(19) Japanese Patent Office
`(JP)
`
`(12) JAPANESE UNEXAMINED PATENT APPLICATION
`PUBLICATION (A)
`
`(51) Int. Cl.7
`A43B
`1/04
`7/06
`13/02
`23/02
`21/16
`
`D04B
`
`Ident. Code
`
`101
`
`FI
`A43B
`
`(11) Patent Application
`Disclosure No.
`JP 2002-65303 A
`(P2002-65303A)
`(43) Publication Date March 5,
`2002 (Heisei 14)
`Theme Code (Reference)
`4F050
`4L002
`
`1/04
`7/06
`13/02
`23/02
`21/16
` D04B
`Examination Request: Not Yet Total No. of
`Claims: 5 OL (Total 6 pages)
`
`A
`101A
`
`(21) Application
`No.
`
`(22) Date of
`Filing
`
`JP 2000-254957 (P2000-254957)
`
`(71)
`Applicant
`
`000003090
`
`August 25, 2000 (Heisei 12)
`
`Toho Tenax Co., Ltd.
`2-38-16 Hongo, Bunkyo-ku, Tokyo
`
`(72)
`Inventor
`
`Norihiko Tani
`
`4-4-9 Fushimi-cho, Chuo-ku, Osaka-
`shi, Osaka
`c/o Toho Textile Co. Ltd.
`Yoshiharu Ueda
`
`4-4-9 Fushimi-cho, Chuo-ku, Osaka-
`shi, Osaka
`c/o Toho Textile Co. Ltd.
`100083688
`
`Yasuyo Takahata
`
`(72)
`Inventor
`
`(74) Agent
`for
`Applicant
`
`Continued on
`last page
`
`(54) [Title of Invention] SHOE
`
`(57) [Abstract]
`[Problem] To provide a shoe having superior lightness,
`breathability, moisture-wicking, deodorizing, and
`antimicrobial properties.
`[Resolution Means] A shoe composed of a shoe sole and
`a shoe instep that covers the shoe sole, in which the
`shoe instep is configured of a double Raschel fabric,
`where looper thread 20 in one surface 16 of the double
`Raschel fabric 200 includes an antimicrobial acrylic
`moisture absorbing/desorbing fiber, and the one
`surface 16 faces the inside of the shoe.
`
`-1-
`
`lululemon Ex. 1012
`IPR Petition - USP 8,266,749
`
`

`

`
`
`[Scope of Patent Claims]
`[Claim 1] A shoe comprising a shoe sole and a shoe instep
`that covers the shoe sole, wherein the shoe instep is
`configured of a double Raschel fabric, where looper
`thread in one surface of the double Raschel fabric
`includes
`an
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing fiber, and the one surface faces the
`inside of the shoe.
`[Claim 2] The shoe according to claim 1, wherein a
`bacteriostatic activity value pertaining to Trichophyton
`in
`the
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing fiber is 2 or higher.
`[Claim 3] The shoe according to claim 1 or 2, wherein a
`moisture absorbing ratio of the antimicrobial acrylic
`moisture absorbing/desorbing fiber at 20ºC and a
`relative humidity of 60% is 20% by mass or higher.
`[Claim 4] The shoe according to any of claims 1 to 3,
`wherein a degree of knot elongation of the antimicrobial
`acrylic moisture absorbing/desorbing fiber is 8% or
`higher.
`[Claim 5] The shoe according to any of claims 1 to 4,
`wherein a fineness of the antimicrobial acrylic moisture
`absorbing/desorbing fiber is 1 to 2 denier.
`[Detailed Description of Invention]
`[0001]
`[Field of Art of Invention] The present invention relates
`to a shoe used for commuting, work, exercise, and the
`like, and relates in particular to a shoe using an
`antimicrobial moisture absorbing/desorbing fiber.
