EP1221500A1 - Fibres synthétiques acryliques thermochromiques, articles produits à partir de celles-ci et procédé pour leur fabrication - Google Patents

Fibres synthétiques acryliques thermochromiques, articles produits à partir de celles-ci et procédé pour leur fabrication Download PDF

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Publication number
EP1221500A1
EP1221500A1 EP01300031A EP01300031A EP1221500A1 EP 1221500 A1 EP1221500 A1 EP 1221500A1 EP 01300031 A EP01300031 A EP 01300031A EP 01300031 A EP01300031 A EP 01300031A EP 1221500 A1 EP1221500 A1 EP 1221500A1
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Prior art keywords
thermochromic
color
synthetic fiber
acrylic synthetic
pigment composition
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EP01300031A
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German (de)
English (en)
Inventor
Yoshiaki c/o The Pilot Ink Co. Ltd. Ono
Naoya c/o The Pilot Ink Co. Ltd. Ishimura
Yutaka c/o The pilot Ink Co. Ltd. Shibahashi
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Pilot Ink Co Ltd
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Pilot Ink Co Ltd
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Priority to EP01300031A priority Critical patent/EP1221500A1/fr
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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F1/04—Pigments

Definitions

  • thermochromic acrylic synthetic fiber having a thermochromic pigment contained dispersedly in an acrylonitrile polymer, its processed article, and a process for producing the thermochromic acrylic synthetic fiber.
  • thermochromic layer As a means for providing fibers with a thermochromic function, conventionally available are a means of covering fiber surfaces with thermochromic layers having a thermochromic pigment fixed dispersedly in a binder resin (Japanese Patent Applications Laid-Open No. 61-179389, No. 62-156355, etc.) and a means of melt-blending a thermochromic pigment in a thermoplastic fiber-forming polymer such as polyester, polyamide or polyolefin, followed by melt-spinning to form fibers in an integral form.
  • thermochromic pigment integrally, because of thermal properties of the acrylonitrile polymer. Accordingly, it has been indispensable to form on fiber surfaces the above thermochromic layers by post-processing to provide the thermochromic function.
  • thermochromic pigment undergoes high temperature and high pressure in the course of its melt-blending with the fiber-forming polymer and in the course of melt spinning. This causes thermal deterioration of the thermochromic pigment in some cases. Accordingly, there has been obstruction to the use of fiber-forming polymers having high molecular weight and high melting point which are commonly applicable to fibrous products, and it has been difficult to practically satisfy durability such as fiber strength.
  • an object of the present invention is to provide a thermochromic acrylic synthetic fiber, and its processed article, which can effectively lastingly exhibit the thermochromic function without losing the hand inherent in acrylic fibers and other fibrous features, and to provide a process for producing such a thermochromic acrylic synthetic fiber.
  • thermochromic acrylic synthetic fiber comprising an acrylonitrile polymer in which a thermochromic pigment composition with an average particle diameter of from 0.5 ⁇ m to 30 ⁇ m is dispersedly contained in an amount of from 0.5% by weight to 40% by weight based on the weight of the polymer, and being made into fibers; the pigment composition containing (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound and (c) a reaction medium that determines the temperature at which the color-developing reaction of the both compounds takes place.
  • the thermochromic pigment composition may have an average particle diameter [ (length + breadth)/2] in the range of from 0.5 ⁇ m to 15.0 ⁇ m;
  • the thermochromic pigment composition may be a pigment composition having a microcapsular form in which a reversible thermochromic composition containing (a) the electron-donating color-developing organic compound, (b) the electron-accepting compound and (c) the reaction medium that determines the temperature at which the color-developing reaction of the both compounds takes place is enclosed in microcapsules;
  • the thermochromic pigment composition may have a non-round particle cross section; or the thermochromic pigment composition may be a pigment composition having a hollow at some part of a particle outer surface; or the thermochromic pigment composition may be a pigment composition selected from any one of a heat-color-
  • the present invention also provides a fiber processed article comprising a plurality of filaments of long fibers or short fibers of the above thermochromic acrylic synthetic fiber, having a single-fiber external diameter of from 1 ⁇ m to 100 ⁇ m; the filaments being made into a bundled, close-contact or massed state.
