EP2808428A1 - Polyesterverbundfaser mit ausgezeichneter hitzeabschirmungseigenschaft und färbung - Google Patents

Polyesterverbundfaser mit ausgezeichneter hitzeabschirmungseigenschaft und färbung Download PDF

Info

Publication number
EP2808428A1
EP2808428A1 EP13741605.3A EP13741605A EP2808428A1 EP 2808428 A1 EP2808428 A1 EP 2808428A1 EP 13741605 A EP13741605 A EP 13741605A EP 2808428 A1 EP2808428 A1 EP 2808428A1
Authority
EP
European Patent Office
Prior art keywords
core
fiber
composite fiber
sheath
heat
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.)
Granted
Application number
EP13741605.3A
Other languages
English (en)
French (fr)
Other versions
EP2808428B1 (de
EP2808428A4 (de
Inventor
Daisuke OHGA
Hitoshi Nakatsuka
Shinya KAWAKADO
Eriko TAKAHASHI
Shoji SUEYOSHI
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.)
Kuraray Co Ltd
Original Assignee
Kuraray 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 Kuraray Co Ltd filed Critical Kuraray Co Ltd
Publication of EP2808428A1 publication Critical patent/EP2808428A1/de
Publication of EP2808428A4 publication Critical patent/EP2808428A4/de
Application granted granted Critical
Publication of EP2808428B1 publication Critical patent/EP2808428B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter

