EP4324963A1 - Infrarotabsorbierende faser und faserprodukt - Google Patents

Infrarotabsorbierende faser und faserprodukt Download PDF

Info

Publication number
EP4324963A1
EP4324963A1 EP21937002.0A EP21937002A EP4324963A1 EP 4324963 A1 EP4324963 A1 EP 4324963A1 EP 21937002 A EP21937002 A EP 21937002A EP 4324963 A1 EP4324963 A1 EP 4324963A1
Authority
EP
European Patent Office
Prior art keywords
fiber
infrared absorbing
resin
absorbing particles
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21937002.0A
Other languages
English (en)
French (fr)
Inventor
Hirofumi Tsunematsu
Takeshi Chonan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Publication of EP4324963A1 publication Critical patent/EP4324963A1/de
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
    • 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
    • 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
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the present invention relates to an infrared absorbing fiber and a fiber product.
  • the first method is to maintain heat retention by reducing the dissipation of heat generated from the human body.
  • methods of physically increasing the air layer in the cold weather clothing by controlling the weaving structure in the cold weather clothing or making the fibers used hollow or porous have been adopted.
  • the second method is to improve heat retention by accumulating heat by active methods such as radiating the heat generated from the human body back to the human body and converting part of the sunlight received by the cold weather clothing into heat.
  • active methods such as radiating the heat generated from the human body back to the human body and converting part of the sunlight received by the cold weather clothing into heat.
  • methods of chemically or physically processing the entire clothing or fibers constituting the cold weather clothing have been adopted.
  • the first method was to increase the air space in the clothing, thicken the fabric, make the fabric finer, or darken the color.
  • Specific examples include winter clothing such as sweaters, and clothing that is often used as clothing for sports in winter and that has batting inserted between the outer fabric and the lining to maintain heat retention due to the thickness of the air layer in the batting.
  • the air layer is increased by adding the batting or the like, the clothing becomes heavy and bulky, causing problems for sports that require ease of movement.
  • the second method described above which actively and effectively utilizes heat generated inside or from outside, has been adopted.
  • a method is known in which a metal such as aluminum or titanium is deposited on the lining or the like of clothing to reflect radiant heat emitted from the body on the metal deposited surface, thereby actively preventing the dissipation of heat.
  • a metal such as aluminum or titanium
  • the yield deteriorates due to uneven deposition and the like, resulting in an increase in the price of the product itself.
  • PTL 1 discloses a heat ray radiating fiber characterized in that the fiber includes one or more types of inorganic fine particles having a heat ray radiating property that contain at least one of metals having a thermal conductivity of 0.3 kcal/m 2 ⁇ sec ⁇ °C or more and metal ions.
  • the inorganic fine particles having a heat ray radiating property include silica and barium sulfate.
  • PTL 2 discloses a heat retention composite fiber including: a thermoplastic polymer A having a melting point of 110°C or more; and a thermoplastic polymer B having a melting point of 15 to 50°C, a temperature-lowering crystallization temperature of 40°C or less, and a crystallization heat of 10 mJ/mg or more, wherein the composite fiber includes ceramic fine particles having a far-infrared radiation ability of 0.1 to 20 wt% relative to the weight of the fiber, and wherein the polymer A covers the surface of the fiber.
  • PTL 3 discloses an infrared absorbing processed fiber product in which a binder resin containing an infrared absorbing agent consisting of at least one or more predetermined amino compounds is dispersed and adhered to the fiber product.
  • PTL 4 discloses a near infrared absorbing processing method for a cellulose fiber structure in which, by dyeing with a combination of a dye that absorbs more in a near-infrared region than a black dye and other dyes, a spectral reflectance of a fabric is 65% or less within a range of 750 to 1,500 nm as a degree of near infrared absorption.
  • the applicant of the present invention has proposed fibers containing boride fine particles, tungsten oxide fine particles, composite tungsten oxide fine particles, and fiber products obtained by processing the fibers, in PTLs 5, 6, and 7.
  • infrared absorbing fibers containing infrared absorbing particles have been conventionally investigated.
  • infrared absorbing particles such as tungsten oxide fine particles do not have sufficient chemical-resistant properties, and when infrared absorbing fibers and fiber products are exposed to chemical environments such as high-temperature acid or alkali, the infrared absorption properties may deteriorate.
  • an infrared absorbing fiber includes: a fiber; and organic-inorganic hybrid infrared absorbing particles, wherein the organic-inorganic hybrid infrared absorbing particles include infrared absorbing particles and a coating resin that covers at least a part of a surface of the infrared absorbing particles, and wherein the organic-inorganic hybrid infrared absorbing particles are located in one or more parts selected from an interior of the fiber and a surface of the fiber.
  • an infrared absorbing fiber having chemical-resistant properties can be provided.
  • the infrared absorbing fiber according to the present embodiment may include: a fiber; and organic-inorganic hybrid infrared absorbing particles.
  • the organic-inorganic hybrid infrared absorbing particles may include an infrared absorbing particles and a coating resin that covers at least a part of a surface of the infrared absorbing particles.
  • the organic-inorganic hybrid infrared absorbing particles may be located in the one or more parts selected from an interior of the fiber and a surface of the fiber.
  • the infrared absorbing particles used in the infrared absorbing fiber do not have sufficient chemical-resistant properties. Therefore, the inventors of the present invention conducted an intensive study on a method for obtaining infrared absorbing particles having chemical-resistant properties. As a result, it was found that chemical-resistant properties can be exhibited by placing an organic material such as a resin directly on at least a part of the surface of the infrared absorbing particles to form organic-inorganic hybrid infrared absorbing particles.
  • the infrared absorbing particles are usually an inorganic material, and it has been difficult to place an organic material such as a resin on at least a part of the surface of the infrared absorbing particles. For this reason, organic-inorganic hybrid infrared absorbing particles and their production method were not known. Therefore, the inventors of the present invention conducted further studies and found the organic-inorganic hybrid infrared absorbing particles in which the organic material is located on the surface of the infrared absorbing particles and their production method.
  • the infrared absorbing fiber according to the present embodiment may include the organic-inorganic hybrid infrared absorbing particles, as described above.
  • the method for producing the organic-inorganic hybrid infrared absorbing particles may include, for example, the following steps.
  • a dispersion medium reduction step for evaporating the dispersion medium from the dispersion liquid.
  • a raw material liquid mixture preparation step for preparing a raw material liquid mixture by mixing infrared absorbing particles collected after the dispersion medium reduction step, a raw material for a coating resin, an organic solvent, an emulsifier, water, and a polymerization initiator.
  • a dispersion liquid including infrared absorbing particles, a dispersant, and a dispersion medium can be prepared.
  • various infrared absorbing particles which are required to enhance chemical-resistant properties such as acid resistance and alkali resistance, for example, can be used as the infrared absorbing particles.
  • infrared absorbing particles for example, infrared absorbing particles including various materials containing free electrons may be preferably used, and infrared absorbing particles including various inorganic materials containing free electrons may be more preferably used.
  • infrared absorbing particles it is particularly preferable to use infrared absorbing particles including one or more oxides selected from tungsten oxide having oxygen deficiency and composite tungsten oxide.
  • the organic-inorganic hybrid infrared absorbing particles including the infrared absorbing particles can be made light-colored to make them less noticeable.
  • the infrared absorbing particles include, for example, one or more oxides selected from a tungsten oxide represented by a general formula W y O z (W: tungsten, O: oxygen, 2.2 ⁇ z/y ⁇ 2.999) and a composite tungsten oxide represented by a general formula M x W y O z (an element M is one or more elements selected from among H, He, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, 0.001 ⁇ x/y ⁇ 1, 2.0 ⁇ z/y ⁇ 3.0).
  • the infrared absorbing particles are preferable because, for example, when the particles are made smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) can be reduced, and particularly high transparency in the visible light region can be obtained.
  • transparency means “highly transparent with little scattering for light in the visible light region”.
