CN102561027A - Wadding flake with function of intellectualized thermoregulation and preparation method thereof - Google Patents
Wadding flake with function of intellectualized thermoregulation and preparation method thereof Download PDFInfo
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- CN102561027A CN102561027A CN2011104392450A CN201110439245A CN102561027A CN 102561027 A CN102561027 A CN 102561027A CN 2011104392450 A CN2011104392450 A CN 2011104392450A CN 201110439245 A CN201110439245 A CN 201110439245A CN 102561027 A CN102561027 A CN 102561027A
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Abstract
The invention relates to a wadding flake with a function of intellectualized thermoregulation and a preparation method thereof. The wadding flake is a base material which is made from a phase change material and an animal fiber, a plant fiber, a man-made fiber and/or a synthetic fiber by means of a fiber textile method or a fiber weaving method and formed by compounding through a certain method. The compounding method can be achieved by one of the technologies of padding, soaking and water sucking, atomizing and spraying and coating or by any combination of the above technologies. The wadding flake can react to an environmental temperature intelligently and absorb, store and release heat correspondingly with rising or falling of the environmental temperature so as to achieve a bi-directional adjustment of a micro-environmental temperature.
Description
Technical field
The present invention relates to a kind of flocculus and preparation method thereof with intelligent thermoregulating function.
Background technology
The tradition flocculus is by natural cotton, and silk fiber or artificial synthetic fiber are processed, and its principle is space or the interlayer that utilizes fibrous woven or braiding back to form, and isolated inside and outside air flows, and reaches the purpose of insulation.
Keeping the constant of human body temperature, and feel comfortable, is first requirement of dress ornament.Along with improving constantly of living standard, people to quilt, clothes to use and wear requirement also increasingly high, yet the flocculus that is used for quilt, clothes now can't satisfy these requirements.Desirable quilt, clothes should be both frivolous, and be warm again, preferably can the spring, summer, autumn, winter can use.And traditional flocculus is often powerless to these requirements.
In the face of the temperature Change that usually occurs in the daily life (sooner or later the temperature difference, weather, suddenly rise strong wind, be exposed to the sun and shady and cool, from indoor to outdoor, from air conditioner surroundings being arranged to no air conditioner surroundings or the like); Especially when variations in temperature more than ± 5 ℃ the time; People often cause disease because human body can not adapt to rapidly; The old young weakling that particularly body heat regulation ability is relatively poor damages even more serious.In the face of these problems, traditional flocculus is stymied by especially.
The tradition flocculus can be accomplished warming, but to sacrifice the light and thin of quilt, clothes, sacrifices convenient and aesthetic feeling and be cost.And the heat preservation principle of traditional flocculus, determined its can only uniaxially insulation, temperature that can't bidirectional modulation body surface microenvironment just can't realize the response environment temperature and heats up, or cooling.
For reaching such purpose, people have made tireless effort.Chinese patent ZL032055579 proposes water-cooled cooling on clothing; Dress hydrated salt in Chinese patent ZL92105520.X proposes; Utilize electric heating energy-storage to regulate the clothing temperature, Chinese patent ZL00218640.3 proposes on clothes, to be provided with control clothing temperature such as solar cell.Though above-mentioned patent has been pointed out the scheme of possible in theory, efficient is relatively poor, and device is complicated, and profile is too fat to move, also might have the potential danger to human body, such as getting an electric shock or the like.
Abroad, the dress ornament with bidirectional temp regulation function has been obtained important breakthrough, and various Related products have had report.What wherein extremely gaze at is the phase-changing and temperature-regulating material.This material melts when environment temperature raises by the solid-state liquid state that changes into, simultaneously a large amount of heats in the absorbing environmental; And when environment temperature reduces, solidify, become solid-stately by liquid state, emit a large amount of heats simultaneously, if this material is used in field of textiles, just possibly play regulating action to the temperature of the microenvironment between body surface and fabric.Yet these materials also have some problems not solve in actual production with in using.