Definitions

  • the present invention relates to a polyester composite fiber (or conjugated or bicomponent or heterofil fiber) having a heat-shielding property due to high reflectance in an infrared wavelength range (800 to 3000 nm) which is easy to be changed into thermal energy, as well as having color development property comparable to that of conventional polyester fibers.
  • Patent Document 1 a method for giving a fabric a cool sensation obtainable from a heat insulating effect by contriving a fiber shape or a way of weaving
  • Patent Document 2 a method for increasing infrared ray reflectivity by covering a fabric composed of fibers having its surface plated with silver
  • Patent Document 3 a method for reflecting infrared rays of wavelengths (800 to 3000 nm) by incorporating titanium oxide into both core and sheath components
  • Patent Document 1 states that by use of a specific bulky polyester multifilament crimped yarn made of a single filament containing a sunlight shielding material in an amount of 3% by weight or more based on the whole while containing the sunlight shielding material in an amount of 0.8% by weight or less based on a sheath part thereof, a fabric can be obtained which has a large volume of air inside yarns constituting the fabric to exhibit a heat insulating effect, thereby giving an excellent cool sensation.
  • Patent Document 2 states that a fabric product having infrared ray reflectivity which comprises a fabric material made of a fiber having its surface plated with silver can be used as a temporary-type tent building, a roof material of a domed building, or a leisure tent building so as to make infrared rays of solar heat reflected resulting in adjustment of the temperature inside of those buildings.
  • Patent Document 3 states that a fiber comprising a core part containing 3% by weight or more of titanium oxide having an average particle size of 0.8 to 1.8 ⁇ m and a sheath part containing 0.5 to 10% by weight of titanium oxide having an average particle size of 0.4 ⁇ m or smaller reflects the wavelengths of infrared rays, which are easy to be changed into thermal energy, to gain a heat-shielding effect.
  • Patent Document 4 discloses a knitted fabric including 40% by weight or more of a core-sheath synthetic fiber comprising a core part containing an inorganic oxide fine particle in an amount of 3 to 20% by weight and a sheath part containing an inorganic oxide fine particle in an amount of 2% by weight or less, wherein an infrared absorbent being caused to adhere evenly onto this knitted fabric.
  • This knitted fabric can reflect both visible rays and ultraviolet rays by the core-sheath synthetic fiber, as well as can prevent infrared ray penetration due to the adhesion of the infrared absorbent.
  • Patent Document 1 in order to make the yarn bulky, Patent Document 1 requires a step of supplying a highly oriented undrawn yarn to a heat treatment machine so as to be subjected to over-feed treatment, drawing the treated yarn, and false-twisting the drawn yarn. This increases the cost.
  • the silver-plated fabric is essentially used so as to require a step of silver plating, resulting in increase of the cost. Additionally, a drawback is also generated that the fabric unfavorably shields light by the silver plating applied to the fabric.
  • Patent Document 3 has a drawback that the fiber has a deteriorated color development property when it dyed since the sheath component contains 0.5 to 10% by weight of titanium oxide.
  • this core-sheath synthetic fiber does not have sufficient infrared ray reflectivity by itself, as is evident from the fact that the infrared absorbent is applied to the knitted fiber.
  • the present invention is to solve such problems in the conventional technology.
  • An object of the invention is to provide a core-sheath type composite fiber (or core-sheath type conjugated or bicomponent fiber) being capable of reflecting infrared rays so as to achieve a heat-shielding effect as well as being capable of developing a vivid color without causing opacity caused by whitening.
  • Another object of the invention is to provide a core-sheath type composite fiber which is good in spinnability, and can attain an excellent heat-shielding property and color development property.
  • a specific core-sheath type fiber can achieve both heat-shielding effect and coloration by (i) incorporating a sunlight shielding material having a specific mean particle size into the core component, (ii) incorporating, into the sheath component, heat-shielding fine particles having a specific mean particle size smaller than the mean particle size of those in the core, and further (iii) comprising the sheath component having a larger amount than the core component, so that the core part effectively reflects sunlight to while the sheath part can improve the heat-shielding property of the fiber and maintain the color development property thereof.
  • the present invention has been accomplished.
  • the present invention is a core-sheath type composite fiber comprising a core component and a sheath component
  • the core component (component A) comprises a thermoplastic polymer including a sunlight shielding material having an average particle size of 0.5 ⁇ m or smaller (preferably, greater than 0.1 ⁇ m and 0.5 ⁇ m or smaller) in an amount of 8% by weight to 70% by weight
  • the sheath component (component B) comprises a polyester-type (or polyester-based) polymer including heat-shielding fine particles in an amount of 0.5% by weight to 10% by weight, the heat-shielding fine particles being capable of maintaining color development property and having an average particle size of 0.1 ⁇ m or smaller which is smaller than that of the sunlight shielding material.
  • the mass ratio of the core component to the sheath component is 10 : 90 to 30 : 70.