  • tungsten oxide does not have effective free electrons, it has little absorption/reflection properties in the infrared region, and thus it is not effective as an infrared absorbing particle.
  • WO 3 with oxygen deficiency and the composite tungsten oxide in which positive elements such as Na and the like are added to WO 3 are conductive materials and are materials with free electrons. Analysis of the single crystal and the like of the materials with free electrons suggests that the free electrons respond to light in the infrared region.
  • tungsten oxides and composite tungsten oxides that are transparent in the visible light region and have particularly strong absorption in the infrared region can be formed.
  • the tungsten oxide or the composite tungsten oxide which are a kind of materials of the infrared absorbing particles that can be suitably used in the dispersion liquid preparation step, will be further described below.
  • the tungsten oxide is represented by the general formula W y O z (where W is tungsten, O is oxygen, and 2.2 ⁇ z/y ⁇ 2.999).
  • the composition ratio (z/y) of oxygen to tungsten is preferably less than 3, and more preferably 2.2 ⁇ z/y ⁇ 2.999. In particular, the composition ratio is even more preferably 2.45 ⁇ z/y ⁇ 2.999.
  • the infrared absorbing particles are particularly effective because appearance of an undesired WO 2 crystalline phase in the tungsten oxide can be avoided and chemical stability as a material can also be obtained.
  • z/y preferably less than 3 and more preferably to 2.999 or less, a particularly sufficient amount of free electrons can be generated to enhance the absorption/reflection properties in the infrared region, resulting in forming efficient infrared absorbing particles.
  • Magnnelli phase which has the composition ratio of 2.45 ⁇ z/y ⁇ 2.999, is chemically stable and has excellent absorption properties in the near-infrared region, so that the tungsten oxide can be used more preferably as an infrared absorbing material. Therefore, the composition ratio z/y is even more preferably 2.45 ⁇ z/y ⁇ 2.999, as described above.
  • the composite tungsten oxide is obtained by adding the element M, which will be described later, to the WO 3 described above.
  • WO 3 By adding the element M to form the composite tungsten oxide, free electrons are generated in WO 3 , and strong absorption properties derived from free electrons appears especially in the near-infrared region. Such WO 3 becomes effective as near-infrared absorbing particles around 1,000 nm in wavelength.
  • the WO 3 when the WO 3 is made into the composite tungsten oxide by controlling the oxygen amount and adding the element M that generates free electrons, it can exhibit more efficient infrared absorption properties.
  • the general formula of the composite tungsten oxide is represented by M x W y O z , the composition ratios preferably satisfy the relationship of 0.001 ⁇ x/y ⁇ 1 and 2.0 ⁇ z/y ⁇ 3.0.
  • M indicates the element M
  • W indicates tungsten
  • O indicates oxygen.
  • the value of x/y which indicates the additive amount of the element M
  • a particularly sufficient amount of free electrons is generated in the composite tungsten oxide, and a high infrared absorption effect can be obtained.
  • the value of x/y is 1 or less, it is preferable because the formation of impurity phases in the infrared absorbing particles containing the composite tungsten oxide can be avoided.
  • the element M is preferably one or more elements selected from among H, He, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I.
  • the element M is more preferably one or more elements selected from alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, and Re.
  • the element M is even more preferably one or more elements selected from alkali metal elements, alkaline earth metal elements, transition metal elements, group 4B elements, and group 5B elements.
  • the ratio z/y is preferably 2.0 ⁇ z/y ⁇ 3.0, more preferably 2.2 ⁇ z/y ⁇ 3.0, and even more preferably 2.45 ⁇ z/y ⁇ 3.0.
  • the composite tungsten oxide has a hexagonal crystal structure
  • the transmission of light in the visible light region of the infrared absorbing particles including the composite tungsten oxide is improved, and the absorption of light in the infrared region is improved.
  • FIG. 1 is a schematic plan view of the hexagonal crystal structure.
  • FIG. 1 illustrates a projection view of the crystal structure of a composite tungsten oxide having a hexagonal structure when viewed in the (001) direction.
  • the unit lattice 10 is indicated by the dotted line.
  • FIG. 1 six octahedra 11 formed by WO 6 units are assembled to form a hexagonal void 12, and an element 121, which is an element M, is placed in the void 12 to form a single unit, and a large number of these single units are assembled to form a hexagonal crystal structure.
  • the composite tungsten oxide may contain the unit structure described with reference to FIG. 1 , and the composite tungsten oxide may be crystalline or amorphous.
  • the hexagonal crystal is easily formed when an element M having a large ionic radius is added.
  • an element M having a large ionic radius is added as the element M
  • hexagonal crystals are easily formed. Elements other than these elements can also be used, as long as the above-mentioned element M is present in the hexagonal voids formed by WO 6 units, and are not limited to the above-mentioned elements.
  • the composite tungsten oxide having a hexagonal crystal structure has a uniform crystal structure.
  • the additive amount of the element M is preferably 0.2 or more and 0.5 or less in terms of the value of x/y in the general formula described above, and is more preferably 0.33. When the value of x/y is 0.33, the element M is considered to be placed in all of the hexagonal voids.
  • infrared absorbing particles including composite tungsten oxides with hexagonal crystal structure also exert sufficiently effective infrared absorption properties.
  • the absorption position in the infrared region tends to change. In the order of cubic ⁇ tetragonal ⁇ hexagonal, the absorption position tends to move to the long wavelength side.
  • less absorption of light in the visible light region is the order of hexagonal, tetragonal and cubic. Therefore, for applications that transmit more light in the visible light region and shield more light in the infrared region, hexagonal composite tungsten oxide is preferably used.
  • the tendency in optical properties described here is only a general tendency. The tendency of optical properties varies depending on the type of element added, the amount added, and the oxygen amount. The present invention is not limited to these.
  • the infrared absorbing particles containing tungsten oxides or composite tungsten oxides greatly absorb light in the near infrared region, especially around the wavelength of 1,000 nm. Therefore, many of the transmissive color tones are of a blue to green color tone.
  • the dispersed particle size of the infrared absorbing particles can be selected according to their intended use.
  • the infrared absorbing particles with 800 nm or less in the dispersed particle size are preferably used when the particles are used while maintaining the transparency. This is because particles having a dispersed particle size of 800 nm or less do not completely block light due to scattering, and can retain visibility in the visible light region, while maintaining transparency efficiently at the same time. When transparency in the visible light region is particularly important, it is preferable to further consider the reduction of scattering by particles.
  • the dispersed particle size is preferably 200 nm or less, and more preferably 100 nm or less. This is because, when the dispersed particle size is small, scattering of light in the visible light region having a wavelength of 400 nm or more and 780 nm or less due to geometric scattering or Mie scattering is reduced. As a result, for example, an infrared absorbing film having dispersed infrared absorbing particles becomes like frosted glass, and clear transparency cannot be obtained. In other words, when the dispersed particle size is 200 nm or less, the geometric scattering or Mie scattering is reduced and the Rayleigh scattering region is reached. In the Rayleigh scattering region, the scattered light is reduced in proportion to the sixth power of the particle size, so the scattering is reduced as the dispersed particle size is reduced, and transparency is improved.
  • the dispersed particle size is 100 nm or less, the scattered light becomes very small, which is desirable. From the viewpoint of avoiding light scattering, the smaller the dispersed particle size, the more desirable it is.
  • the lower limit of the dispersed particle size of the infrared absorbing particles is not limited, but the dispersed particle size is preferably 1 nm or more, for example, because such particle size is easily manufactured industrially.
  • the haze value of the dispersed infrared absorbing particles in the medium can be set to 30% or less with a visible light transmittance of 85% or less.
  • the haze is set to 30% or less, it is possible to prevent the infrared absorbing particle dispersion from becoming like cloudy glass to obtain particularly clear transparency.
  • the dispersed particle size of the infrared absorbing particles can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. or other instruments based on the principle of dynamic light scattering.
  • the crystallite size of the infrared absorbing particles is preferably 1 nm or more and 200 nm or less, more preferably 1 nm or more and 100 nm or less, and even more preferably 10 nm or more and 70 nm or less.