The relevant departments and the scientific research personnel of China also are unwilling to be lag behind, and have actively developed the research of temperature adjustment function dress ornament, and have obtained good experiment achievement.Like Tianjin University of Technology is core with the low-temperature phase-change material, and polypropylene fibre is skin, through fusion core-skin composite spinning silk, has obtained having the fibrous material of thermal energy storage and release function.
For another example, Chinese invention patent CN00105563.1 has proposed a kind of compound soft material of two-way high temperature, is main raw material with the alginate fibre element, mixes phase transformation milimicron vesicle ball, processes fiber through wet fine method, further is processed into flocculus again; Perhaps with phase transformation milimicron vesicle ball, join in the dimethyl formamide that is dissolved with methyl acrylate, initiated polymerization obtains mixing acrylic-polymer solution again, and the composite of temperature adjustment function is processed in further again spinning.Can see the implementation procedure more complicated of this method, and used a large amount of organic solvents, obviously be not environmental protection.
For another example, Chinese utility model patent CN201020170181.X has proposed a kind of two-way high temperature energy-storage mattress; And Chinese invention patent CN201010175141.9, a kind of core with temperature adjustment function is proposed.Though the implementation method of above-mentioned two patents is different, its core concept all is through utilizing temperature-regulating fiber, these temperature-regulating fibers is processed that flocculus realizes again.The temperature-regulating fiber that said method uses only is applicable to a few material such as polypropylene fibre, acrylic fibers etc.; To natural fabric such as wool, silk etc. are powerless, and can not cover all kinds of fibers; And complicate fabrication process, cost are unfavorable for actual promoting the use of also than higher.
Summary of the invention
The purpose of this invention is to provide a kind of flocculus with intelligent thermoregulating function, and preparation method thereof.This flocculus can respond environment temperature intelligently, carries out correspondingly heat absorption storage and release with the rising or the reduction of environment temperature, thereby realizes the bidirectional modulation of microenvironment temperature.
The present invention provides a kind of flocculus with temperature adjustment function, and this flocculus is the flocculus base material that utilizes fibrous woven or braiding back to form by phase-change material and animal fiber, string, artificial fibre and/or synthetic fiber, is compounded to form through certain way; Said compoundly realize through padding, soak one of suction, spraying technology in spraying, applying or its combination in any.
The preferred above-mentioned phase-change material of flocculus with temperature adjustment function of the present invention is that 5-85 ℃, latent heat of phase change are the organic phase change material of 100-290J/g for the phase transition temperature scope.
Further, any one or its combination in any in the aliphatic acid of the fatty alcohol of the preferred above-mentioned phase-change material of flocculus with temperature adjustment function of the present invention n-alkane that is phase transformation paraffin, C14-22, C8-18 or C8-18 and the ester thereof.
Further, the preferred above-mentioned phase-change material of flocculus with temperature adjustment function of the present invention is any one or its combination in any in lightweight paraffin, 20# phase transformation paraffin, 25# phase transformation paraffin, 30# phase transformation paraffin, hexadecane, octadecane, eicosane, the positive butyl ester of hard ester acid.
Further, the preferred above-mentioned phase-change material of flocculus with temperature adjustment function of the present invention is micro mist, emulsion or other forms of solid-liquid mixed dispersion.
Further, the preferred above-mentioned phase-change material of flocculus with temperature adjustment function of the present invention is microcapsules of storing energy through phase change or Na capsule form, and range scale is 10nm-1000 μ m.
In addition; The invention still further relates to the preparation method of flocculus with temperature adjustment function; Suction is padded, is soaked in employing to the flocculus base material, spraying is sprayed and/or coated technique, makes physical absorption or bonding takes place between phase-change material and substrate fiber, perhaps combines through the generation chemical bond.
Compared with prior art, the flocculus with temperature adjustment function of the present invention has following advantage:
1, flocculus material of the present invention has intelligent bidirectional temp regulation function, can carry out neither endothermic nor exothermic with environmental change, thereby reaches the purpose of regulating the microenvironment temperature.