`[0002]
`[Conventional Art] Moisture absorbing/desorbing fibers
`that absorb water and generate heat are conventionally
`known. Clothing and underlay materials for shoes using
`a moisture absorbing/desorbing fiber that utilize this
`property are likewise conventionally known. Clothing and
`underlay materials for shoes manufactured using this
`moisture absorbing/desorbing fiber directly absorb sweat
`and the like generated by the human body such as by the
`soles in a liquid state or absorb evaporated sweat and
`the like from a gas phase. Furthermore, rain or moisture
`penetrating from outside is absorbed, which generates
`heat, with the intention of further enhancing a heat
`retention effect of the clothing and underlay material
`for shoes.
`[0003] An aim of the moisture absorbing/desorbing fiber
`is to absorb sweat and the like expelled by the human
`body such as by the soles, and due to being used often
`in clothing and underlay materials for shoes, the quality
`of tactile sensation on the skin and presence of
`antimicrobial properties are important.
`[0004] Among the moisture absorbing/desorbing fibers
`described
`above,
`antimicrobial
`moisture
`absorbing/desorbing fibers that are an improvement over
`acrylic fibers having low water absorbing/moisture
`absorbing properties are also known. JP H5-132858 A
`discloses
`an
`acrylic
`thread
`highly
`moisture
`absorbent/desorbent
`fiber
`having
`antimicrobial
`properties
`pertaining
`to
`Klebsiella
`pneumoniae.
`Furthermore,
`an
`acrylic
`thread
`moisture
`absorbing/desorbing
`fiber
`having
`antimicrobial
`resistance
`to
`Staphylococcus
`aureus
`is
`also
`conventionally known (JP H9-308 A).
`moisture
`a
`not
`[0005]
`In
`addition,
`although
`absorbing/desorbing fiber, JP H9-13221 A discloses an
`acrylic fiber having antimicrobial properties pertaining
`to Staphylococcus aureus-like bacteria and the
`antifungal properties stipulated in JIS Z2911.
`[0006] However, no shoes that use these moisture
`absorbing/desorbing fibers are known.
`
`(2) 2002-65303 (P2002-65303)
`
`[0007]
`[Problem to be Solved by Invention] The present inventors
`took a variety of considerations into account in order
`to manufacture a shoe that is light, breathable,
`moisture-wicking, deodorizing, and is provided with
`antimicrobial properties, cushioning properties, and the
`like, and as a result, learned that configuring a shoe
`instep from a double Raschel fabric interwoven with a
`moisture absorbing/desorbing fiber is suitable for the
`aforementioned purpose.
`[0008] Therefore, an object of the present invention is
`to provide a shoe having superior lightness,
`breathability,
`moisture-wicking,
`deodorizing,
`and
`antimicrobial properties.
`[0009]
`[Means for Solving the Problem] The present invention
`achieves the above object as described below.
`[0010] (1) A shoe composed of a shoe sole and a shoe
`instep that covers the shoe sole, in which the shoe
`instep is configured of a double Raschel fabric, where
`looper thread in one surface of the double Raschel fabric
`includes
`an
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing fiber, and the one surface faces the
`inside of the shoe.
`[0011] (2) The shoe according to (1), wherein a
`bacteriostatic activity value pertaining to Trichophyton
`in
`the
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing fiber is 2 or higher.
`[0012] (3) The shoe according to (1) or (2), wherein a
`moisture absorbing ratio of the antimicrobial acrylic
`moisture absorbing/desorbing fiber at 20ºC and a
`relative humidity of 60% is 20% by mass or higher.
`[0013] (4) The shoe according to any of (1) to (3),
`wherein a degree of knot elongation of the antimicrobial
`acrylic moisture absorbing/desorbing fiber is 8% or
`higher.
`[0014] (5) The shoe according to any of (1) to (4),
`wherein a fineness of the antimicrobial acrylic moisture
`absorbing/desorbing fiber is 1 to 2 denier.
`[0015] The present invention is described in detail below.
`[0016]
`[Embodiment of Invention] FIG. 1 is a schematic drawing
`illustrating one example of the shoe of the present
`invention.
`[0017] In the drawing, a shoe 100 is composed of a shoe
`sole 2 formed of rubber, leather, resin, or the like and
`a shoe instep 4 integrated by adhesion or sewing covering
`the shoe sole 2.
`[0018] In the present invention, the shoe instep 4
`utilizes a double Raschel fabric in which a moisture
`absorbing/desorbing fiber is interwoven.