  • the present invention still also provides a process for producing a thermochromic acrylic synthetic fiber, comprising the step of; subjecting to wet spinning a spinning dope comprising a concentrated aqueous inorganic salt solution in which an acrylonitrile polymer has been dissolved and in which a thermochromic pigment composition with an average particle diameter of from 0.5 ⁇ m to 30 ⁇ m is dispersedly blended in an amount of from 0.5% by weight to 40% by weight based on the weight of the polymer; the pigment composition containing (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound and (c) an reaction medium that determines the temperature at which the color-developing reaction of the both compounds takes place.
  • the concentrated aqueous inorganic salt solution may contain as a chief component a thiocyanate or zinc chloride.
  • Fig. 1 is a cross-sectional illustration of the thermochromic acrylic synthetic fiber of the present invention.
  • Figs. 2A and 2B show an example of the thermochromic pigment composition applied in the thermochromic acrylic synthetic fiber of the present invention
  • Fig. 2A is an enlarged view of its appearance
  • Fig. 2B its cross section.
  • Figs. 3A and 3B show another example of the thermochromic pigment composition applied in the thermochromic acrylic synthetic fiber of the present invention
  • Fig. 3A is an enlarged view of its appearance
  • Fig. 3B its cross section.
  • Figs. 4A and 4B show still another example of the thermochromic pigment composition applied in the thermochromic acrylic synthetic fiber of the present invention
  • Fig. 4A is an enlarged view of its appearance
  • Fig. 4B its cross section.
  • Figs. 5A and 5B show a further example of the thermochromic pigment composition applied in the thermochromic acrylic synthetic fiber of the present invention
  • Fig. 5A is an enlarged view of its appearance
  • Fig. 5B its cross section.
  • Fig. 6 is a graph showing metachromatic behavior of a heat-color-extinguishing thermochromic composition.
  • Fig. 7 is a graph showing metachromatic behavior of a color-memorizing thermochromic composition.
  • Fig. 8 is a graph showing metachromatic behavior of a heat-color-developing thermochromic composition.
  • the present invention is a thermochromic acrylic synthetic fiber comprising an acrylonitrile polymer 1 in which a thermochromic pigment composition 2 with an average particle diameter of from 0.5 ⁇ m to 30 ⁇ m is contained dispersedly as shown in Fig. 1, in an amount of from 0.5% by weight to 40% by weight based on the weight of the polymer, and being made into fibers.
  • the pigment composition contains (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound and (c) a reaction medium that determines the temperature at which the color-developing reaction of the both compounds takes place.
  • thermochromic pigment composition it is effective to use a conventionally known pigment composition containing three essential components which are (a) the electron-donating color-developing organic compound, (b) the electron-accepting compound and (c) the reaction medium that determines the temperature at which the color-developing reaction of the both compounds takes place.
  • three essential components which are (a) the electron-donating color-developing organic compound, (b) the electron-accepting compound and (c) the reaction medium that determines the temperature at which the color-developing reaction of the both compounds takes place.
  • usable are those disclosed in United States Patent No. 4,028,118 and United States Patent No. 4,732,810.
  • those having a system with ⁇ H A of 3°C or below [which makes use as the component (c) an aliphatic ester showing a ⁇ T value (melting point -cloud point) of 3°C or below as disclosed in United States Patent No. 4,732,810] can sharply respond to temperature changes at the color-changing point making a border, to exhibit heat-color-extinguishing performance in a high sensitivity, and are effectively applicable according to purposes (see Fig. 6).
  • a region embracing a normal temperature region e.g., 15 to 35°C
  • a region embracing a normal temperature region can be general-purpose, but it is by no means specified to such a temperature range.
  • thermochromic pigment composition may also include, as heat-color-developing type thermochromic compositions (C) , which are capable of developing a color upon heating from the color-extinguished state, those disclosed in Japanese Patent Applications Laid-Open No. 11-129623 and No. 11-5973, in which a specific alkoxyphenolic compound having a straight-chain or side-chain alkyl group having 3 to 18 carbon atoms is used as the component- (b) electron-accepting compound (see Fig. 8).
  • C heat-color-developing type thermochromic compositions
  • thermochromic acrylic synthetic fiber which has various forms of color changes.