  • the core component may contain the sunlight shielding material in an amount of more than 20% by weight and 70% by weight or less (i.e., less than or equal to 70% by weight).
  • the fiber may have an official moisture regain of 0.3% or more as the entire fiber.
  • the sunlight shielding material may comprise at least one member selected from the group consisting of titanium oxide, zinc oxide, and barium sulfate.
  • the heat-shielding fine particles may comprise at least one member selected from the group consisting of silicon dioxide and barium sulfate.
  • the core-sheath type composite fiber may satisfy the following formula: R / r ⁇ 1.8 wherein "R” represents the linear distance between a centroidal point "G” and a point of the fiber circumference at the farthest from the centroidal point "G”, and “r” represents the linear distance between the centroidal point "G” and a point of the core external boundary at the farthest from the centroidal point "G".
  • the core-sheath type composite fiber may have an average reflectance of 70% or higher against an infrared ray having a wavelength of 800 to 1200 nm.
  • the fiber may have an L* value of 16.5 or less.
  • the meaning of the wording "can maintain the color development property” is equivalent to the meaning that the coloring matter is secured to exhibit its coloring to fiber so that the fiber is not substantially lowered in color development property.
  • titanium oxide functions as a delustering agent to hinder the color development property of the fiber; thus, titanium oxide does not fall under the category of the heat-shielding fine particles.
  • the sunlight shielding material and the heat-shielding fine particles may be made of the same inorganic compound with each other.
  • a core-sheath type composite fiber comprises a sheath part which comprises a polyester-type polymer including heat-shielding fine particles having a specific particle size in a specific proportion and a core part which comprises a thermoplastic polymer including a sunlight shielding material having a specific particle size in a specific proportion, and the core-sheath type composite fiber further satisfies the specific relationship that the mass proportion of the sheath is larger than that of the core.
  • the core-sheath type composite fiber has a high reflectance against infrared rays, which are easy to be changed into thermal energy, so that the fiber can achieve a heat-shielding effect, and further the fiber can have good color development property comparable to that of conventional polyesters.
  • the core-sheath type composite fiber comprises the sheath and core parts in the specific relationship that the mass proportion of the sheath is larger than that of the core, even when a large quantity of the shielding material is incorporated into the core component, the fiber can maintain color development property as well as spinnability.
  • the fiber can be further improved in the heat-shielding effect.
  • the fiber when the core-sheath type composite fiber has the specific cross-sectional shape, the fiber can be further improved in color development property.
  • the core component (component A) comprises a thermoplastic polymer including a specific amount of a sunlight shielding material having an average particle size of 0.5 ⁇ m or smaller
  • the sheath component (component B) is a polyester-type polymer including a specific amount of heat-shielding fine particles capable of maintaining color development property of the fiber, the heat-shielding fine particles having an average particle size of 0.1 ⁇ m or smaller, the mean particle size being smaller than that of the sunlight shielding material
  • the mass ratio of the core component to the sheath component is 10 : 90 to 30 : 70.
  • thermoplastic polymer constituting the core (component A) in the core-sheath type composite fiber of the present invention and including the sunlight shielding material (the polymer may be referred to merely as the component A polymer hereinafter).
  • the component A polymer, i.e., the sunlight shielding material-including thermoplastic polymer may be, for example, a polyamide, a polyester or a polypropylene. Particularly preferred are a polyamide and a polyester such as a polyethylene terephthalate, since the sunlight shielding material can be filled in these polymers in a high proportion, and these polymers are advantageous in cost and high in versatility.
  • the sunlight shielding material (preferably, an infrared shielding substance) referred to in the present invention needs to be fine particles that do not reflect or transmit the wavelengths of infrared rays (800 to 3000 nm, particularly, 800 to 1200 nm) which are easy to be changed into thermal energy, and further that can be filled into the thermoplastic polymer in a high proportion.
  • examples thereof include titanium oxide, zinc oxide and barium sulfate, as simple substance, and a mixture of these substances of two or more. Particularly preferred is titanium oxide, which is used as a delustering agent, and is high in versatility.
  • the sheath-core composite fiber efficiently reflects infrared rays, which are easy to be changed into thermal energy, so as to exhibit a heat-shielding effect. If the content of the sunlight shielding material is less than 8% by weight, the fiber cannot efficiently reflect the wavelengths of infrared rays and cannot gain a sufficient heat-shielding effect. Contrarily, if the content of the sunlight shielding material is more than 70% by weight, the composition for the fiber is extremely deteriorated in spinnability (or thread-forming property), and is further lowered in color development property when dyed.