  • the crystallite size can be measured by measuring the X-ray diffraction pattern using a powder X-ray diffraction method ( ⁇ -2 ⁇ method) and analysis using Rietveld method.
  • the X-ray diffraction pattern can be measured using, for example, a powder X-ray diffractometer "X'Pert-PRO/MPD" manufactured by PANalytical, Spectris Co., Ltd.
  • the dispersant is used to treat the surface of the infrared absorbing particles to make the surface of the infrared absorbing particles hydrophobic.
  • the dispersant can be selected according to the dispersion system, which is a combination of the infrared absorbing particles, the dispersion medium, the raw material for the coating resin, and the like. Among them, dispersants having one or more functional groups selected from amino group, hydroxyl group, carboxyl group, sulfo group, phosphate group, and epoxy group can be suitably used.
  • the infrared absorbing particles are tungsten oxides or composite tungsten oxides
  • the dispersant more preferably has amino group as the functional group.
  • the dispersant more preferably has amino group as the functional group as described above, that is, the dispersant is preferably an amine compound.
  • the amine compound is more preferably a tertiary amine.
  • the dispersant is preferably a polymeric material because the dispersant is used for the purpose of hydrophobizing the surface of the infrared absorbing particles. For this reason, a dispersant having one or more types selected from long-chain alkyl groups and benzene rings is preferably used, for example.
  • a dispersant having one or more types selected from long-chain alkyl groups and benzene rings is preferably used, for example.
  • a polymer dispersant or the like having a copolymer of styrene and a tertiary amine 2-(dimethylamino) ethyl methacrylate in the side chain, can be more preferably used.
  • This polymer dispersant can also be used as a raw material for a coating resin.
  • the long-chain alkyl group preferably has 8 or more carbon atoms.
  • the dispersant that is the polymeric material and is the amine compound may be used.
  • the additive amount of the dispersant is not particularly limited, and can be freely selected.
  • the suitable amount of the dispersant can be selected according to the type of the dispersant, the type of the infrared absorbing particles, the specific surface area of the infrared absorbing particles, and the like.
  • the amount of the dispersant added is 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the infrared absorbing particles, because it is particularly easy to prepare a dispersion liquid with a favorable dispersion state.
  • the additive amount of the dispersant is more preferably 10 parts by mass or more and 100 parts by mass or less, and even more preferably 20 parts by mass or more and 50 parts by mass or less.
  • the dispersion medium may be any dispersion media that can disperse the infrared absorbing particles and dispersants to prepare a dispersion liquid.
  • various organic compounds may be used.
  • the dispersion medium for example, one or more selected from aromatic hydrocarbons such as toluene and xylene can be suitably used.
  • the dispersion liquid may be prepared by mixing the infrared absorbing particles, the dispersant, and the dispersion medium. It is preferable to pulverize the infrared absorbing particles at the time of mixing in order to reduce the dispersed particle size of the infrared absorbing particles and to disperse them uniformly in the dispersion liquid.
  • the mixing means used for mixing and pulverizing the infrared absorbing particles, the dispersant, and the dispersion medium are not particularly limited, but one or more types selected from, for example, a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, and the like may be used.
  • media stirring mills such as a bead mill, a ball mill, a sand mill, a paint shaker, and the like that use media such as beads, balls, and Ottawa sand are more preferably used. This is because, by using the media stirring mills, it is possible to achieve a desired dispersed particle size for the infrared absorbing particles, especially in a short time, and it is preferable from the viewpoint of productivity and control of impurities.
  • the dispersion medium can be evaporated from the dispersion liquid and dried.
  • the dispersion medium is sufficiently evaporated from the dispersion liquid to recover the infrared absorbing particles.
  • the specific means of evaporating the dispersion medium are not particularly limited, but for example, a dryer such as an oven, a vacuum fluid dryer such as an evaporator or a vacuum grinder, a spray dryer such as a spray drying device, and the like may be used.
  • the degree to which the dispersion medium is evaporated is also not particularly limited, but it is preferable that the percentage of the dispersion medium can be sufficiently reduced so that powdered infrared absorbing particles can be obtained after the dispersion medium reduction step, for example.
  • the dispersion medium By evaporating the dispersion medium, it is possible to obtain the infrared absorbing particles in which the dispersant is placed around the infrared absorbing particles and the surface is hydrophobized. Therefore, it is possible to enhance the adhesion between the hydrophobized infrared absorbing particles and the coating resin in which the raw material for the coating resin is polymerized. Thus, it is possible to place the coating resin on at least a part of the surface of the infrared absorbing particles by the polymerization step described later and the like.
  • the infrared absorbing particles collected after the dispersion medium reduction step the raw material for the resin coating, the organic solvent, the emulsifier, water, and the polymerization initiator are mixed to prepare the raw material liquid mixture.
  • the infrared absorbing particles collected after the dispersion medium reduction step may be infrared absorbing particles containing the dispersant, due to the attachment of the dispersant supplied in the dispersion liquid preparation step to the surface of the particles. Therefore, when the dispersant is attached to the infrared absorbing particles, the infrared absorbing particles containing the dispersant collected after the dispersion medium reduction step are used as the infrared absorbing particles, in the raw material liquid mixture preparation step.
  • the raw material for the coating resin is polymerized in the polymerization step described later, and becomes the coating resin that is placed on at least a part of the surface of the infrared absorbing particles. Therefore, as the raw material for the coating resin, various monomers or the like that can form the desired coating resin by polymerization can be selected.
  • the coating resin after polymerization is not particularly limited, but for example, one or more types of resins selected from a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like can be used.
  • thermoplastic resin examples include polyester resin, polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, vinyl chloride resin, olefin resin, fluorine resin, polyvinyl acetate resin, thermoplastic polyurethane resin, acrylonitrile butadiene styrene resin, polyvinyl acetal resin, acrylonitrile-styrene copolymer resin, ethylene-vinyl acetate copolymer resin, and the like.
  • thermosetting resin examples include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, thermosetting polyurethane resin, polyimide resin, silicone resin, and the like.
  • Examples of the photocurable resin include a resin to be cured by irradiation of any one of ultraviolet, visible, or near-infrared light.
  • the coating resin preferably contains one or more types of resins selected from polyester resin, polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, vinyl chloride resin, olefin resin, fluorine resin, polyvinyl acetate resin, polyurethane resin, acrylonitrile butadiene styrene resin, polyvinyl acetal resin, acrylonitrile-styrene copolymer resin, ethylene-vinyl acetate copolymer resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, and silicone resin.
  • the polyurethane resin both thermoplastic polyurethane and thermosetting polyurethane may be used.
  • a photocurable resin may also be suitably used.
  • a resin to be cured by irradiation of any one of ultraviolet, visible, or infrared light may be suitably used, as described above.
  • the coating resin is a resin to which a mini-emulsion polymerization method can be applied, and it is more preferable that the coating resin contains a polystyrene resin, for example.
  • the coating resin is polystyrene, styrene can be used as the raw material for the coating resin.
  • a crosslinking agent a multi-functional vinyl monomer such as divinylbenzene, ethylene glycol dimethacrylate, or the like may also be added.
  • the organic solvent is not particularly limited, but any water-insoluble solvent may be used. Among them, an organic solvent having a low molecular weight is preferable.
  • the organic solvent include one or more types selected from long-chain alkyl compounds such as hexadecane and the like; alkyl esters of methacrylic acid having a long-chain alkyl moiety such as dodecyl methacrylate, stearyl methacrylate, and the like; higher alcohols such as cetyl alcohol and the like; oils such as olive oil and the like; and the like.
  • the organic solvent particularly, the long-chain alkyl compounds are more preferable, and hexadecane is even more preferable.
  • the emulsifier that is, a surfactant, may be cationic, anionic, nonionic, and the like, and is not particularly limited.
  • Examples of the cationic emulsifier include alkylamine salts, quaternary ammonium salts, and the like.
  • anionic emulsifier examples include acid salts, ester salts, and the like.