2, adjusting temperature principle of the present invention and traditional flocculus are essentially different, and have solved the lightening and thermoregulator problem of clothing preferably.
3, utilize the present invention, can produce thinner clothing, this means raw-material saving; Simultaneously, realization of the present invention is little to complicated machinery and complicated process dependency.Therefore the present invention is rich in actual effect more economically more.
4, scheme of the present invention is applied widely, generally is applicable to various natural fabrics, artificial fibre and synthetic fiber.
5, the present invention can be widely used in sportswear, wind coat, jacket, insulated cold wear, overcoat, cold-proof shoes boots, bed clothes etc.The present invention can be made into pattern comfortable clothes attractive in appearance, light and warm.But also be not limited to field of textiles, also can further apply to building energy conservation, the recycling of industrial exhaust heat and used heat, heat-insulating, fire-preventing, and the maintenance of instrument and equipment, numerous areas such as health care.
Description of drawings
Fig. 1 is the figure that shows phase-change material and flocculus base material combination in the flocculus with temperature adjustment function of the present invention.
The specific embodiment
The present invention aims to provide a kind of flocculus with temperature adjustment function, and this flocculus is compounded to form through certain way by phase-change material and flocculus base material.Compound can the realization here through padding, soak one of suction, spraying technology in spraying, applying or its combination in any.
Phase-change material involved in the present invention and flocculus base material compound is meant the surface of phase-change material at flocculus or flocculus fiber, or between the flocculus fiber, between flocculus or flocculus sheet and the lamella, through physics chemical action carry out compound.Described in scheme of the present invention and the existing patent of invention be core with the phase-change material, be wall material or cortex with other materials such as polymer etc.; Through methods such as electrostatic spinning, solvent spinnings, directly phase-change material is coated on the temperature-regulating fiber of processing in the fiber has basic difference.
Above-mentioned flocculus base material can be the material that animal fiber, string, artificial fibre and/or synthetic fiber utilize fibrous woven or braiding back to form.For example above-mentioned flocculus base material can be: a) animal and plant fiber, like cotton, fiber crops, silk, wool, cashmere etc.; B) artificial fibre is like viscose, CUP, acetate fiber etc.; C) synthetic fiber process through weaving or weaving like any one or its combination in any in polyester fiber, polyacrylonitrile fibre, the polyamide fiber etc.But above-mentioned material does not comprise the temperature-regulating fiber that existing method is made, and promptly through methods such as electrostatic spinning, solvent spinnings, it is within the rule directly phase-change material to be coated on the temperature-regulating fiber of processing in the fiber.
Above-mentioned phase-change material is selected organic phase change material usually, and the phase transition temperature scope is that 5-85 ℃, latent heat of phase change are 100-290J/g.This phase-change material for example comprises any one or its combination in any in aliphatic acid and the ester thereof of fatty alcohol or C8-18 of n-alkane, C8-18 of phase transformation paraffin, C14-22.Be preferably lightweight paraffin, 20# phase transformation paraffin, 25# phase transformation paraffin, 30# phase transformation paraffin, hexadecane, octadecane, eicosane, the positive butyl ester of hard ester acid etc. respectively.
Above-mentioned phase-change material also can be with the further regularization of phase-change material, like polyethylene-wax phase change energy storage material, and micro mist, emulsion and other form solid-liquid mixed dispersions of haydite-wax phase change energy storage material etc.Can also be microcapsules of storing energy through phase change or the Na capsule that phase-change material is further passed through prepared in various methods, its range scale be 10nm-1000 μ m, comprises pulvis, emulsion and other form solid-liquid mixed dispersions etc. of microcapsules.
