 | Stable suspensions containing microcapsules and methods for their preparation |
US12/304,326 US20090278074A1 (en) | 2006-07-04 | 2007-06-15 | Stable Suspensions Containing Microcapsules and Methods for Preparation Thereof |
EP07853493A EP2041361A4 (en) | 2006-07-04 | 2007-06-15 | Stable suspensions containing microcapsules and methods for the preparation thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IL176693A IL176693A0 (en) | 2006-07-04 | 2006-07-04 | Stable suspensions containing microcapsules and methods for the preparation thereof |
IL176693 | 2006-07-04 |
Publications (1)
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WO2008030648A1 true WO2008030648A1 (en) | 2008-03-13 |
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PCT/US2007/071373 WO2008030648A1 (en) | 2006-07-04 | 2007-06-15 | Stable suspensions containing microcapsules and methods for the preparation thereof |
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US (1) | US20090278074A1 (en) |
EP (1) | EP2041361A4 (en) |
JP (1) | JP2010509505A (en) |
KR (1) | KR20090025348A (en) |
CN (1) | CN101484630A (en) |
IL (1) | IL176693A0 (en) |
TW (1) | TW200815641A (en) |
WO (1) | WO2008030648A1 (en) |
Cited By (3)
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WO2009057135A2 (en) | 2007-07-03 | 2009-05-07 | Aditya Birla Science & Technology Co. Ltd. | Acrylic fiber with modified property and a process for making therefor |
WO2016191203A1 (en) * | 2015-05-22 | 2016-12-01 | Primaloft, Inc. | Self-warming insulation |
US10590321B2 (en) | 2008-07-16 | 2020-03-17 | Outlast Technologies, Gmbh | Articles containing functional polymeric phase change materials and methods of manufacturing the same |
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BRPI0918391B1 (en) * | 2008-12-22 | 2019-12-24 | Dow Global Technologies Llc | method for preparing a woven rug and woven rug |
KR101486938B1 (en) * | 2010-09-29 | 2015-02-04 | 엠파이어 테크놀로지 디벨롭먼트 엘엘씨 | Phase change energy storage in ceramic nanotube composites |
EP2633123A4 (en) * | 2010-10-29 | 2016-04-20 | Quantum Group Inc | Artificial turf systems and applications thereof |
WO2013076909A1 (en) | 2011-11-21 | 2013-05-30 | パナソニック株式会社 | Resin for electrical components, semiconductor device, and wiring board |
CN103113853A (en) * | 2013-01-18 | 2013-05-22 | 青岛科技大学 | Suspension stabilized phase change energy storage fluid and preparation method thereof |
CN105518100B (en) * | 2013-08-23 | 2019-06-21 | 国立大学法人神户大学 | Hard shell microencapsulation latent heat transmission material and preparation method thereof |
TWI601539B (en) * | 2016-05-30 | 2017-10-11 | 靜宜大學 | Sunblock microcapsule and production method thereof |
KR102225007B1 (en) * | 2016-07-11 | 2021-03-08 | 마이크로텍 라보라토리즈, 인코포레이티드 | Capsule having an outer shell bound to a surfactant and a method for producing the capsule |
CN106808744A (en) * | 2016-12-31 | 2017-06-09 | 重庆家宝装饰材料有限公司 | A kind of wallpaper for adjusting room temperature |
CN107268098B (en) * | 2017-07-20 | 2020-04-07 | 恒天生物基材料工程技术(宁波)有限公司 | Polymer/phase change microcapsule composite fiber and preparation method thereof |
CN114540972A (en) * | 2022-02-08 | 2022-05-27 | 武汉中科先进技术研究院有限公司 | Thermochromic fiber and method for preparing thermochromic fabric by using thermochromic fiber |
CN115301170A (en) * | 2022-08-08 | 2022-11-08 | 广东工业大学 | Method for regulating viscosity of paraffin phase-change microcapsule suspension |
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WO2009057135A2 (en) | 2007-07-03 | 2009-05-07 | Aditya Birla Science & Technology Co. Ltd. | Acrylic fiber with modified property and a process for making therefor |
WO2009057134A2 (en) | 2007-07-03 | 2009-05-07 | Aditya Birla Science & Technology Co. Ltd. | A viscose fiber with modified property and a process for making therefor |
WO2009063479A2 (en) | 2007-07-03 | 2009-05-22 | Aditya Birla Science & Technology Co. Ltd. | A lyocell fiber with modified property and a process for making therefor |
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Also Published As
Publication number | Publication date |
---|---|
CN101484630A (en) | 2009-07-15 |
TW200815641A (en) | 2008-04-01 |
EP2041361A1 (en) | 2009-04-01 |
EP2041361A4 (en) | 2012-06-06 |
JP2010509505A (en) | 2010-03-25 |
US20090278074A1 (en) | 2009-11-12 |
KR20090025348A (en) | 2009-03-10 |
IL176693A0 (en) | 2006-10-31 |
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