  • the thermochromic pigment composition may be in the form of fine particles containing the above three components (a), (b) and (c), and may effectively be a particulate composition produced by blending the three components with a binder resin (such as a thermosetting epoxy resin containing a curing agent), a composition obtained by further coating such a particulate composition with a different resin (such as a watersoluble polymeric compound such as a polyvinyl alcohol resin), or a composition having a microcapsular form in which the above three components (a), (b) and (c) are enclosed in microcapsules having wall films (such as a thermosetting resin including, e.g., bisphenol-A type epoxy resins, novolak type epoxy resins and polyurethane resins (reaction products of aromatic isocyanate prepolymers with polyhydroxyl compounds)).
  • a binder resin such as a thermosetting epoxy resin containing a curing agent
  • a composition obtained by further coating such a particulate composition with a different resin such as a
  • thermochromic pigment composition may have an average particle diameter [(length + breadth)/2] in the range of from 0.5 ⁇ m to 30 ⁇ m, preferably from 0.5 ⁇ m to 15 ⁇ m, and more preferably from 0.5 ⁇ m to 10 ⁇ m. This is effective in view of sharpness in metachromatism, durability, processing suitability and so forth.
  • the pigment composition may non-homogeneously be dispersed to make it difficult to form fibers capable of showing thermochromic performance in a stable quality.
  • a system having an average particle diameter smaller than 30 ⁇ m especially in the system of the pigment composition having a microcapsular form, although a thermochromic pigment composition made into microcapsules in a state suspended in an aqueous medium can be obtained, there is a difficulty in separation of the encapsulated pigment composition therefrom by a means such as filtration or centrifugation, and also an insufficient strength may result.
  • thermochromic pigment composition is a pigment composition having a non-spherical form and a flat particle shape, and hence can appropriately undergo elastic deformation to relieve stress, against any load caused by pressure or heat, bringing about the effect of keeping capsule wall films from breaking. More specifically, in the course of heating, wall films undergo elastic deformation in accordance with thermal expansion and constriction of capsules to bring about the effect of keeping capsule wall films from breaking, and function effectively as a thermochromic pigment composition having a microcapsular form which is tough enough to protect the reversible thermochromic composition enclosed therein and make it retain the intended thermochromic function.
  • the proportion of the reversible thermochromic composition to wall film in each capsule i.e., reversible thermochromic composition/wall film may preferably be in the range of 7/1 to 1/1 (weight ratio). If the reversible thermochromic composition is in a proportion beyond the above range, the wall film may have so small a thickness as to have a low function of protecting the reversible thermochromic composition enclosed therein. If on the other hand the wall film is in a proportion beyond the above range, a low coloring density may inevitably result, undesirably.
  • thermochromic pigment composition of the present invention having the particle diameter range and external particle shape that satisfy the requirements described above, interfacial polymerization or interfacial polycondensation is preferred, which may hardly cause agglomeration and coalescence.
  • the resultant capsule suspension may optionally be diluted with water, and impurities and coarse particles may be filtered off by means of a filter to remove unwanted impurities and coarse particles.
  • thermochromic pigment composition may be blended in a proportion of from 0.5% by weight to 40% by weight based on the weight of the acrylonitrile polymer that forms fibers. If it is less than 0.5% by weight, the resultant product can not exhibit any sharp thermochromic performance. If on the other hand it is more than 40% by weight, the resultant product tends to cause color ghost at the time of color extinguishing. It may preferably be in the range of from 1% by weight to 20% by weight.
  • thermochromic acrylic synthetic fiber processed article of the present invention comprises a plurality of filaments of long fibers or short fibers of the thermochromic acrylic synthetic fiber described above, having a single-fiber external diameter of from 1 ⁇ m to 100 ⁇ m; the filaments being made into a bundled, close-contact or massed state.
  • the fiber processed article may have a sized form such as tow, a sliver, or a cottony aggregate produced by aggregating staple fibers, a fiber-to-fiber close contact form such as yarn or cloth, or a massed form such as flocked fabric, raised fabric or papermaked fabric.
  • a sized form such as tow, a sliver, or a cottony aggregate produced by aggregating staple fibers, a fiber-to-fiber close contact form such as yarn or cloth, or a massed form such as flocked fabric, raised fabric or papermaked fabric.
  • the yarn may include filament yarn, spun yarn and wool-yarn-like crimped yarn.
  • the filament yarn includes filament textured yarn subjected to stretch or bulky texturing.
  • the spun yarn includes bulky yarn produced by spinning a blend of hot drawn staple fibers and hot non-drawn staple fibers.
  • the cloth may include woven fabric, knitted fabric, nonwoven fabric and pile fabric.