  • the content may be preferably 10% by weight or more, and more preferably more than 20% by weight. In order to improve spinnability, the content of the sunlight shielding material may be preferably 60% by weight or less, and is more preferably 50% by weight or less.
  • the mean particle size of the sunlight shielding material is more than 0.5 ⁇ m, the fiber composition is lowered in spinnability and cannot efficiently reflect rays in the wavelengths of infrared rays, resulting in insufficient heat-shielding effect.
  • the mean particle size of the sunlight shielding material is preferably 0.4 ⁇ m or smaller, more preferably 0.3 ⁇ m or smaller.
  • the mean particle size of the sunlight shielding material is not limited to a specific one as far as the material can reflect infrared rays.
  • the mean particle size may be preferably 0.05 ⁇ m or greater, more preferably greater than 0.1 ⁇ m.
  • the fiber can effectively reflect the near infrared rays to gain a high heat-shielding effect by incorporating the sunlight shielding material, such as titanium oxide, into the core component in a higher proportion rather than dispersing the material into the whole fiber.
  • the concentration of the sunlight shielding material in the core is higher than that of the heat-shielding fine particles in the sheath, the fiber composition can maintain not only color development property but also the good spinnability.
  • polyester polymer constituting the sheath (component B) of the core-sheath type composite fiber of the present invention and including the heat-shielding fine particles (hereinafter, the polymer may be referred to merely as the component B polymer).
  • the component B polymer i.e., the polyester polymer including the heat-shielding fine particles capable of maintaining the color development property is preferably a polyester such as a polyethylene terephthalate or a polybutene terephthalate, or a copolymerized polyester having, at its main skeleton, such a polyester and modified with a third component such as an aromatic dicarboxylic acid such as isophthalic acid or isophthalic acid having a metal sulfonate group, an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, or a polyhydric alcohol such as diethylene glycol, butanediol, hexanediol, cyclohexanedimethanol, bisphenol A, a polyalkylene glycol or pentaerythritol.
  • a polyester such as a polyethylene terephthalate or a polybutene terephthalate
  • the heat-shielding fine particles contained in the component B referred to in the present invention are desirably inorganic fine particles capable of maintaining the color development property. It is particularly preferred to use, for example, silicon dioxide or barium sulfate as a simple substance, or a mixture of these substances.
  • the mean particle size of the heat-shielding fine particles is 0.1 ⁇ m or smaller, and is preferably 0.03 to 0.08 ⁇ m both inclusive.
  • the component B contains heat-shielding fine particles made of a heat-shielding material such as silicon dioxide in an amount of 0.5 to 10% by weight both inclusive (preferably less than 10% by weight), the component B can exhibit a heat-shielding effect while maintaining the original dye-ability of a polyester. If the content of the heat-shielding fine particles is less than 0.5% by weight, the fiber composition is lowered in spinnability, and cannot gain a heat-shielding effect by the heat-shielding fine particles. On the contrary, if the content of the heat-shielding fine particles is more than 10% by weight, the fiber composition is extremely deteriorated in spinnability (or thread-forming property).
  • a heat-shielding material such as silicon dioxide
  • the content is preferably 0.5 to 8% by weight both inclusive, more preferably 1 to 7% by weight both inclusive.
  • the core-sheath type composite fiber of the present invention can be produced by a production method that will be described later.
  • the core-sheath type composite fiber of the invention may have preferably an official moisture regain of 0.4% or more in the entire fiber. If the official moisture regain in the conjugate fiber is less than 0.3%, the vaporization latent heat which follows the vaporization of the contained water is small so that the fiber may fail to gain a sufficient heat-shielding effect.
  • the fiber preferably satisfies the formula of R/r ⁇ 2, and more preferably satisfies the formula of R/r ⁇ 3. If the fiber satisfies the formula of R/r ⁇ 1.8, the conjugate fiber may be unfavorably poor in color development property by the effect of the sunlight shielding material (for example, titanium oxide) contained in the core.
  • the sunlight shielding material for example, titanium oxide
  • the mass ratio of the component A to the component B i.e., "(Component A) : (Component B)" ranges of 10 : 90 to 30 : 70, preferably 10 : 90 to 25 : 75, even more preferably 10 : 90 to 20 : 80. If the proportion of the component A polymer is less than 10% by mass, the core is unfavorably lowered in the heat-shielding effect. If the proportion of the component A polymer is more than 30% by mass, the composite fiber is unfavorably poor in color development property.
  • the fineness of the fiber is not particularly limited to the specific one, and may be any fineness.
  • the fineness of monofilaments of the composite fiber may be preferably set into the range of about 0.3 to 11 dtex. The effects of the present invention can be expected regardless of whether the fiber is a long or continuous fiber (filament) or a short fiber (staple).
  • the core-sheath type composite fiber of the present invention is high in reflectance against infrared rays.
  • the average reflectance thereof may be 70% or higher, preferably 70.5% or higher, even more preferably 71% or higher against an infrared ray having a wavelength of 800 to 1200 nm.
  • the core-sheath type composite fiber of the present invention can be restrained from being whitened to be opaque in color.