`[0019] FIG. 2 is a schematic drawing illustrating one
`example of the double Raschel fabric configuring the
`instep of the shoe of the present invention.
`[0020] As illustrated in FIG. 2, a double Raschel fabric
`200 is configured of a front surface 12, a knotted
`portion 14, and a rear surface 16. Furthermore, the rear
`surface 16 (one surface of the double Raschel fabric 200)
`is configured of a chain thread 18 and a looper thread
`20. 22 is in the knotted portion 14, being the knotted
`thread that knots the front surface 12 and the rear
`surface 16 together.
`[0021] The looper thread 20 in the rear surface 6
`includes
`an
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing fiber. An amount of moisture
`absorbing/desorbing fiber used in the looper thread is
`preferably 5% by mass or more, more preferably 10 to 90%
`by mass, and particularly preferably 20 to 60% by mass.
`
`-2-
`
`lululemon Ex. 1012
`IPR Petition - USP 8,266,749
`
`

`

`
`
`[0022] For another fiber used in the double Raschel
`fabric other than the moisture absorbing/desorbing
`fiber described above, a hydrophobic fiber such as
`nylon, polyester, or the like is preferable.
`[0023] Note that the front surface 12 is also
`configured of a chain thread and a looper thread, and
`this looper thread may include the moisture
`absorbing/desorbing fiber described above. However,
`because the front surface 12 does not directly contact
`the instep of the foot, even if the looper thread of
`the front surface 12 does include the moisture
`absorbing/desorbing
`fiber
`described
`above,
`antimicrobial properties do not increase much, while
`a strength of the double Raschel fabric 200 decreases.
`Therefore, it is preferable that inclusion of the
`moisture absorbing/desorbing fiber described above in
`looper thread be limited to the looping thread 20 of
`the rear surface 16.
`[0024] In addition, to reinforce the double Raschel
`fabric 200, for example, the double Raschel fabric
`200 may be adhered to the outer material of a course
`mesh as a lining.
`[0025] Moreover, the double Raschel fabric 200 may be
`inserted or adhered onto the shoe sole 2 as a shoe
`underlay material.
`[0026] In the present invention, a rear surface 16 of
`the double Raschel fabric 200 faces inside of a shoe
`100, that is, one surface including the moisture
`absorbing/desorbing fiber faces inside of the shoe
`100, configuring the shoe instep 4.
`moisture
`[0027]
`The
`antimicrobial
`acrylic
`absorbing/desorbing fiber used in the present
`invention is not particularly limited, and a
`conventionally known fiber can be used as appropriate.
`[0028] One preferable example of a raw material for
`manufacturing the antimicrobial acrylic moisture
`absorbing/desorbing fiber used in the present
`invention is an acrylic fiber or an acrylic fiber
`composed of an acrylic copolymer including 5% by mass
`or less of a monomer unit having an acid group.
`[0029] A comonomer having an acid group is a commonly
`used vinyl monomer having an acid group capable of
`copolymerizing with an acrylonitrile. Specific
`examples include monomers having a carboxyl group
`such as acrylic acid, methacrylic acid, and itaconic
`acid, or a salt thereof, and monomers having a
`sulfonic acid group, such as allylsulfonic acid and
`methallylsulfonic acid, or a salt thereof. When the
`acrylic fiber contains 1 to 5% by mass of a comonomer
`unit having an acid group, crosslinking and
`hydrolysis reactions described later are promoted,
`which is preferable.
`[0030] When the content of the acid group-containing
`comonomer unit exceeds 5% by mass, as a characteristic
`of the acid-containing comonomer, coagulability
`decreases during wet spinning, accompanied by the
`occurrence of thread adhesion. In addition, heat
`resistance of the copolymer is drastically reduced,
`and is therefore not preferable.
`[0031] When the acrylic fiber includes a comonomer
`unit other than an acid group-containing comonomer,
`it is preferable that a total of the comonomer unit
`be adjusted to less than 20% by mass and made to
`contain at least 80% by mass of an acrylonitrile
`monomer unit. When the content of the acrylonitrile
`monomer unit is less than 80% by mass, reaction rates
`of crosslinking and hydrolysis described below are
`reduced due to a reduction in copolymer nitrile groups,
`and this is therefore not preferable.