  • the woven fabric may be exemplified by plain-weave fabric, twill weave (or twill) fabric, satin weave fabric, double warp fabric, double weft fabric, double warp-weft fabric, pile weave fabric, leno weave fabric and Jacquard fabric.
  • the knitted fabric may also be exemplified by warp knitted fabric, weft knitted fabric, and lace.
  • the fiber processed article of the present invention can be obtained by processing the component thermochromic acrylic synthetic fiber by a conventional general-purpose processing means into the various forms described above.
  • any forms are effective as long as a plurality of filaments of the above fibers are made into the bundled, close-contact or massed state.
  • the fiber processed article of the present invention is a fiber processed article constituted as described above, and hence responds sharply to temperature changes to undergo a change in color, depending on the extent of uncovered outer surfaces of individual fibers . Moreover, since the fiber-forming acrylonitrile polymer capable of forming general-purpose acrylic synthetic fiber is used and besides the thermochromic pigment composition is dispersedly contained in the fiber, the fiber has the same durability and fibrous properties as those of general-purpose fibers.
  • fiber processed articles having the same forms as those of general-purpose fibers as described above can be obtained, and can be used in knitted products as exemplified by various types of sweaters, polo shirts, sport shirts, cloth (dress material), underwears, pajamas, tights, gloves and stockings or socks, and textiles as exemplified by blankets, child's cloth (dress material), sport shirts and coats, as well as carpets, chair-covering cloth, curtains and so forth.
  • the fiber processed article of the present invention can further be used in wigs, hairpieces or doles' or animal toys' hair of the head, hair of bodies and outer garments part or the whole of which is formed of filament yarn, spun yarn, wool-yarn-like crimped yarn or pile fabric; and doles' or animal toys' clothes, outer garments or accessories constituted of any of woven fabric, knitted fabric, nonwoven fabric and pile fabric.
  • the fiber processed article may also be blended with a non-thermochromic fiber in an amount of from 0.01 part by weight to 20 parts by weight (usually from 5 to 15 parts by weight) based on 1 part by weight of the thermochromic acrylic synthetic fiber.
  • a non-thermochromic fiber is blended in order to regulate glossiness or drape and to regulate the thermochromic effect.
  • acrylic fibers general-purpose common fibers are effective.
  • thermochromic acrylic synthetic fiber A process for producing the thermochromic acrylic synthetic fiber according to the present invention is described below.
  • the production process of the present invention comprises the step of;
  • the concentrated aqueous inorganic salt solution may include concentrated aqueous solutions of thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate and calcium thiocyanate, and concentrated aqueous solutions of inorganic salts such as zinc chloride and lithium chloride .
  • thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate and calcium thiocyanate
  • concentrated aqueous solutions of inorganic salts such as zinc chloride and lithium chloride .
  • these inorganic salts act as good solvents of the acrylonitrile polymer without causing any deterioration of metachromatic function of the thermochromic pigment composition.
  • a coagulating bath in which filamentous material ejected from a spinning nozzle is made to coagulate
  • preferred is water or an aqueous solution of the above inorganic salts in a concentration of 20% or less which is conventionally in general use.
  • the spinning dope its mixing quantity may be regulated in accordance with the degree of polymerization of the above polymer so as to provide a spinning dope having appropriate properties. Usually, those having a viscosity of about 40 to 200 poises at 30°C are effective.
  • the acrylonitrile polymer may include those containing i) polyacrylonitrile or a copolymer of acrylonitrile with a compound copolymerizable therewith and ii) a second component such as vinyl chloride. Preferred are those containing acrylonitrile in an amount of 50% by weight or more, and preferably 80% by weight or more.
  • the compound copolymerizable with acrylonitrile to produce an acrylonitrile copolymerization product effective for practicing the present invention it may include, but not particularly limited to, e.g.
  • acrylic acid or methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate; acrylamide, methacrylamide, and alkyl-substituted products or nitrogen substituted products of these; vinyl pyridines such as 2-vinyl pyridine and 2-methyl-5-vinyl pyridine; styrene and alkyl-substituted products thereof; and also monomers such as vinyl chloride, vinylidene chloride, vinyl bromide and vinylidene bromide.
  • the single-polymer acrylonitrile or copolymer acrylonitrile may usually have a molecular weight (average molecular weight) appropriately selected within the range of from 15,000 to 150,000 (for general purpose, from 25,000 to 800,000).