  • the L* value thereof may be 16.5 or less, and may be preferably 16 or less.
  • the composite fiber obtained in the present invention may be preferably classified in the level 4 or higher with respect to all of the criteria of change in color, color fastness to washing against adherence pollution, and color fastness to washing against liquid pollution. If any one of these properties is in the level 3 or lower, the composite fiber is not preferred for being used for ordinary clothes from the viewpoint of the handle-ability.
  • the composite fiber obtained in the present invention may be preferably classified in the level 4 or higher with respect to the criterion of color fastness to light. If the fastness to light is in the level 3 or lower, the composite fiber is not preferred for being used for ordinary clothes from the viewpoint of the handle-ability.
  • the core-sheath type composite fiber of the present invention also has a sufficient breaking strength for practical use.
  • the breaking strength may be, for example, about 1.5 to 10 cN/dtex, preferably about 1.8 to 8 cN/dtex, more preferably about 2 to 6 cN/dtex, when the breaking strength is calculated from a load-elongation curve obtained by use of an Instron type tensile tester.
  • the core-sheath type composite fiber of the present invention also has a sufficient breaking elongation for practical use.
  • the breaking elongation may be, for example, about 10 to 80%, preferably about 20 to 70%, more preferably about 30 to 60%, when the breaking elongation is measured from a load-elongation curve obtained by use of an Instron type tensile tester.
  • a component A polymer and a component B polymer are independently melt-extruded in different extruders, respectively, and introduced into respective parts of a spinning head.
  • melt-spinning procedure is conducted to produce a composite or conjugate fiber.
  • an optimal spinning/drawing method is selectable.
  • the composite fiber product having a good heat-shielding effect and color development property can be obtained by any one of a one-step or direct spinning-drawing manner performing spinning and drawing in one-step process; a two-step spinning-drawing manner performing spinning and drawing separately, in which collected spun filaments are drawn as another step; or a non-drawing step in which undrawn raw spun filaments (as-spun filaments) are directly wound at a winding speed of 2000 m/min. or faster.
  • the spinning step of the production method of the present invention can employ an ordinary melt-spinning machine used to spin out the fiber through a spinneret.
  • the cross-sectional shape and the diameter of the resultant fiber can be set as desirable one depending on the shape or size of the spinneret.
  • the composite fiber obtained in the present invention is usable as various fiber assemblies (fibrous structures).
  • the fiber assembly may include a woven, knitted or nonwoven fabric consisting essentially of the fiber of the present invention; a woven, knitted or nonwoven fabric comprising a part consisting essentially of the fiber of the present invention (for example, a woven or knitted fabric comprising a fiber of the invention and another fiber other than the fiber of the present invention such as a natural fiber, chemical fiber or synthetic fiber, a woven or knitted fabric comprising a blended yarn or a combined filament yarn comprising a fiber of the invention and another fiber other than the fiber of the present invention, or a cotton-mixed nonwoven fabric).
  • the proportion of the fiber of the invention in such a woven, knitted or nonwoven fabric is preferably 10% by weight or more, more preferably 30% by weight or more.
  • the fiber of the present invention may be mainly used in a continuous fiber form (filament), alone or as a part, to produce a woven or knitted fabric or the like to be a material suitable for clothes having a good texture or feeling.
  • the fiber may be used in a short fiber form as staples for clothes, or used for a dry nonwoven fabric or wet nonwoven fabric, or for some other; and can preferably be used not only as clothing material but also as non-clothing material, such as various residential materials and industrial materials.
  • ⁇ T of a sample With respect to the ⁇ T of a sample, the following procedure was conducted. A composite fiber with the uniformly adjusted fiber diameter was knitted to form a cylindrical knitted fabric having a basis weight of 200 g/m 2 , and then the resultant fabric was scoured to give a sample. The resultant sample was irradiated with a reflective type lamp. After 15 minutes, the temperature of a point just below the sample was measured. The temperature was measured with an adhesive-type sensor TNA-8A manufactured by Tasco Japan Co., Ltd. The sample was evaluated by analyzing the temperature difference ( ⁇ T °C) denoting a temperature difference of the sample from a control sample made of a polyethylene terephthalate fiber containing 0.05% by weight of TiO 2 .
  • a composite fiber with the uniformly adjusted fiber diameter was knitted to form a cylindrical knitted fabric having a basis weight of 200 g/m 2 , and then the resultant fabric was scoured to give a sample. Thereafter, the reflectance and the transmittance thereof were measured using the following measuring instrument.
  • Spectral reflectance meter Spectrophotometer C-2000S Color Analyzer, HITACHI
  • Dispersing aid Disper TL (manufactured by Meisei Chemical Works, Ltd.): 1 g/L
  • pH adjustor ULTRA MT LEVEL: 1 g/L Bath ratio: 1/50; Temperature: 130°C for 40 minutes
  • the L* value of the resultant dyed fabric was obtained by making a measurement using a Hitachi 307-model color analyzer (automatic recoding type spectrophotometer, manufactured by Hitachi Ltd.).