`
`(3) 2002-65303 (P2002-65303)
`[0032] A dry strength of an acrylic fiber of 2.5 to
`15. 0 g/d (denier) can be used. If attempting to
`obtain a dry strength of 1 g/d or more for the
`antimicrobial acrylic moisture absorbing/desorbing
`fiber, a dry strength of 3.0 to 8.0 g/d for a raw
`material to be treated is preferable. Moreover, a
`thickness of an acrylic fiber of a raw material is
`not
`particularly
`limited,
`however,
`when
`an
`antimicrobial acrylic moisture absorbing/desorbing
`fiber of 1 to 2 denier is manufactured, 0.5 to 1.0
`denier (d) is preferable.
`[0033] In the present invention, a principle nitrile
`group in the acrylic fiber described above is
`hydrolyzed using sodium carbonate at the same time as
`a crosslinking treatment or after a crosslinking
`treatment using a hydrazine compound.
`[0034] First, a method of hydrolyzing using sodium
`carbonate following crosslinking treatment using a
`hydrazine compound is described.
`[0035] The crosslinking treatment causes a hydrazine
`compound to react with an acrylic fiber containing 5%
`by mass or less of the comonomer unit having the acid
`group described above, which introduces a crosslinked
`structure such that nitrogen content of an acrylic
`fiber increases to 0.1 to 10% by mass.
`[0036] Reaction conditions are not particularly
`limited; for example, an acrylic fiber including 5%
`by mass or less of an acid group-containing comonomer
`unit is preferably crosslink treated using an aqueous
`solution having a hydrazine concentration of 0.5 to
`5% by mass (solvent ratio 1:10) at a temperature lower
`than 98ºC for 0.5 to 2 hours.
`[0037] Hydrazine hydrochloride, hydrazine sulfate,
`hydrazine hydrate, hydrazine carbonate, and the like
`can be used as the hydrazine compound, which is not
`particularly limited.
`[0038] Here, hydrazine concentration refers to a
`concentration of a hydrazine component within the
`hydrazine compound.
`[0039] Next, the principle nitrile group within the
`acrylic fiber introducing the crosslinked structure
`is hydrolyzed using sodium carbonate.
`[0040] It is desirable for the hydrolysis reaction
`that an amount of a carboxyl group in the acrylic
`fiber be controlled to 0.6 to 4 mmol/g.
`[0041] It is preferable that hydrolysis reactions
`using sodium carbonate be performed in an aqueous
`solution or a mixed solution of water and a miscible
`solvent. A concentration of the sodium carbonate is
`preferably 5 to 30% by mass. A reaction temperature
`is preferably 80 to 100°C. A reaction time is
`preferably 2 to 5 hours.
`[0042] A reaction rate of hydrolysis by the sodium
`carbonate is substantially unaffected by the type of
`comonomer.As a result of earnest study, the present
`inventors found that a rate of hydrolysis is also
`promoted when crosslinking is increased. That is, if
`crosslinking is sufficiently performed, a used amount
`of sodium carbonate can be reduced and a treatment
`time can be shortened as a result.
`[0043] Conventionally, hydrolysis reactions are
`performed using an alkali metal hydroxide . However,
`when an alkali metal hydroxide is used, reactions can
`be intense, and it can be difficult to reduce a degree
`of swelling by water in the fiber to 100% by mass or
`lower. In order to overcome this issue, sodium
`carbonate is used in the present invention, which
`slows reactions, enabling a degree of swelling by
`water to be reduced to 100% by mass or lower.
`
`-3-
`
`lululemon Ex. 1012
`IPR Petition - USP 8,266,749
`
`

`

`[0044] Hereinafter, a method for simultaneously
`performing an acrylic fiber crosslinking treatment
`and a hydrolyzing treatment is described.