  • the spinning dope in the present invention may be composed of from 5 to 30% by weight (preferably from about 10 to 20% by weight) of the acrylonitrile polymer and from 30 to 60% by weight of the thiocyanate or zinc chloride.
  • the thermochromic pigment composition may be dispersed in an amount of from 0.5 to 40% by weight (preferably from 1 to 20% by weight) based on the weight of the polymer. Any of commonly available pigments and lustrous materials may further be added.
  • the above spinning dope may be extruded at 45°C to 75°C from a spinning nozzle into the coagulating bath such as a dilute aqueous thiocyanate solution to cause it to coagulate, followed by known steps of washing with water, heat treatment, drying, and further crimping treatment, lubricant treatment and so forth to produce the fiber.
  • a spinning nozzle into the coagulating bath such as a dilute aqueous thiocyanate solution to cause it to coagulate, followed by known steps of washing with water, heat treatment, drying, and further crimping treatment, lubricant treatment and so forth to produce the fiber.
  • the pigment composition having a microcapsular form In the system in which the pigment composition having a microcapsular form is used as the thermochromic pigment composition, the pigment composition has a durability and also is readily dispersible at the time the spinning dope is prepared.
  • the pigment composition having a non-round particle cross section can relieve stress because of its own elastic deformation, against any load caused by pressure or high-temperature heat in the course of spinning and in the course of the formation of fibers by drawing.
  • the microcapsules by no means break.
  • the fiber that satisfies the intended thermochromic function can be obtained.
  • the single fiber in the present invention may have a fiber diameter of from 1 ⁇ m to 100 ⁇ m (preferably from 10 ⁇ m to 40 ⁇ m).
  • the fiber may be treated in the same way as general-purpose non-thermochromic acrylic fibers so as to be made into tow, staple fibers and any other desired fibrous form, and may be put into practical use.
  • the fiber In a fiber diameter smaller than 1 ⁇ m, the fiber can not have a proper fibrous form in relation to the particle diameter of the thermochromic pigment composition and the spinning properties. On the other hand, in a fiber diameter larger than 100 ⁇ m, the fiber may show a property of rigid filaments and may satisfy fibrous properties with difficulty.
  • the single fiber may have any external shape without limitation to a round shape, and may have a flat shape, a polygonal shape or any other known irregular shape.
  • the fiber can continuously and stably be formed when a relationship of d ⁇ D ⁇ 20d (wherein d represents particle diameter of the pigment composition, and D, fiber diameter) is satisfied.
  • thermochromic acrylic synthetic fiber of the present invention can be obtained using the spinning dope in which the thermochromic pigment composition having a specific particle diameter has been dispersed in a specific quantity in the concentrated aqueous inorganic salt solution containing the acrylonitrile polymer, and by ejecting the spinning dope from a spinning nozzle into the coagulating bath, followed by post treatment such as drawing by any known means so as to be made into a fibrous form.
  • the single fibers thus obtained are put into practical use in the form of various fiber processed articles made into a bundled, close-contact or massed state. Examples of the fiber processed article are as described previously, but in the present invention by no means limited thereto, and those satisfying the above state are effective.
  • part(s) refers to “part(s) by weight”.
  • thermochromic pigment composition (color-extinguishing temperature t4: about 33°C; color-developing temperature t1: about 28°C; blue in the color-developed state and colorless in the color-extinguished state; average particle diameter: 3 ⁇ m; particle cross-sectional shape: as shown in Figs.
  • thermochromic composition/wall film 5.6/1.0
  • reversible thermochromic composition/wall film 5.6/1.0
  • the reversible thermochromic composition being comprised of 1 part of (a) 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl indol-3-yl)4-azaphthalide, 5 parts of (b) 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 25 parts of (c) cetyl alcohol and 25 parts of stearyl caprate.
  • the mixture obtained was uniformly dispersed to prepare a spinning dope comprised of 1% by weight of the reversible thermochromic pigment composition, 10% by weight of the acrylonitrile copolymer, 44.5% by weight of sodium thiocyanate and 44.5% by weight of water.
  • the spinning dope was ejected at -2°C into an aqueous sodium thiocyanate solution of 15% by weight in concentration from a spinning nozzle of 0.04 mm in aperture diameter to carry out wet spinning, further followed by washing with water, drawing, drying densification, crimping treatment, heat treatment, lubricant treatment and so forth under conventionally known conditions to obtain a thermochromic acrylic synthetic fiber having a fiber diameter of 20 ⁇ m.