  • the fastness to washing was measured by a measuring method in accordance with JIS L-0844.
  • the fastness to light was measured by a measuring method in accordance with JIS L-0842.
  • the fineness was measured by a measuring method in accordance with JIS L-1013.
  • the breaking strength (tenacity) was analyzed from a load-elongation curve obtained using an Instron type tensile tester.
  • the breaking elongation was analyzed from a load-elongation curve obtained using an Instron type tensile tester.
  • a polyamide (component A polymer) containing 70% by weight of titanium oxide having an average particle size of 0.4 ⁇ m and a polyethylene terephthalate (component B polymer) containing 1.0% by weight of silicon dioxide were fed to a spinneret as core component and sheath component, respectively under the condition that the composite ratio (mass ratio) of the component A polymer to the component B polymer was 10 : 90.
  • the spinning procedure of the fed polymers was conducted with the spinneret having 24 holes (hole diameter: 0.25 mm) at a spinning temperature of 260°C and a discharge rate of 1.42 g/minute per hole.
  • the discharged filaments were then blown with cooling wind having a temperature of 25°C and a humidity of 60% at a rate of 0.4 m/second to make the filaments have a temperature of 60°C or lower.
  • the cooled filaments were introduced into a tube heater, 1.0 m in length and 30 mm in inner diameter (internal temperature: 185°C), which had an inlet-guide diameter of 8 mm and an outlet-guide diameter of 10 mm and was set at a position apart downward from the spinneret by 1.2 m, so as to be drawn inside the tube heater.
  • An oil was supplied through an oil nozzle to the filaments drawn in the tube heater, and then the filaments were wound at a rate of 4000 m/min.
  • This composite fiber had an R/r value of 3.2 wherein "R” represents the linear distance between a centroidal point “G” and a point of the fiber circumference at the farthest from the point "G”, and “r” represents the linear distance between the point “G” and a point of the core external boundary (interface) at the farthest from the point "G” in the cross section of the fiber.
  • the L* value at this time, the reflectance, the ⁇ T (°C) and the spinnability of the obtained fiber are shown in Table 1.
  • the L* value of the composite fiber obtained by the production method of the present invention was 15.56, which exhibited color development property comparable to that of conventional polyester fibers.
  • the ⁇ T was -3.6°C, which showed a high heat-shielding effect. Furthermore, the fastness to washing and the fastness to light were each classified in the level 4 or higher.
  • Composite fiber filaments (84T/24f) were produced in the same spinning way as in Example 1 except that the respective particle species added into the components A and B and/or the respective contents thereof were changed from Example 1. Physical properties of the resultant fibers are shown in Table 1. The fibers each had a good L* value and a good ⁇ T to show a quality causing no problem.
  • the use of barium sulfate for the fine particles incorporated into the sheath made it possible that the fiber gained a high heat-shielding effect while maintaining color development property. Furthermore, the fastness to washing and the fastness to light of each of the fibers were each classified in the level 4 or higher.
  • Composite fiber filaments (84T/24f) were produced in the same spinning way as in Example 1 except that the ratio of the core to the sheath in the composite fiber was changed.
  • the resultant fibers were each excellent in heat-shielding property and color development property to show a quality causing no problem.
  • the fastness to washing and the fastness to light of each of the fibers were each classified in the level 4 or higher.
  • Composite fiber filaments (84T/24f) were produced in the same spinning way as in Example 1 except that the component A and B polymers, the respective particle species added into the components A and B, and the respective contents thereof were changed. Physical properties of the resultant fibers are shown in Table 1.
  • Comparative Example 1 since the proportion of titanium oxide contained in the core was 0%, the fiber failed to gain a heat-shielding effect.
  • Comparative Example 2 the content of titanium oxide was an excessively large amount of 80% by weight; thus, the fiber composition was extremely deteriorated in spinnability, so as to be impossible to produce fibers.
  • Comparative Example 3 since the proportion of silicon dioxide contained in the sheath was 0%, the fiber had an insufficient heat-shielding effect. This fiber failed to be yielded in direct spinning and drawing step (conducting spinning and drawing in one- step process), which was different from the situation of Examples 1 to 13.
  • Comparative Example 4 the content of silicon dioxide was an excessively large amount of 15% by weight; thus, the fiber composition was extremely deteriorated in spinnability, so as to be impossible to produce fibers.
  • the composite fiber obtained according to the present invention has a high reflectance in an infrared wavelength range (for example, 800 to 3000 nm, in particular, 800 to 1200 nm) which is easy to be changed into thermal energy, and further has color development property comparable to that of conventional polyesters.
  • the fiber is suitable for various clothing materials.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Multicomponent Fibers (AREA)
EP13741605.3A 2012-01-27 2013-01-17 Polyesterverbundfaser mit ausgezeichneter hitzeabschirmungseigenschaft und färbung Not-in-force EP2808428B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012014682 2012-01-27
PCT/JP2013/050752 WO2013111661A1 (ja) 2012-01-27 2013-01-17 遮熱性及び発色性に優れたポリエステル系複合繊維