`[0045] In this method, a solution of hydrazine and
`sodium carbonate is used to simultaneously perform an
`acrylic
`fiber
`crosslinking
`treatment
`and
`hydrolyzation. It is preferable that the treatment
`conditions include a hydrazine concentration of 0.5
`to 5% by mass and a sodium carbonate concentration of
`5 to 30% by mass. It is preferable that a reaction
`temperature be 80 to 100ºC. It is preferable that the
`reaction time be 2 to 5 hours.
`[0046] Acrylic fibers containing 5% by mass or less
`of an acidic comonomer unit promote crosslinking
`reactions compared to acrylic fibers not containing
`an acidic comonomer unit. For example, in a treatment
`at a hydrazine concentration of 2% by mass (solvent
`ratio 1:10), 10% by mass of sodium carbonate, and
`98ºC, a moisture absorbing/desorbing fiber is
`obtained within one hour. Therefore, in this case, by
`obtaining
`a
`crosslinked
`acrylic
`moisture
`absorbing/desorbing fiber having a conventionally
`equivalent degree of crosslinking, an amount of
`hydrazine used and a treatment time can be reduced.
`[0047] By controlling an amount of a carboxyl group
`to 0.6 to 4 mmol/g via a hydrolysis reaction using
`sodium carbonate, an antimicrobial crosslinked
`acrylic moisture absorbing/desorbing fiber can be
`manufactured having the properties: a saturated
`moisture absorption rate at 20ºC and a relative
`humidity of 60% of 20 to 40% by mass, a degree of
`swelling by water of 10 to 100% by mass, and a degree
`of knot elongation of 8% or higher.
`[0048] When a raw material acrylonitrile fiber having
`a fineness of 0.5 to 1.0 denier is used, an
`antimicrobial acrylic moisture absorbing/desorbing
`fiber having a fineness of 1 to 2 denier can be
`obtained by the above hydrolyzing conditions.
`[0049]
`The
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing fiber used in the sole of the
`shoe of the present invention, which is manufactured
`according to the manufacturing method described above,
`has a degree of knot elongation of 8% or higher, and
`therefore has superior workability, a spun thread
`mixed with another material can be easily produced,
`and
`the
`antimicrobial
`acrylic
`moisture
`absorbing/desorbing
`fiber
`effectively
`improves
`strength and texture.
`Knitting machine
`Knitting specifications
`
`(4) 2002-65303 (P2002-65303)
`
`[0050] Examples of the other blended fiber include a
`hydrophobic fiber such as nylon or polyester.
`[0051] In the case of blending, it is preferable that
`a raw cotton blend mixing method be adopted in a
`batting process. This supports physical properties of
`the counterpart blended material and makes for easy
`manufacture of a blended thread. Blend percentages
`may be arbitrarily selected within a commonly
`performed range.
`moisture
`acrylic
`[0052]
`The
`antimicrobial
`absorbing/desorbing fiber used in the instep of the
`shoe of the present invention has antimicrobial
`properties pertaining to a variety of microbes such
`as
`Trichophyton,
`Klebsiella
`pneumoniae,
`and
`Staphylococcus aureus, and according to the test
`results
`described
`below,
`exhibits
`a
`high
`bacteriostatic value of 2.3 or higher. Moreover,
`fungal resistance and deodorizing properties are also
`high.
`[0053]
`[Examples] The present invention is more specifically
`described below using examples. In the examples, “%”
`is “% by mass” unless negated.
`[0054] Example 1
`An acrylic fiber formed of a copolymer of 89% by mass
`of acrylonitrile, 9% by mass of methyl acrylate, and
`2% by mass of sodium methallylsulfonate was used as
`a raw material fiber 1 at a fineness of 0.6 denier
`and a degree of knot elongation of 12%.
`[0055] The raw material fiber 1 was treated in a mixed
`solution of 5% by mass of hydrazine hydrate and 20%
`by mass of sodium carbonate at 100ºC for 180 minutes.
`Following indirect cooling, neutralization was
`performed using hydrochloric acid and a hydrothermal
`treatment was performed (100ºC x 30 minutes) for the
`purpose of decolorization. Following centrifugal
`dehydration, this was dried at 100ºC for 20 minutes
`to obtain the antimicrobial acrylic moisture
`absorbing/desorbing fiber.