Flocculus with intelligent thermoregulating function of the present invention can prepare through following arbitrary method:
In the processing or production process of flocculus base material; Physics or chemical methodes such as employing is padded, immersion absorbs water, spraying is sprayed, coating; Make physical absorption or bonding takes place between phase-change material and flocculus fiber; Perhaps phase-change material is combined with the flocculus fiber through generating chemical bond, with the compound surface (like A in the accompanying drawing 1) of adding flocculus to of above-mentioned phase-change material, or between flocculus sheet and the lamella (like B in the accompanying drawing 1); Or between flocculus fiber and the fiber (like C in the accompanying drawing 1), promptly obtain the flocculus with intelligent thermoregulating function of the present invention;
After the processing or production completion of flocculus base material; The flocculus base material is adopted physics or chemical methodes such as padding, soak suction, spraying sprinkling, coating; Make physical absorption or bonding takes place between phase-change material and flocculus fiber; Perhaps phase-change material is combined with the flocculus fiber through generating chemical bond, with the compound surface (like A in the accompanying drawing 1) of adding flocculus to of above-mentioned phase-change material, or between flocculus sheet and the lamella (like B in the accompanying drawing 1); Or between flocculus fiber and the fiber (like C in the accompanying drawing 1), promptly obtain the flocculus with intelligent thermoregulating function of the present invention.
In the implementation procedure of above-mentioned technology; Can add various additives according to actual conditions,, preferably not contain the environment-friendly adhesive of formaldehyde like adhesive; Like the anionic wetting agent; Like a kind of or its combination in any in the compounds such as alkyl sulfate, amber acidic group sulfonated ester, succinamic acid alkyl ester sulfonate, alkyl sulfosuccinic acid amides, preferably these compound carbon numbers are 6-24, and; Can carry out ethoxylation or propoxylation to these compounds, preferred degree of ethoxylation is between 1-50.Viscosity modifier can be organic salt or inorganic salts for another example, organic salt such as urea, urea derivative or amino acid, and alkali metal salt or alkali salts such as inorganic salts such as sodium chloride, magnesium chloride are preferably inorganic salts.Additive of the present invention also comprises other additives commonly used in flocculus processing or the textile finishing.
Through embodiment flocculus of the present invention is described more specifically below.
Embodiment 1:
(this dispersion is an emulsion, and promptly phase-change microcapsule is dispersed in water or other solvent, and main component is that capsule-core is a phase transformation alkane with 200g phase-change microcapsule dispersion of materials body; Shell is a Lauxite; Or like other polymer such as polyurethane, size is controlled between 100 nanometers to 1000 micron, and the preparation method can be with reference to article Journal of Applied Polymer Science; 2005,97:390; Colloidal and Polymer Science 280:290), mixes with 800g distilled water, 1.5g polypropylene sodium and 2g dialkyl sulfosuccinic salt, up to no obvious solid matter.With the commercial pump formula spray bottle that can get; Evenly spray on the flocculus that makes with the traditional handicraft method with the dispersion of spray pattern above-mentioned gained; Selected commercially available cashmere-wadded and commercially available flocculus gum sprayed cotton in this example for use; Quantity for spray is 20% of a flocculus quality of materials, and the flocculus to spray treatment carries out 100 ℃ of oven dry then, can obtain the flocculus with temperature adjustment function of the present invention.
Characterize through SEM, most of phase-change materials are compounded on the surface fiber of flocculus material; Learn that through the analysis of differential scanning calorimetry gained has the cashmere-wadded material crystallization enthalpy of temperature adjustment function and becomes 21.29J/g, melting enthalpy is 19.23J/g; The gum sprayed cotton flocculus crystallization enthalpy of gained temperature adjustment function is 33.65J/g, and melting enthalpy is 32.02J/g.
Embodiment 2:
Each fibrous raw material quality proportioning is following:
Eider down (duck's down or goose down) 30%, polyester fiber 62%, viscose fibre (polypropylene fibre) 8%.
With phase change material emulsion and adhesive (environment protective adhesives free of formaldehyde is selected for use to be prone to sunshine chemical industry PUD aqueous polyurethane composite gel stick, or east ROHM AND HAAS ST954 type aqueous binder etc.), evenly mix at 9: 1 by mass ratio.