Publications (3)

Publication Number Publication Date
EP2808428A1 true EP2808428A1 (de) 2014-12-03
EP2808428A4 EP2808428A4 (de) 2015-09-23
EP2808428B1 EP2808428B1 (de) 2018-06-13

Family

ID=48873382

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13741605.3A Not-in-force EP2808428B1 (de) 2012-01-27 2013-01-17 Polyesterverbundfaser mit ausgezeichneter hitzeabschirmungseigenschaft und färbung

Country Status (6)

Country Link
US (1) US20140335354A1 (de)
EP (1) EP2808428B1 (de)
JP (1) JP6005070B2 (de)
CN (1) CN104066875B (de)
TW (1) TWI580831B (de)
WO (1) WO2013111661A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6212822B2 (ja) * 2013-11-22 2017-10-18 平岡織染株式会社 採光性に優れた遮熱膜材
JP6355388B2 (ja) * 2014-03-31 2018-07-11 Ｋｂセーレン株式会社 複合繊維
CN106319685A (zh) * 2015-06-19 2017-01-11 香港理工大学 一种反射近红外线的隔热核壳复合纤维及制备方法
CN109512038A (zh) * 2017-09-20 2019-03-26 绿能奈米科技有限公司 远红外线纤维于制备增进男性性功能的内裤的用途
TW201930668A (zh) * 2017-11-10 2019-08-01 大陸商東麗纖維研究所（中國）有限公司 一種高防透芯鞘複合纖維及織物
CN111455483A (zh) * 2020-04-05 2020-07-28 华中科技大学 一种辐射制冷纤维及其织物的制备方法
TWI754922B (zh) 2020-04-28 2022-02-11 財團法人紡織產業綜合研究所 紅外線反射纖維及其製備方法
WO2025097102A1 (en) * 2023-11-04 2025-05-08 Don Chernoff Reflective fiber and reflective garment incorporating same

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222632A (ja) * 1992-02-13 1993-08-31 Unitika Ltd 清涼感を有するフアンシーヤーン
JPH05239724A (ja) * 1992-02-21 1993-09-17 Unitika Ltd 柄効果を有する清涼感素材
JPH0892842A (ja) 1994-09-21 1996-04-09 Mitsufuji Seni Kogyo Kk 銀メッキした繊維を使用した赤外線反射性を有する布帛製品
JP3464062B2 (ja) 1994-11-29 2003-11-05 ユニチカ株式会社 清涼感を有する嵩高性ポリエステル捲縮糸
JPH11350256A (ja) * 1998-06-12 1999-12-21 Kuraray Co Ltd 特殊複合繊維
JP4357627B2 (ja) * 1999-03-30 2009-11-04 旭化成せんい株式会社 紫外線遮蔽性布帛
US7338877B1 (en) * 2002-11-27 2008-03-04 Fiber Innovation Technology, Inc. Multicomponent fiber including a luminescent colorant
JP4228856B2 (ja) * 2003-09-22 2009-02-25 東レ株式会社 熱可塑性繊維、布帛および繊維製品
JP2005273085A (ja) * 2004-03-25 2005-10-06 Toray Ind Inc 芯鞘型ポリエステル複合繊維およびその製造方法
WO2006008785A1 (ja) * 2004-07-15 2006-01-26 Sumitomo Metal Mining Co., Ltd. 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
JP2006161248A (ja) * 2004-12-10 2006-06-22 Kawashima Selkon Textiles Co Ltd 遮熱線性繊維と遮熱線採光性布帛
JP2006249625A (ja) * 2005-03-14 2006-09-21 Toray Ind Inc 芯鞘型ポリエステル繊維
CN1912199A (zh) * 2005-08-08 2007-02-14 东丽纤维研究所（中国）有限公司 双组分聚酯皮芯复合纤维及生产方法
CN100395400C (zh) * 2005-09-29 2008-06-18 上海交通大学 可用于深染色纤维的聚酯纳米复合材料制备方法
CN100355831C (zh) * 2005-10-28 2007-12-19 四川大学 含磷阻燃共聚酯/硫酸钡纳米复合材料及其制备方法
JPWO2008093560A1 (ja) * 2007-01-29 2010-05-20 株式会社ワイ・ジー・ケー 発光性複合糸条
JP2008223171A (ja) * 2007-03-13 2008-09-25 Asahi Kasei Fibers Corp 赤外線透過防止性に優れた編地
CN101358387A (zh) * 2008-09-09 2009-02-04 江苏省纺织研究所有限公司 一种白色复合导电纤维
CN101570901B (zh) * 2009-03-24 2011-01-26 舟山欣欣化纤有限公司 高光学遮蔽性的化学纤维
JP5777391B2 (ja) * 2010-04-21 2015-09-09 Ｋｂセーレン株式会社 インテリア内装材
JP2011241529A (ja) * 2010-04-21 2011-12-01 Kb Seiren Ltd 芯鞘型複合繊維
JP5379076B2 (ja) * 2010-05-26 2013-12-25 Ｋｂセーレン株式会社 複合合成繊維
US20120289107A1 (en) * 2011-04-22 2012-11-15 OSUS, Inc. Metal/polymer composite fibers