  • nonionic emulsifier examples include various esters, various ethers, various ester ethers, alkanolamides, and the like.
  • emulsifier for example, one or more types selected from the materials as described above may be used.
  • a cationic emulsifier that is a surfactant that exhibits cationic properties, is preferably used from the viewpoint that the infrared absorbing particles particularly easily form organic-inorganic hybrid infrared absorbing particles.
  • the emulsifier is preferably one or more cationic emulsifiers selected from dodecyltrimethylammonium chloride (DTAC), cetyltrimethylammonium chloride (CTAC), and the like.
  • the emulsifier can be added as an aqueous solution, for example, by simultaneously adding the emulsifier with water.
  • the emulsifier is preferably added as an aqueous solution adjusted to a concentration of 1 time or higher and 10 times or lower of the critical micelle concentration (CMC) .
  • the polymerization initiator is not particularly limited, but one or more types selected from various polymerization initiators such as radical polymerization initiators, ionic polymerization initiators, and the like may be used.
  • radical polymerization initiator examples include azo compounds, dihalogen, organic peroxides, and the like.
  • examples also include a redox initiator that combines an oxidizing agent and a reducing agent, such as hydrogen peroxide and an iron (II) salt, persulfate and sodium bisulfite, and the like.
  • ionic polymerization initiator examples include nucleophiles such as n-butyl lithium, an electrophilic agent such as a protonic acid, a Lewis acid, a halogen molecule, and a carbocation, and the like.
  • polymerization initiator for example, one or more types selected from 2,2'-azobisisobutyronitrile (AIBN), potassium peroxodisulfate (KPS), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50), 2,2'-azobis(2-methyl-N-(2-hydroxyethyl) propionamidine) (VA-086), and the like may be suitably used.
  • AIBN 2,2'-azobisisobutyronitrile
  • KPS potassium peroxodisulfate
  • V-50 2,2'-azobis(2-methylpropionamidine) dihydrochloride
  • VA-086 2,2'-azobis(2-methyl-N-(2-hydroxyethyl) propionamidine)
  • the polymerization initiator can be added to the organic phase or the aqueous phase, depending on the type. For example, when 2,2'-azobisisobutyronitrile (AIBN) is used, AIBN can be added to the organic phase. When potassium peroxodisulfate (KPS) or 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50) is used, KPS or V-50 can be added to the aqueous phase.
  • KPS potassium peroxodisulfate
  • V-50 2,2'-azobis(2-methylpropionamidine) dihydrochloride
  • the raw material liquid mixture preparation step it is sufficient to prepare the raw material liquid mixture by mixing the infrared absorbing particles collected after the dispersion medium reduction step, the raw material for the coating resin, the organic solvent, the emulsifier, water, and the polymerization initiator. Accordingly, the preparation procedure and the like of the raw material liquid mixture is not particularly limited, but for example, as the aqueous phase, a liquid mixture containing the emulsifier can be prepared in advance.
  • a liquid mixture can be prepared in which the raw material for the coating resin and the infrared absorbing particles collected after the dispersion medium reduction step are dispersed in the organic solvent.
  • the polymerization initiator may be added to the aqueous phase or to the organic phase, according to the type of the polymerization initiator used as described above.
  • the raw material liquid mixture may be prepared by adding and mixing the organic phase to the aqueous phase.
  • the raw material liquid mixture preparation step further includes a stirring step of stirring the obtained liquid mixture in addition to the mixing step of mixing the infrared absorbing particles collected after the dispersion medium reduction step, the raw material for the coating resin, the organic solvent, the emulsifier, water, and the polymerization initiator.
  • stirring may be performed using a stirrer, for example.
  • the degree of stirring is not particularly limited, but for example, it is preferable to carry out the stirring so that an oil-in-water in which the infrared absorbing particles encapsulated in the raw material for the coating resin are dispersed in the aqueous phase, are formed.
  • the additive amount of the polymerization initiator is not particularly limited and may be freely selected.
  • the additive amount of the polymerization initiator may be selected according to the type of the raw material for the coating resin, the type of the polymerization initiator, the size of the oil droplets that are mini-emulsions, the ratio of the raw material for the coating resin to the infrared absorbing particles, and the like.
  • the additive amount of the polymerization initiator is 0.01 mol% or more and 1,000 mol% or less with respect to the raw material for the coating resin, it is preferable because it is easy to obtain the organic-inorganic hybrid infrared absorbing particles in which the infrared absorbing particles are sufficiently covered with the coating resin.
  • the additive amount of the polymerization initiator is more preferably 0.1 mol% or more and 200 mol% or less with respect to the raw material for the coating resin, and even more preferably 0.2 mol% or more and 100 mol% or less.
  • the raw material liquid mixture obtained in the raw material liquid mixture preparation step may be stirred while being cooled.
  • the degree of the stirring in the stirring step is not particularly limited and may be freely selected.
  • the mini-emulsion is obtained by adding a substance that is almost insoluble in water, that is, a hydrophobe, to the organic phase and applying a strong shear force thereto.
  • a substance that is almost insoluble in water that is, a hydrophobe
  • the hydrophobe include the organic solvent described above in the raw material liquid mixture preparation step.
  • a method of applying the strong shear force for example, ultrasonic vibration is applied to the raw material liquid mixture by a homogenizer or the like.
  • the stirring is preferably performed while cooling the raw material liquid mixture as described above. This is because by cooling the raw material liquid mixture, a mini-emulsion can be formed while minimizing the progress of the polymerization reaction.
  • the degree of cooling of the raw material liquid mixture is not particularly limited, but it is preferable to cool the raw material liquid mixture by using a refrigerant of 0°C or lower, for example, by means of an ice bath or the like.
  • the polymerization reaction of the raw material for the coating resin may be carried out after deoxygenation to reduce the oxygen amount in the raw material liquid mixture.
  • the raw material for the coating resin may be polymerized, and the coating resin may be placed on at least a part of the surface of the infrared absorbing particles.
  • the conditions in the polymerization step are not particularly limited.
  • the deoxygenation to reduce the oxygen amount in the raw material liquid mixture may be carried out before starting the polymerization.
  • Specific methods of the deoxygenation are not particularly limited, but include a method for performing ultrasonic irradiation and a method for blowing an inert gas into the raw material liquid mixture.
  • the specific conditions for carrying out the polymerization reaction may be freely selected according to the raw material for the coating resin or the like added to the raw material liquid mixture.
  • the polymerization reaction may be carried out by, for example, heating the raw material liquid mixture or irradiating the raw material liquid mixture with light of a predetermined wavelength.
  • the organic-inorganic hybrid infrared absorbing particles can be obtained by placing an organic material such as a resin on at least a part of the surface of the infrared absorbing particles, which has been difficult in the conventional technique. Accordingly, even when exposed to an environment of chemicals such as acids or alkalis at high temperatures, the infrared absorbing particles can be prevented from coming into direct contact with the chemical components such as acids or alkalis. Therefore, the infrared absorbing particles have excellent chemical resistance properties and it is possible to minimize the deterioration of the infrared absorption properties.
  • the organic-inorganic hybrid infrared absorbing particles according to the present embodiment, which can be suitably used in the infrared absorbing fiber, will be described.
  • the organic-inorganic hybrid infrared absorbing particles may include infrared absorbing particles and a coating resin that covers at least a part of a surface of the infrared absorbing particles.
  • the organic-inorganic hybrid infrared absorbing particles may be produced, for example, by the method for producing the organic-inorganic hybrid infrared absorbing particles described above. For this reason, explanations of some of the matters already explained will be omitted.
  • the coating resin is placed on the surface of the infrared absorbing particle and the coating resin covers at least a part of the surface of the infrared absorbing particles, which has been difficult in the conventional technique. Accordingly, even when exposed to an environment of chemicals such as acids or alkalis at high temperatures, the infrared absorbing particle can be prevented from coming into direct contact with the chemical components such as acids or alkalis. Therefore, the infrared absorbing fiber according to the present embodiment, which includes the organic-inorganic hybrid infrared absorbing particles, has excellent chemical resistance properties and it is possible to minimize the deterioration of the infrared absorption properties.