  • This fiber had a heat-color-extinguishing thermochromic performance (see Fig. 6), which stood blue at room temperature (25°C), and turned colorless upon heating to a temperature of about 33°C or above. In this state the fiber was left at room temperature (25°C), whereupon it again became blue at about 28°C.
  • thermochromic pigment composition (color-extinguishing temperature t4: about 15°C; color-developing temperature t1: about 10°C; pink in the color-developed state and colorless in the color-extinguished state; average particle diameter: 5 ⁇ m; particle cross-sectional shape: as shown in Figs.
  • thermochromic composition/wall film 5.8/1.0
  • reversible thermochromic composition/wall film 5.8/1.0
  • the reversible thermochromic composition being comprised of 3 part of (a) 1,2-benzo-6-diethylaminofluorane, 5 parts of (b) 2,2-bis(4-hydroxyphenyl)propane, 25 parts of (c) myristyl alcohol and 25 parts of decyl myristate.
  • the mixture obtained was uniformly dispersed to prepare a spinning dope comprised of 1% by weight of the reversible thermochromic pigment composition, 10% by weight of the acrylonitrile copolymer, 53.4% by weight of zinc chloride and 35.6% by weight of water.
  • the spinning dope was ejected at -2°C into an aqueous zinc chloride solution of 15% by weight in concentration from a spinning nozzle of 0.06 mm in aperture diameter to carry out wet spinning, further followed by washing with water, drawing, drying densification, crimping treatment, heat treatment, lubricant treatment and so forth under conventionally known conditions to obtain a thermochromic acrylic synthetic fiber having a fiber diameter of 30 ⁇ m.
  • This fiber had a heat-color-extinguishing thermochromic performance (see Fig. 6), which stood colorless at room temperature (25°C), and turned pink upon cooling to a temperature of about 10°C or below. In this state the fiber was left at room temperature (25°C), whereupon it again became colorless at about 15°C.
  • thermochromic color-memorizing pigment composition (color-extinguishing temperature t4: about 32°C; color-developing temperature t1: about 15°C; orange in the color-developed state and colorless in the color-extinguished state; average particle diameter: 2 ⁇ m; particle cross-sectinal shape: as shown in Figs.
  • thermochromic composition/wall film 5.8/1.0
  • reversible thermochromic composition/wall film 5.8/1.0
  • the reversible thermochromic composition being comprised of 3 parts of (a) 1,3-dimethyl-6-diethylaminofluorane, 5 parts of (b) 1,1-bis(4-hydroxyphenyl)-2-ethylhexane and 50 parts of (c) neopentyl stearate.
  • the mixture obtained was uniformly dispersed to prepare a spinning dope comprised of 1% by weight of the reversible thermochromic color-memorizing pigment composition, 10% by weight of the acrylonitrile copolymer, 44.5% by weight of sodium thiocyanate and 44.5% by weight of water.
  • the spinning dope was ejected at -2°C into an aqueous sodium thiocyanate solution of 15% by weight in concentration from a spinning nozzle of 0.04 mm in aperture diameter to carry out wet spinning, further followed by washing with water, drawing, drying densification, crimping treatment, heat treatment, lubricant treatment and so forth under conventionally known conditions to obtain a thermochromic acrylic synthetic fiber having a fiber diameter of 15 ⁇ m.
  • This fiber kept in the color-extinguished state at room temperature (25°C), was cooled to about 15°C or below, whereupon it colored in orange, and this color-developed state was retainable also when again heated to room temperature (25°C). Also, when heated from the orange-color-developed state, the fiber came into the color-extinguished state at about 32°C, and this state was retainable until it was again cooled to about 15°C or below, showing a color-memorizing thermochromic performance (see Fig. 7).
  • the fiber had a color-memorizing performance, and this metachromatism was repeatable.
  • thermochromic acrylic synthetic fiber having a fiber diameter of 20 ⁇ m.
  • thermochromic pigment composition had a heat-color-developing thermochromic performance (see Fig. 8), which was in the color-extinguished state (colorless) at room temperature of 25°C, began to develop a color at about 33°C (T1), came into a blue-color-developed state at 43°C (T2) and then, in the course of temperature drop, maintained the color-developed state until 32°C (T3), became color-extinguished little by little with a drop of temperature, and completely came into the color-extinguished state at 27°C (T4), and the resultant fiber had the corresponding thermochromic performance.