`[0056] 30% by mass of the antimicrobial acrylic
`moisture absorbing/desorbing fiber and 70% by mass of
`a polyester fiber were blended to obtain a 40/2 spun
`thread of 30% moisture absorbing/desorbing fiber and
`70% polyester fiber.
`[0057] A double Raschel fabric was produced under the
`following conditions.
`
`: KARL MAYER, Double Raschel machine
`: Gauge 18/inch
`Stitch 24. 3/inch
`Bar interval 2.5 mm
`Used thread specifications : Front surface
`Chain thread Nylon 240d/34
`Looper thread Nylon 240d/34
`Rear surface
`Chain thread Nylon 240d/34
`Looper thread 30% moisture absorbing/desorbing
`fiber, 70% polyester fiber, 40/2 spun thread
`Knotted portion
`Knotted thread Nylon 100d/24
`: 106 cm (width on knitting machine)
`: 98 cm (knitting unloaded width)
`: 473 g/m2
`
`Knitting width
`Knitted fabric width
`Apertures
`
`-4-
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`IPR Petition - USP 8,266,749
`
`

`

`A shoe instep produced by the double Raschel fabric
`described above was manufactured into sneakers
`integrating this shoe instep with a shoe sole. Upon
`performing a shoe test of the sneakers, superior
`lightness, strength, cushioning, breathability,
`moisture-wicking, deodorizing, and antimicrobial
`properties were confirmed.
`[0058] Example 2
`
`Used thread specifications: : Front surface
`
`(5) 2002-65303 (P2002-65303)
`
`Apart from the used thread specification conditions
`below, a double Raschel fabric was produced similarly
`to Example 1, and upon performing the following shoe
`test for the sneakers, superior lightness, strength,
`cushioning,
`breathability,
`moisture-wicking,
`deodorizing, and antimicrobial properties were
`confirmed.
`
`Chain thread Polyester 75d
`Looping thread Polyester fiber 40/2 spun thread
`Rear surface
`Chain thread Polyester 75d
`Looping thread 30% moisture absorbing/desorbing fiber, 70%
`polyester fiber, 40/2 spun thread Knotted portion
`Knotted thread Polyester 250d
`
`[0059]
`[Effect of Invention] The shoe of the present
`invention has superior breathability, moisture-
`wicking, deodorizing, and antimicrobial properties,
`and can be suitably used for any shoe for commuting,
`working, exercising, and the like.
`[0060] In addition, among the shoes above, the shoe
`of the present invention is particularly suited to
`shoes used for exercise such as sneakers.
`[Brief Description of Drawings]
`[FIG. 1] is a schematic drawing illustrating one
`example of the shoe of the present invention.
`[FIG. 2] is a schematic drawing illustrating one
`example of the double Raschel fabric configuring the
`shoe instep of the present invention.
`[Description of Reference Numerals]
`
`100 Shoe
`2 Shoe sole
`4 Shoe instep
`200 Double Raschel fabric
`12 Front surface
`14 Knotted portion
`16 Rear surface
`18 Chain thread
`20 Looper thread
`22 Knotted thread
`
`[FIG. 1]
`
`[FIG. 2]
`
`-5-
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`
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`
`
`Continued from front page
`
`
`
`
`
`
`
`F term
`(reference)
`
`
`
`
`
`4F050 AA01 AA06 BA01 BA43 BC03
`BC43 HA28 HA30 HA33 HA67
`HA91 HA96
`
`4L002 AA08 AC00 CA03 CA04 CB01
`EA00
`
`(6) 2002-65303 (P2002-65303)
`
`-6-
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`
`

`

`July 27, 2023
`
`Certification
`
`Welocalize Translations
`
`TRANSLATOR'S DECLARATION:
`
`I, Nicholas Abraham, hereby declare:
`
`That I possess advanced knowledge of the Japanese and English languages.
`The attached Japanese into English translation has been translated by me and
`to the best of my knowledge and belief, it is a true and accurate translation of
`Patent Number JP2002065303A
`
`________________________________________
`
`Nicholas Abraham
`
`Project Number: KNMA_2307_P0009
`
`15 W. 37th Street 4th Floor
`New York, NY 10018
`212.581.8870
`
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