  • infrared absorbing particles are already explained in the method for producing the organic-inorganic hybrid infrared absorbing particles, the explanations will be omitted.
  • infrared absorbing particles including various materials containing free electrons may be preferably used, and infrared absorbing particles including various inorganic materials containing free electrons may be more preferably used.
  • the infrared absorbing particles it is particularly preferable to use infrared absorbing particles including one or more oxides selected from tungsten oxide having oxygen deficiency and composite tungsten oxide.
  • the infrared absorbing particles include, for example, one or more oxides selected from tungsten oxide represented by a general formula W y O z (W: tungsten, O: oxygen, 2.2 ⁇ z/y ⁇ 2.999) and a composite tungsten oxide represented by a general formula M x W y O z (an element M is one or more elements selected from among H, He, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb
  • the coating resin is also already explained in the method for producing the organic-inorganic hybrid infrared absorbing particles, the explanations will be omitted.
  • resins selected from a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like can be used.
  • the coating resin preferably contains one or more types of resins selected from polyester resin, polycarbonate resin, acrylic resin, polystyrene resin, polyamide resin, vinyl chloride resin, olefin resin, fluorine resin, polyvinyl acetate resin, polyurethane resin, acrylonitrile butadiene styrene resin, polyvinyl acetal resin, acrylonitrile-styrene copolymer resin, ethylene-vinyl acetate copolymer resin, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyimide resin, and silicone resin.
  • the polyurethane resin both thermoplastic polyurethane and thermosetting polyurethane may be used.
  • a photocurable resin may also be suitably used.
  • a resin to be cured by irradiation of any one of ultraviolet, visible, or infrared light may be suitably used, as described above.
  • the coating resin is a resin to which a mini-emulsion polymerization method can be applied, and it is more preferable that the coating resin contains a polystyrene resin, for example.
  • the coating resin which is an organic material
  • the coating resin is placed on at least a part of the surface of the infrared absorbing particles, which has been difficult in the conventional technique. Accordingly, even when exposed to an environment of chemicals such as acids or alkalis at high temperatures, the infrared absorbing particles can be prevented from coming into direct contact with the chemical components such as acids or alkalis. Therefore, the organic-inorganic hybrid infrared absorbing particles has excellent chemical resistance properties and it is possible to minimize the deterioration of the infrared absorption properties.
  • the infrared absorbing fiber using the organic-inorganic hybrid infrared absorbing particles can also has chemical resistance properties.
  • the infrared absorbing fiber according to the present embodiment may include fibers in addition to the organic-inorganic hybrid infrared absorbing particles described so far.
  • the infrared absorbing fiber according to the present embodiment can be produced by dispersing the organic-inorganic hybrid infrared absorbing particles described above in a suitable medium and by including the dispersion in one or more parts selected from the interior of the fiber and the surface of the fiber.
  • the fiber and the like will be explained below.
  • the fiber included in the infrared absorbing fiber according to the present embodiment may be selected from various types of fiber according to the application.
  • the fiber included in the infrared absorbing fiber may include one or more fibers selected from a synthetic fiber, a semisynthetic fiber, a natural fiber, a reclaimed fiber, and an inorganic fiber, for example.
  • any one or more of the following fibers may be used as the fiber: one or more fibers selected from a synthetic fiber, a semisynthetic fiber, a natural fiber, a reclaimed fiber, and an inorganic fiber; or one or more fibers selected from mixed yarns such as a blended yarn, a doubled yarn, or a combined filament yarn using one or more fibers selected from the above fiber groups; and the like.
  • the fibers include synthetic fibers, and more preferably the fibers are synthetic fibers.
  • the specific type of the synthetic fiber is not particularly limited.
  • one or more fibers selected from a polyurethane fiber, a polyamide fiber, an acrylic fiber, a polyester fiber, a polyolefin fiber, a polyvinyl alcohol fiber, a polyvinylidene chloride fiber, a polyvinyl chloride fiber, a polyether ester fiber, and the like, may be suitably used.
  • polyamide fiber examples include one or more fibers selected from nylon, nylon 6, nylon 66, nylon 11, nylon 610, nylon 612, aromatic nylon, aramid, and the like.
  • acrylic fiber examples include one or more fibers selected from polyacrylonitrile, acrylonitrile-vinyl chloride copolymer, modacrylic fiber, and the like.
  • polyester fiber examples include one or more fibers selected from polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and the like.
  • polyolefin fiber examples include one or more fibers selected from polyethylene, polypropylene, polystyrene, and the like.
  • polyvinyl alcohol fiber examples include vinylon and the like.
  • polyvinylidene chloride fiber examples include vinylidene and the like.
  • polyvinyl chloride fiber examples include polyvinyl chloride and the like.
  • polyether ester fiber examples include one or more fibers selected from Rexe, Success and the like.
  • the infrared absorbing fiber includes the semisynthetic fiber as the fiber
  • the semisynthetic fiber preferably includes one or more fibers selected from, for example, a cellulose fiber, a protein fiber, chlorinated rubber, hydrochlorinated rubber, and the like.
  • Examples of the cellulose fiber include one or more fibers selected from acetate, triacetate, acetate oxide, and the like.
  • Examples of the protein fiber include Promix and the like.
  • the natural fiber preferably includes one or more fibers selected from, for example, a vegetable fiber, an animal fiber, a mineral fiber, and the like.
  • Examples of the vegetable fiber include one or more fibers selected from cotton, Ciba, flax, hemp, jute, manila hemp, sisal hemp, New Zealand flax, luobuma, palm fibers, rush, straw, and the like.
  • animal fiber examples include one or more fibers selected from wool, goat hair, mohair, cashmere, alpaca, angora, camel, vicuna, and other wools; and silk, down, feathers, and the like.
  • Examples of the mineral fiber include one or more fibers selected from asbestos and the like.
  • the reclaimed fiber preferably includes one or more fibers selected from, for example, a cellulose fiber, a protein fiber, an algin fiber, a rubber fiber, a chitin fiber, a mannan fiber, and the like.
  • cellulose fiber examples include one or more fibers selected from rayon, viscous rayon, cupra, polynosic fiber, cuprammonium rayon, and the like.
  • the protein fiber examples include one or more fibers selected from a casein fiber, a peanut protein fiber, a maize protein fiber, a soy protein fiber, a reclaimed silk, and the like.
  • the inorganic fiber preferably includes one or more fibers selected from, for example, a metal fiber, a carbon fiber, a silicate fiber, and the like.
  • the metal fiber examples include one or more fibers selected from a metal fiber, a gold thread, a silver thread, a heat resistant alloy fiber, and the like.
  • silicate fiber examples include one or more fibers selected from a glass fiber, a slag fiber, a rock fiber, and the like.
  • the cross sectional shape of the fiber of the infrared absorbing fiber according to the present embodiment is not particularly limited.
  • the cross sectional shape include one or more shapes selected from a circular shape, a triangular shape, a hollow shape, a flat shape, a Y-shape, a star shape, a core-sheath shape, and the like.
  • the infrared absorbing fiber according to the present embodiment may include fibers with different cross sectional shapes at the same time.
  • the organic-inorganic hybrid infrared absorbing particles may be located in one or more parts selected from the interior of the fiber and the surface of the fiber in various ways depending on the cross sectional shape of the fiber and the like.
  • the organic-inorganic hybrid infrared absorbing particles may be included in the core portion or in the sheath portion of the fiber.
  • the shape of the fiber included in the infrared absorbing fiber according to the present embodiment may be a filament (long fiber) or a staple (short fiber).
  • the infrared absorbing fiber according to the present embodiment may include an antioxidant, a flame retardant, a deodorant, an insect repellent, an antibacterial agent, an ultraviolet absorber, and the like, depending on the purpose, within a range that does not impair the performance of the fiber included.
  • the infrared absorbing fiber according to the present embodiment may further contain particles having a far-infrared radiation ability.
  • the particles having the far-infrared radiation ability may be located in one or more parts selected from, for example, the interior of the fiber and the surface of the fiber.
  • one or more compounds selected from, for example, metal oxides such as ZrO 2 , SiO 2 , TiO 2 , Al 2 O 3 , MnO 2 , MgO, Fe 2 O 3 , CuO, and the like; carbides such as ZrC, SiC, TiC, and the like; nitrides such as ZrN, Si 3 N 4 , AlN, and the like; and the like may be suitably used.