Also Published As

Publication number Publication date
CN104066875B (zh) 2015-12-30
JP6005070B2 (ja) 2016-10-12
TW201335451A (zh) 2013-09-01
US20140335354A1 (en) 2014-11-13
CN104066875A (zh) 2014-09-24
JPWO2013111661A1 (ja) 2015-05-11
WO2013111661A1 (ja) 2013-08-01
EP2808428B1 (de) 2018-06-13
EP2808428A4 (de) 2015-09-23
TWI580831B (zh) 2017-05-01

Similar Documents

Publication Publication Date Title
EP2808428B1 (de) Polyesterverbundfaser mit ausgezeichneter hitzeabschirmungseigenschaft und färbung
TWI551742B (zh) 芯鞘複合纖維、含有同芯鞘複合纖維的假撚加工紗及其製造方法以及包含這些纖維的織編物
JP4228856B2 (ja) 熱可塑性繊維、布帛および繊維製品
JP5297331B2 (ja) 芯鞘型複合繊維
JP6882942B2 (ja) ポリエステル系複合繊維及び繊維集合体
JP6129608B2 (ja) 防透性に優れたポリエステル系芯鞘型複合繊維及びその製造方法
JP2011241529A (ja) 芯鞘型複合繊維
JP5777391B2 (ja) インテリア内装材
JP2016113714A (ja) 仮撚中空マルチフィラメント糸、及び織編物
JP2014177716A (ja) 遮熱性及び防透性に優れた芯鞘型異形断面複合繊維
JP5324360B2 (ja) 芯鞘型複合仮撚加工糸を含む布帛および繊維製品
JP4866103B2 (ja) 複合繊維
JPH11107048A (ja) 染色性及び紫外線遮蔽性に優れた芯鞘型ポリエステル繊維及びその製造方法
JP6355388B2 (ja) 複合繊維
JP6355351B2 (ja) 合成繊維
KR100421920B1 (ko) 불투명성 중공섬유의 제조방법
JP2012021245A (ja) 遮熱性編物および繊維製品
WO2026038407A1 (ja) 異型扁平断面繊維、布帛、および繊維製品
JP3908851B2 (ja) ポリエステル太細マルチフィラメント
JP7005188B2 (ja) 仮撚マルチフィラメント糸、その製造方法、及び織編物
JPH11181627A (ja) ポリエステル複合短繊維
JP2020084358A (ja) 仮撚中空マルチフィラメント糸、その製造方法、および織編物
JPH0559607A (ja) 涼感性を有する繊維および布帛
JPH1161552A (ja) 太細を有する合成繊維マルチフィラメントおよび織物
JP2007239139A (ja) 複合仮撚加工糸

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20140821

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

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150825

RIC1 Information provided on ipc code assigned before grant

Ipc: D01F 1/10 20060101ALI20150819BHEP

Ipc: D01F 8/14 20060101AFI20150819BHEP

RIC1 Information provided on ipc code assigned before grant

Ipc: D01F 8/14 20060101AFI20171214BHEP

Ipc: D01F 1/10 20060101ALI20171214BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180125

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1008619

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013038893

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180613

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180913

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180913

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180914

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1008619

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181013

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013038893

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190314

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190117

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190131

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181015

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130117

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20211206

Year of fee payment: 10

Ref country code: FR

Payment date: 20211214

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20211130

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20211213

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180613

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602013038893

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230117

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230117