  • thermochromic raw cotton materials were each cut on the bias in a length of from 100 mm to 150 mm to obtain five kinds of thermochromic raw cotton materials.
  • the thermochromic raw cotton materials showed the same metachromatic behavior as the fibers of Examples 1 to 5.
  • the raw cotton materials obtained by cutting on the bias were obtained using a means conventionally in general use.
  • Fiber processed articles in the following Examples 7 to 12 were also obtained using a means conventionally in general use.
  • thermochromic raw cotton materials in Example 6 were each set on a card machine and made into a sliver, followed by spinning to obtain five kinds of thermochromic spun yarn.
  • the respective thermochromic spun yarn showed the same metachromatic behavior as the corresponding fibers of Examples 1 to 5.
  • thermochromic plain-weave fabrics showed the same metachromatic behavior as the corresponding fibers of Examples 1 to 5.
  • thermochromic satin-weave fabrics showed the same metachromatic behavior as the corresponding fibers of Examples 1 to 5.
  • thermochromic nonwoven fabrics showed the same metachromatic behavior as the corresponding fibers of Examples 1 to 5.
  • Example 7 Each spun yarn of Example 7 was woven into a circular knit by means of a knitting machine to obtain five kinds of thermochromic circular knitted fabrics. These thermochromic circular knitted fabrics showed the same metachromatic behavior as the corresponding spun yarn.
  • Example 7 Each spun yarn of Example 7 was woven into towel fabric by means of a knitting machine to obtain five kinds of thermochromic towel fabrics. These thermochromic towel fabrics showed the same metachromatic behavior as the corresponding spun yarn.
  • thermochromic flocked fabrics showed the same metachromatic behavior as the corresponding fibers of Examples 1 to 5.
  • thermochromic high-pile fabrics were obtained by means of a high-pile stitching machine to obtain five kinds of thermochromic high-pile fabrics of 30 mm in pile length. These thermochromic high-pile fabrics showed the same metachromatic behavior as the corresponding row cotton materials.
  • thermochromic satin-weave fabrics of Example 9 were sewed to obtain five kinds of stuffed toys.
  • thermochromic high-pile fabrics of Example 14 were sewed to obtain five kinds of stuffed toys.
  • thermochromic raw cotton materials obtained by cutting on the bias in a length of from 80 mm to 130 mm, having been crimped, were each set on a card machine, followed by twisting by a conventional method to obtain bulky yarn. Three strands of this bulky yarn were bundled, and then twisted to obtain five kinds of thermochromic woolen yarn.
  • thermochromic woolen yarn was cut in appropriate dimensions, and ends were bonded to obtain thermochromic artificial hairs. These artificial hairs showed the same metachromatic behavior as the corresponding fibers.
  • thermochromic acrylic synthetic fiber of the present invention contains the thermochromic pigment composition having a specific particle diameter, standing dispersed in the fiber in a specific quantity, and hence, compared with a system in which the thermochromic pigment composition is fixed with a binder resin on the surface, can satisfy durability such as wash-fastness, scratch resistance or light-fastness and also does not damage the drape, bulkiness and other fibrous properties that are inherent in acrylic fibers.
  • thermochromic function without damaging the fibrous properties and processing suitability that are inherent in acrylic fibers, and moreover can effectively exhibit the thermochromic function.
  • the fiber processed article of the present invention can be effective as yarn for weaving (warp yarn and weft yarn), for knitting (knitting raw yarn and yarn for knitting by hand), for sewing (sewing yarn, yarn for sewing by hand, tacking thread and so forth), and for handicraft (lace yarn, embroider thread, lace raw yarn and so forth), and besides as yarn for industrial use.
  • the fiber processed article in the forms of woven fabric, knitted fabric, nonwoven fabric and pile fabric, can effectively be used in the field of, e.g., articles of clothing, articles of bedding, articles of accessories and articles of the interior as a matter of course, and also in the field of, e.g., artificial hair and stuffed toys.
  • the pigment composition having a microcapsular form In the system in which the pigment composition having a microcapsular form is used as the thermochromic pigment composition, it has a durability and also a good dispersibility when the spinning dope is prepared, and can further be effective in the courses of spinning and heat treatment. Especially in the system in which it has non-round particle cross section, it is rich in elastic deformation due to external pressure, and can relieve stress because of its own elastic deformation, against any load caused by pressure in the step of blending and pressure in the step of forming fibers. In addition, in company with the properties that the microcapsular pigment composition itself tends to be oriented in the lengthwise direction at the time of fiber formation, there is no possibility that the microcapsules are broken.