  • the organic-inorganic hybrid infrared absorbing particles included in the infrared absorbing fiber according to the present embodiment are an infrared absorbing material and are a near infrared absorbing material.
  • the organic-inorganic hybrid infrared absorbing particles according to the present embodiment have a property of absorbing solar light energy having a wavelength of 0.3 um or more and 3 pm or less.
  • the organic-inorganic hybrid infrared absorbing particles according to the present embodiment selectively absorbs the near infrared region having a wavelength of 0.9 um or more and 2.2 um or less, and converts it into heat, or re-radiates it.
  • the particles having the far-infrared radiation ability described above has an ability of receiving the energy absorbed by the organic-inorganic hybrid infrared absorbing particles, which are a near infrared absorbing material, and converting the energy into heat energy of mid/far infrared wavelengths and radiating the heat energy.
  • the particles of ZrO 2 convert the energy into heat energy having a wavelength of 2 um or more and 20 um or less, and radiate the heat energy.
  • the particles having the far-infrared radiation ability and the organic-inorganic hybrid infrared absorbing particles are present in the interior and on the surface of the fiber together, so that the solar energy absorbed by the organic-inorganic hybrid infrared absorbing particles can be efficiently consumed in the interior and on the surface of the fiber, and heat is retained more effectively, for example.
  • the organic-inorganic hybrid infrared absorbing particles may be located in one or more parts selected from the interior of the fiber and the surface of the fiber. That is, the organic-inorganic hybrid infrared absorbing particles may be located in both the interior of the fiber and the surface of the fiber, or in either the interior of the fiber or the surface of the fiber.
  • the infrared absorbing fiber according to the present embodiment including the organic-inorganic hybrid infrared absorbing particles can also have excellent chemical resistance.
  • the method for producing the infrared absorbing fiber according to the present embodiment is not particularly limited.
  • the infrared absorbing fiber may be produced by placing the organic-inorganic hybrid infrared absorbing particles on one or more parts selected from the surface of the fiber and the interior of the fiber.
  • the infrared absorbing fiber according to the present embodiment may be produced by the following production method (a) to (d).
  • polyester fiber is used as the fiber.
  • An organic-inorganic hybrid infrared absorbing particles dispersion liquid is added to a pellet of polyethylene terephthalate resin, which is a thermoplastic resin, and mixed uniformly with a blender, and then the solvent is removed.
  • the mixture in which the solvent is removed is melt-kneaded with a twin-screw extruder to obtain a master batch containing the organic-inorganic hybrid infrared absorbing particles.
  • the master batch containing the organic-inorganic hybrid infrared absorbing particles is melt-mixed near the melting temperature of the resin and spun according to various known methods, for example.
  • a dispersant may be added to improve the dispersibility of the organic-inorganic hybrid infrared absorbing particles to the polyethylene terephthalate resin.
  • the dispersant is not limited as long as it can disperse the organic-inorganic hybrid infrared absorbing particles into the polyethylene terephthalate resin or into a fiber obtained by spinning the master batch containing the resin.
  • the dispersant applied to the polyethylene terephthalate resin is not particularly limited, but is preferably, for example, a polymer dispersant, and is more preferably a dispersant having a main chain selected from polyester, polyether, polyacrylic, polyurethane, polyamine, polystyrene, and aliphatic, or having a main chain copolymerized with two or more types of unit structures selected from polyester, polyether, polyacrylic, polyurethane, polyamine, polystyrene, and aliphatic.
  • the dispersant preferably includes one or more types of functional groups selected from amine containing groups, hydroxyl groups, carboxyl groups, carboxyl group containing groups, sulfo groups, phosphate groups, or epoxy groups.
  • a polyacrylic dispersant having amine containing groups as the functional groups is preferable.
  • the dispersant including any of the above functional groups can adsorb on the surface of the organic-inorganic hybrid infrared absorbing particles and more reliably prevent the agglomeration of the organic-inorganic hybrid infrared absorbing particles. Therefore, the organic-inorganic hybrid infrared absorbing particles can be dispersed more uniformly, and the dispersant including any of the above functional groups can be suitably used.
  • dispersant examples include Solsperse (registered trademark) (hereinafter the same) 9000, 12000, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 32000, 35100, 54000, Solthix 250, manufactured by Lubrizol Japan Ltd.; EFKA (registered trademark) (hereinafter the same) 4008, EFKA 4009, EFKA 4010, EFKA 4015, EFKA 4046, EFKA 4047, EFKA 4060, EFKA 4080, EFKA 7462, EFKA 4020, EFKA 4050, EFKA 4055, EFKA 4585, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4300, EFKA 4320, EFKA 4330, EFKA 4340, EFKA 6220, EFKA 6225, EFKA 6700, EFKA 6780, EFKA 6782, EFKA 8503, manufactured by Solsper
  • a polymer diol containing organic-inorganic hybrid infrared absorbing particles is reacted with an organic diisocyanate in a twin-screw extruder to synthesize an isocyanate group-terminated prepolymer, and a chain extender is reacted to produce a polyurethane solution (a starting material polymer).
  • the polyurethane solution is spun according to various known methods.
  • a treatment liquid is prepared by mixing the organic-inorganic hybrid infrared absorbing particles, one or more types of binder resins selected from acrylic, epoxy, urethane, and polyester, and a solvent such as water.
  • the natural fiber is immersed in the prepared treatment liquid, or the prepared treatment liquid is impregnated into the natural fiber by padding, printing, or spraying, and dried.
  • the organic-inorganic hybrid infrared absorbing particles can be attached to the natural fiber.
  • the method described in (d) can be applied to any one of: in addition to the natural fiber described above, a semisynthetic fiber, a reclaimed fiber, and an inorganic fiber; a blended yarn, a doubled yarn, and a combined filament yarn of these fibers; and the like.
  • the dispersion method for dispersing the organic-inorganic hybrid infrared absorbing particles in the solvent (dispersion medium) is not particularly limited, and any method can be used as long as the organic-inorganic hybrid infrared absorbing particles can be uniformly dispersed in a liquid, that is, a solvent.
  • a method such as a medium stirring mill, a ball mill, a sand mill, an ultrasonic dispersion, or the like can be suitably applied.
  • the solvent of the organic-inorganic hybrid infrared absorbing particles is not particularly limited but can be selected according to the fiber to be mixed.
  • one or more types selected from common organic solvents such as alcohols, ethers, esters, ketones, aromatic compounds, and the like, and water, can be used.
  • the dispersion liquid of the organic-inorganic hybrid infrared absorbing particles may be directly mixed with the fiber or the polymer used as the raw material thereof.
  • acid or alkali may be added to the dispersion liquid of the organic-inorganic hybrid infrared absorbing particles to adjust the pH, or various surfactants, coupling agents, and the like may be added to further improve the dispersion stability of the organic-inorganic hybrid infrared absorbing particles.
  • the content of the organic-inorganic hybrid infrared absorbing particles contained in the infrared absorbing fiber according to the present embodiment is not particularly limited.
  • the percentage of the organic-inorganic hybrid infrared absorbing particles in the infrared absorbing fiber according to the present embodiment is preferably 0.001 mass% or more and 80 mass% or less.
  • the percentage of the organic-inorganic hybrid infrared absorbing particles in the infrared absorbing fiber is more preferably 0.005 mass% or more and 50 mass% or less.
  • the percentage of the organic-inorganic hybrid infrared absorbing particles in the infrared absorbing fiber is 0.001 mass% or more, a sufficient infrared absorption effect can be obtained even when the fabric using the infrared absorbing fiber is thin, for example.
  • the percentage of the organic-inorganic hybrid infrared absorbing particles of the infrared absorbing fiber is 80 mass% or less, because it is possible to prevent a reduction of spinning ability due to filter clogging, thread breakage, and other problems in the spinning process. Particularly, it is even more preferable that the percentage is 50 mass% or less. It is preferable because the additive amount of the organic-inorganic hybrid infrared absorbing particles is reduced, and the physical properties of the fiber are hardly compromised.
  • the infrared absorbing fiber according to the present embodiment by placing the infrared absorbing particles on the interior or the surface of the fiber, it is possible to provide a fiber which efficiently absorbs infrared rays from sunlight and the like and has excellent heat retention.
  • the infrared absorbing fiber according to the present embodiment has high chemical resistance properties, the infrared absorption properties do not deteriorate even when exposed to an environment of chemicals such as acids or alkalis at high temperatures.