Wherein, phase change material emulsion prescription (parts by mass) is:
570 parts of phase transformation paraffin
The ammonia spirit of 200 parts of sz25010 (polyscope) (solid content 15%)
230 parts of deionized waters
Raw fiber is mixed, the fiber that mixes is carried out combing, lapping behind the formation fibre web, is carried out drawing-off to fibre web.With phase-change material and adhesive mixed liquor the fibre web two sides is sprayed, the sprinkling amount is 15% of a fibre web quality.
Fibre web is sent into 150 ℃ of baking ovens, make the fusing of viscose fibre top layer, and, also carry out phase-change material and fiber bonding simultaneously fiber bonding around it.Can obtain the flocculus with temperature adjustment function of the present invention.
Characterize through SEM, most of phase-change materials are compound at the interlayer of flocculus fiber; The test shows of differential scanning calorimetry, the crystallization enthalpy of this temperature adjustment function flocculus is 13.90J/g, the fusion enthalpy is 12.87J/g.
Embodiment 3:
Each fibrous raw material quality proportioning is following:
Eider down (duck's down or goose down) 30%, polyester fiber 62%, viscose fibre (polypropylene fibre) 8%.
Raw fiber is mixed, the fiber that mixes is carried out combing, lapping behind the formation fibre web, is carried out drawing-off to fibre web.Spray adhesive (environment-friendly adhesive that does not contain formaldehyde is selected for use to be prone to sunshine chemical industry PUD aqueous polyurethane composite gel stick, or east ROHM AND HAAS ST954 type aqueous binder etc.) is carried out on the fibre web two sides, and the sprinkling amount is 10% of a fibre web quality.
(this pulvis is to be capsule-core with the lauryl alcohol, is the microcapsules powder of shell material with the Lauxite, makes through the said method of following document with the phase-change material pulvis; Refilter the powder that obtains, the pulvis particle diameter is at 2 to 50 microns, and the preparation method is referring to " functional material "; 2005,11 (36), 1722) be sprayed on the fibre web; Make phase-change material under the adhesive effect, tentatively bonding with fiber.Again fibre web is sent into 150 ℃ of baking ovens, make the fusing of viscose fibre top layer, and, also carry out phase-change material and fiber bonding simultaneously fiber bonding around it.Can obtain the flocculus with temperature adjustment function of the present invention.
Characterize through SEM, most of phase-change materials are compound at the interlayer of flocculus fiber; The test shows of differential scanning calorimetry, the crystallization enthalpy of this temperature adjustment function flocculus is 9.14J/g, the fusion enthalpy is 7.87J/g.
Embodiment 4:
Each fibrous raw material quality proportioning is following:
Cashmere 20%, rabbit suede 20%, polyester fiber 50%, viscose fibre (polypropylene fibre) 10%.
With phase change material emulsion (preparation method is with embodiment 2) and adhesive (environment protective adhesives free of formaldehyde is selected for use to be prone to sunshine chemical industry PUD aqueous polyurethane composite gel stick, or east ROHM AND HAAS ST954 type aqueous binder etc.), evenly mix at 9: 1 by mass ratio.
Wool, the rabbit hair are mixed, and the animal fiber to mixing carries out immersion treatment with phase-change material and adhesive mixed liquor.Then the animal fiber that soaks is dried processing, oven dry in 70 ℃ then.
The animal fiber of oven dry is mixed with polyester fiber, viscose fibre, carry out the fiber that mixes is carried out combing, lapping behind the formation fibre web, is carried out drawing-off to fibre web.To fibre web two sides spray adhesive, the sprinkling amount is 15% of a fibre web quality.
Fibre web is sent into 150 ℃ of baking ovens, make the fusing of viscose fibre top layer, and, can obtain the flocculus with temperature adjustment function of the present invention fiber bonding around it.
Characterize through SEM, most of phase-change materials are compound between flocculus fiber and fiber; The test shows of differential scanning calorimetry, the crystallization enthalpy of this temperature adjustment function flocculus is 10.90J/g, the fusion enthalpy is 9.12J/g.