  • thermochromic acrylic synthetic fiber processed article which shows the same durability as the above also against any load caused by the heat and pressure in the course of secondary processing or in actual service and can make the thermochromic function last long.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
EP01300031A 2001-01-04 2001-01-04 Fibres synthétiques acryliques thermochromiques, articles produits à partir de celles-ci et procédé pour leur fabrication Withdrawn EP1221500A1 (fr)

Priority Applications (1)

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Publication number Priority date Publication date Assignee Title
WO2008115682A3 (fr) * 2007-03-20 2009-04-16 Albany Int Corp Etoffe industrielle ayant un capteur thermochromique
CN102433672A (zh) * 2011-11-01 2012-05-02 常熟新诚鑫织造有限公司 一种遮阳绒布
FR2993888A1 (fr) * 2012-07-30 2014-01-31 Inst Polytechnique Bordeaux Materiau composite thermochrome et procede de fabrication d'un tel article
CN103549684A (zh) * 2013-11-11 2014-02-05 苏州工业园区友顺制衣厂 一种感温预警手套
US20200240041A1 (en) * 2017-10-18 2020-07-30 University Of Central Florida Research Foundation, Inc. Fibers having electrically conductive core and color-changing coating
US11708649B2 (en) 2020-05-21 2023-07-25 University Of Central Florida Research Foundation, Inc. Color-changing fabric having printed pattern
US11976389B2 (en) 2020-05-21 2024-05-07 University Of Central Florida Research Foundation, Inc. Color-changing fabric and applications

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EP0665119A1 (fr) * 1993-12-24 1995-08-02 The Pilot Ink Co., Ltd. Composition thermochrome à mémoire couleur
EP0787779A2 (fr) * 1996-02-05 1997-08-06 The Pilot Ink CO., Ltd. Procédé pour préparer des encres pour stylos à bille aqueuses et fluidifiables par cisaillement, compositions de ces encres et stylos à bille en faisant usage
EP0873881A1 (fr) * 1997-04-23 1998-10-28 The Pilot Ink CO., Ltd. Compositions thermochromiques réversibles
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JPS62149907A (ja) * 1985-12-20 1987-07-03 Kanegafuchi Chem Ind Co Ltd かつら・ド−ルヘア用フイラメント
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008115682A3 (fr) * 2007-03-20 2009-04-16 Albany Int Corp Etoffe industrielle ayant un capteur thermochromique
RU2471905C2 (ru) * 2007-03-20 2013-01-10 Олбани Интернешнл Корп. Промышленная ткань с термохромным индикатором
CN101641473B (zh) * 2007-03-20 2014-01-15 阿尔巴尼国际公司 具有热致变色感应元件的工业织物
US8728373B2 (en) 2007-03-20 2014-05-20 Albany International Corp. Industrial fabric having a thermochromic sensor
TWI457477B (zh) * 2007-03-20 2014-10-21 Albany Int Corp 具有熱色感測器（ｔｈｅｒｍｏｃｈｒｏｍｉｃ ｓｅｎｓｏｒ）之工業織物及形成該工業織物的方法
CN102433672A (zh) * 2011-11-01 2012-05-02 常熟新诚鑫织造有限公司 一种遮阳绒布
FR2993888A1 (fr) * 2012-07-30 2014-01-31 Inst Polytechnique Bordeaux Materiau composite thermochrome et procede de fabrication d'un tel article
WO2014020266A1 (fr) * 2012-07-30 2014-02-06 Institut Polytechnique De Bordeaux Matériau composite thermochrome et procédé de fabrication d'un tel article
CN103549684A (zh) * 2013-11-11 2014-02-05 苏州工业园区友顺制衣厂 一种感温预警手套
US20200240041A1 (en) * 2017-10-18 2020-07-30 University Of Central Florida Research Foundation, Inc. Fibers having electrically conductive core and color-changing coating
US11708649B2 (en) 2020-05-21 2023-07-25 University Of Central Florida Research Foundation, Inc. Color-changing fabric having printed pattern
US11976389B2 (en) 2020-05-21 2024-05-07 University Of Central Florida Research Foundation, Inc. Color-changing fabric and applications

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