  • the infrared absorbing fiber according to the present embodiment can be used for various applications such as fiber products such as cold weather clothing, sports clothing, stockings, curtains, and the like, and other industrial fiber products, and the like, that require heat retention.
  • the fiber product according to the present embodiment may be made by processing the infrared absorbing fiber described above, and may include the infrared absorbing fiber described above.
  • the fiber product according to the present embodiment may also be made of the infrared absorbing fiber described above.
  • the fiber product according to the present embodiment including the infrared absorbing fiber has excellent characteristics having a visible light absorption of 20% or less and a solar radiation absorption of 47% or more.
  • the visible light absorption is 20% or less and the solar radiation absorption is 47% or more, it indicates that the fiber product is light-colored and has an excellent infrared absorption effect.
  • the fiber product according to the present embodiment including the infrared absorbing fiber according to the present embodiment has excellent chemical resistance properties. For example, even when the fiber product is immersed in a 0.01 mol/l sodium hydroxide aqueous solution held at 80°C for 30 minutes, the solar radiation absorption described above is maintained at 47% or more. That is, the fiber product according to the present embodiment can have chemical resistance properties.
  • the optical properties of the fiber products obtained in the Examples and Comparative Examples were measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.).
  • the visible light transmittance, visible light reflectance, solar radiation transmittance, and solar radiation reflectance were measured according to JIS R 3106.
  • infrared absorbing particles dry powder of infrared absorbing particles obtained by removing the solvent from the dispersion liquid of infrared absorbing particles was used.
  • the X-ray diffraction pattern of the infrared absorbing particles was measured by powder X-ray diffraction method ( ⁇ -2 ⁇ method) using a powder X-ray diffractometer (X'Pert-PRO/MPD manufactured by PANalytical, Spectris Co., Ltd.).
  • the crystal structure included in the infrared absorbing particles was identified from the obtained X-ray diffraction pattern, and the crystallite size was calculated using Rietveld method.
  • Infrared absorbing fibers and fiber products were prepared and evaluated by the following procedure.
  • Organic-inorganic hybrid infrared absorbing particles for use in an infrared absorbing fiber were produced according to the following step.
  • a dispersion liquid containing infrared absorbing particles, a dispersant, and a dispersion medium was prepared.
  • a polymer dispersant which is a copolymer of styrene and 2-(dimethylamino) ethyl methacrylate, was prepared.
  • toluene As the dispersion medium, toluene was prepared.
  • a liquid mixture obtained by mixing 10 mass% of the infrared absorbing particles, 3 mass% of the dispersant, and 87 mass% of the dispersion medium was loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and subjected to pulverizing and dispersing treatment for 10 hours, and a dispersion liquid of Cs 0.33 WO z particles according to Example 1 was obtained.
  • Toluene of the dispersion medium was removed from the dispersion liquid of Cs 0.33 WO z particles obtained in the dispersion liquid preparation step using an evaporator, and the infrared absorbing particles were collected.
  • the collected infrared absorbing particles were to be a dry powder of Cs 0.33 WO z particles including a polymer dispersant.
  • the crystallite size of the collected infrared absorbing particles that is, Cs 0.33 WO z particles, was measured to be 16 nm.
  • the crystallite size was measured and calculated by the method described above.
  • dodecyltrimethylammonium chloride as an emulsifier, 0.013 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50) as a polymerization initiator, and water were mixed to form 10 g of an aqueous phase.
  • dodecyltrimethylammonium chloride as the emulsifier was added to the water so that the concentration was 1.5 times the critical micelle concentration.
  • the polymerization initiator was added at 0.5 mol% of styrene added to the organic phase.
  • a raw material liquid mixture was prepared by adding the organic phase to the aqueous phase.
  • the raw material liquid mixture prepared in the raw material liquid mixture preparation step was irradiated with high-power ultrasonic waves for 15 minutes while cooling under an ice bath, and a mini-emulsion was obtained.
  • the raw material liquid mixture was subjected to nitrogen bubbling under an ice bath for 15 minutes and deoxygenated.
  • the obtained dispersion liquid containing the organic-inorganic hybrid infrared absorbing particles was diluted and transferred to a microgrid for TEM observation, and TEM observation of the transferred material was carried out.
  • the TEM image is presented in FIG. 2 . From the TEM image, it was confirmed that particles 21 including the composite tungsten oxide, which are infrared absorbing particles and are presented in black, are encapsulated in a coating film 22 of polystyrene, which is a coating resin and is presented in gray, to form organic-inorganic hybrid infrared absorbing particles 23. When the organic-inorganic hybrid infrared absorbing particles were visually checked, it was observed that they were light-colored.
  • a microgrid 24 is also presented in FIG. 2 , but it is not included in the organic-inorganic hybrid infrared absorbing particles.
  • the obtained dispersion liquid of the organic-inorganic hybrid infrared absorbing particles was mixed with a water-soluble acrylic binder resin, and a treatment liquid was prepared.
  • the prepared treatment liquid was then impregnated with polyester-based fibers and dried, and an infrared absorbing fiber according to Example 1 to which the organic-inorganic hybrid infrared absorbing particles were attached, was prepared.
  • the obtained infrared absorbing fiber was cut to produce polyester staples, which were used to produce a spun yarn.
  • a knit product according to Example 1 was obtained using the spun yarn.
  • the solar radiation absorption of the knit product samples was adjusted to be around 50%. It was also adjusted in the following Comparative Example.
  • the optical properties of the fiber product according to Example 1 were measured by the method described above.
  • the calculated visible light absorption and solar radiation absorption were 18% and 51%, respectively.
  • the fiber product according to Example 1 was immersed in 0.01 mol/l sodium hydroxide aqueous solution held at 80°C for 30 minutes, and the alkali resistance test was performed. After that, the optical properties were measured again.
  • the visible light absorption and solar radiation absorption after the alkali resistance test were 17% and 49%, respectively.
  • the difference in the visible light absorption and the difference in the solar radiation absorption were 1% and 2%, respectively, when compared before and after the alkali resistance test.
  • the evaluation results are presented in Table 1.
  • the infrared absorbing fiber and the fiber product obtained in the present Example have chemical resistance properties, especially alkaline resistance properties.
  • a dispersion liquid containing infrared absorbing particles and a dispersion medium was prepared.
  • a liquid mixture obtained by mixing 10 mass% of the infrared absorbing particles and 90 mass% of the dispersion medium was loaded into a paint shaker containing 0.3 mm ⁇ ZrO 2 beads and subjected to pulverizing and dispersing treatment for 10 hours, and a dispersion liquid of Cs 0.33 WO z particles according to Comparative Example 1 was obtained.
  • Pure water of the dispersion medium was removed from the dispersion liquid of Cs 0.33 WO z particles obtained in the dispersion liquid preparation step using an evaporator, and the infrared absorbing particles were collected.
  • the collected infrared absorbing particles were to be a dry powder of Cs 0.33 WO z particles.
  • the crystallite size of the collected infrared absorbing particles that is, Cs 0.33 WO z particles, was measured to be 16 nm.
  • the crystallite size was measured and calculated by the method described above.
  • the infrared absorbing fiber and the fiber product according to Comparative Example 1 were obtained by the same operation as in Example 1 except that the dispersion liquid of Cs 0.33 WO z particles according to Comparative Example 1 that was obtained in the dispersion liquid preparation step was used instead of the dispersion liquid of the organic-inorganic hybrid infrared absorbing particles according to Example 1.
  • the obtained fiber product was evaluated in the same manner as in Example 1. The evaluation results are presented in Table 1.
  • the infrared absorbing fiber using the organic-inorganic hybrid infrared absorbing particles of Example 1 and the fiber product containing the infrared absorbing fiber had excellent alkaline resistance properties, that is, excellent chemical resistance properties, and excellent infrared absorption properties. Although only an alkali resistance test was performed here, these organic-inorganic hybrid infrared absorbing particles also have acid resistance properties because the coating resin is located on at least a part of the surface of the infrared absorbing particles.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP21937002.0A 2021-04-16 2021-04-16 Infrarotabsorbierende faser und faserprodukt Pending EP4324963A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2021/015721 WO2022219808A1 (ja) 2021-04-16 2021-04-16 赤外線吸収繊維、繊維製品