The flocculus with temperature adjustment function of the present invention of above-mentioned each embodiment preparation is compared with existing this type of material has very excellent effect, contrasts as follows:
China utility model patent CN201020170181.X has proposed a kind of two-way high temperature energy-storage mattress; And Chinese invention patent CN201010175141.9 proposed a kind of core with temperature adjustment function, and these two schemes are the outstanding representatives in the art methods.Though the implementation method of above-mentioned two patents is different, its core concept all is through utilizing temperature-regulating fiber, these temperature-regulating fibers is processed that flocculus realizes again.The temperature-regulating fiber that said method uses only is applicable to a few material such as polypropylene fibre, acrylic fibers etc., and to natural fabric such as wool, silk etc. are powerless, can not cover all kinds of fibers.
And the temperature-regulating fiber of these kinds its essence is with the phase-change material to be core, is wall material or cortex with other materials such as polymer etc., and through electrostatic spinning, methods such as solvent spinning directly are coated on phase-change material and process in the fiber.Complicate fabrication process often needs complicated and expensive equipment and device.Process flocculus again with these schemes, often need increase operation and equipment, significantly change the manufacture craft of existing flocculus, increased cost virtually, be unfavorable for actual promoting the use of with temperature adjustment function.
By contrast, the flocculus with temperature adjustment function of the present invention can change under the situation of flocculus manufacture craft more by a small margin, need not to increase complex apparatus; Through padding of mild condition, or soak suction, or spraying is sprayed; Or technology such as coating, the simple physics chemical process realizes.And the present invention program's universality is strong, not only goes for like cotton fiber crops, silk, wool, animal and plant fibers such as cashmere; And for viscose, CUP, artificial fibres such as acetate fiber, and polyester fiber, polyacrylonitrile fibre, synthetic fiber such as polyamide fiber, same being suitable for.
Claims (8)
1. flocculus with temperature adjustment function, said flocculus is compounded to form through certain way by the flocculus base material that phase-change material and animal fiber, string, artificial fibre and/or synthetic fiber utilize fibrous woven or braiding back to form; Said compoundly realize through padding, soak one of suction, spraying technology in spraying, applying or its combination in any.
2. the flocculus with temperature adjustment function according to claim 1, wherein said phase-change material is that 5-85 ℃, latent heat of phase change are the organic phase change material of 100-290J/g for the phase transition temperature scope.
3. the flocculus with temperature adjustment function according to claim 2, wherein said phase-change material are any one or its combination in any in aliphatic acid and the ester thereof of fatty alcohol or C8-18 of n-alkane, C8-18 of phase transformation paraffin, C14-22.
4. the flocculus with temperature adjustment function according to claim 3, wherein said phase-change material are any one or its combination in any in lightweight paraffin, 20# phase transformation paraffin, 25# phase transformation paraffin, 30# phase transformation paraffin, hexadecane, octadecane, eicosane, the positive butyl ester of hard ester acid.
5. the flocculus with temperature adjustment function according to claim 1, wherein phase-change material is micro mist, emulsion or other forms of solid-liquid mixed dispersion.
6. the flocculus with temperature adjustment function according to claim 1, wherein said phase-change material are microcapsules of storing energy through phase change or Na capsule form, and range scale is 10nm-1000 μ m.
7. preparation method with flocculus of temperature adjustment function; In the processing or production process of flocculus base material; Employing is padded, immersion absorbs water, spraying is sprayed and/or coated technique, makes physical absorption or bonding takes place between phase-change material and substrate fiber, perhaps combines through generating chemical bond.
8. preparation method with flocculus of temperature adjustment function; After the processing or production completion of flocculus base material; Employing is padded, immersion absorbs water, spraying is sprayed and/or coated technique, makes physical absorption or bonding takes place between phase-change material and substrate fiber, perhaps combines through generating chemical bond.
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Application publication date: 20120711 |