Publications (1)

Publication Number Publication Date
EP4324963A1 true EP4324963A1 (de) 2024-02-21

Family

ID=83640296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21937002.0A Pending EP4324963A1 (de) 2021-04-16 2021-04-16 Infrarotabsorbierende faser und faserprodukt

Country Status (3)

Country Link
EP (1) EP4324963A1 (de)
CN (1) CN117157437A (de)
WO (1) WO2022219808A1 (de)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05239716A (ja) 1992-02-21 1993-09-17 Nippon Ester Co Ltd 保温性複合繊維
JPH083870A (ja) 1994-06-13 1996-01-09 Japan Carlit Co Ltd:The 赤外線吸収加工繊維製品及びその加工方法
JPH09291463A (ja) 1996-04-19 1997-11-11 Nisshinbo Ind Inc セルロース系繊維構造物の近赤外線吸収加工方法
JP3664585B2 (ja) 1998-03-26 2005-06-29 株式会社クラレ 熱線放射性に優れる繊維
JP3883007B2 (ja) 2003-06-19 2007-02-21 住友金属鉱山株式会社 ホウ化物微粒子含有繊維およびこれを用いた繊維製品
JP4355945B2 (ja) 2004-11-08 2009-11-04 住友金属鉱山株式会社 近赤外線吸収繊維およびこれを用いた繊維製品
CN102337603A (zh) * 2010-07-27 2012-02-01 财团法人工业技术研究院 具有吸收红外线功能的纤维、其制法及纺织品
US11787949B2 (en) * 2017-07-24 2023-10-17 Sumitomo Metal Mining Co., Ltd. Infrared absorbing fine particle dispersed powder, dispersion liquid containing infrared absorbing fine particle dispersed powder, ink containing infrared absorbing fine particle dispersed powder, and anti-counterfeit ink, and anti-counterfeit printed matter
JP7226321B2 (ja) 2017-09-14 2023-02-21 住友金属鉱山株式会社 近赤外線吸収繊維およびこれを用いた繊維製品、並びにそれらの製造方法
JP2020026595A (ja) * 2018-08-16 2020-02-20 帝人株式会社 布帛および防護製品
JP7285633B2 (ja) * 2018-11-07 2023-06-02 共同印刷株式会社 光熱変換性樹脂組成物及びそれを含む繊維
CN113195410B (zh) * 2018-12-18 2023-11-24 住友金属矿山株式会社 有机无机混合红外线吸收颗粒的制造方法和有机无机混合红外线吸收颗粒
JP7363394B2 (ja) * 2019-11-12 2023-10-18 住友金属鉱山株式会社 赤外線吸収繊維、繊維製品

Also Published As

Publication number Publication date
WO2022219808A1 (ja) 2022-10-20
CN117157437A (zh) 2023-12-01

Similar Documents

Publication Publication Date Title
EP1847635B1 (de) Infrarotnahe strahlung absorbierendefaser und darauf basierendes textilprodukt
JP7363394B2 (ja) 赤外線吸収繊維、繊維製品
TWI816696B (zh) 近紅外線吸收纖維及使用其之纖維製品
US20110091720A1 (en) Boride nanoparticle-containing fiber and textile product that uses the same
TWI769267B (zh) 近紅外線吸收纖維及其製造方法暨使用其之纖維製品
JP3883007B2 (ja) ホウ化物微粒子含有繊維およびこれを用いた繊維製品
EP3626758A1 (de) Graphenverbundmaterial und herstellungsverfahren dafür
GB2303375A (en) Far I.R.-radiating polyester fibres
KR101212986B1 (ko) 적외선 흡수용 기능성 섬유원단
EP4324963A1 (de) Infrarotabsorbierende faser und faserprodukt
EP4414485A1 (de) Infrarotabsorbierende faser und faserprodukt
TW202242219A (zh) 紅外線吸收纖維、纖維製品
WO2024080084A1 (ja) 赤外線遮蔽繊維構造物とこれを用いた衣類
JP2023151572A (ja) 近赤外線吸収繊維、繊維製品、近赤外線吸収繊維の製造方法
CN117468120B (zh) 一种稀土基降温隔热异形纤维及其制备方法
KR920007108B1 (ko) 보온성이 우수한 폴리에스테르 섬유의 제조방법

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20231011

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)