US20200291571A1 - Dyed artificial leather base material, napped artificial leather, resin layer-equipped artificial leather, shoes, decorating sheet, and decorative molded body - Google Patents

Dyed artificial leather base material, napped artificial leather, resin layer-equipped artificial leather, shoes, decorating sheet, and decorative molded body Download PDF

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Publication number
US20200291571A1
US20200291571A1 US16/328,440 US201716328440A US2020291571A1 US 20200291571 A1 US20200291571 A1 US 20200291571A1 US 201716328440 A US201716328440 A US 201716328440A US 2020291571 A1 US2020291571 A1 US 2020291571A1
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Prior art keywords
artificial leather
base material
molded body
leather base
cationic dye
Prior art date
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Abandoned
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US16/328,440
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English (en)
Inventor
Michinori Fujisawa
Daisuke Matsuda
Toshiyuki Ito
Yasunori Murate
Tetsuya Ando
Masato Warita
Naoto Narumoto
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
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Publication date
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Assigned to KURARAY CO., LTD. reassignment KURARAY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJISAWA, MICHINORI, WARITA, MASATO, ANDO, TETSUYA, ITO, TOSHIYUKI, MATSUDA, DAISUKE, MURATE, YASUNORI, NARUMOTO, NAOTO
Publication of US20200291571A1 publication Critical patent/US20200291571A1/en
Abandoned legal-status Critical Current

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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)

Definitions

  • the present invention relates to a dyed artificial leather base material, a napped artificial leather, a resin layer-equipped artificial leather, a shoe, a decorating sheet, and a decorative molded body.
  • an artificial leather base material is used for the surface members of various articles for daily use.
  • an artificial leather base material can be used, for example, as the upper material of shoes by being integrated with an outsole made of a rubber, a synthetic resin or the like, or as the surface member of a car seat, a general merchandise or the like by being attached to a member made of a different material with an adhesive.
  • the artificial leather base material is formed into a napped artificial leather by forming fiber naps on the surface thereof, or formed into a resin layer-equipped artificial leather by integrating therewith a resin of a film, a urethane foam, a hard plastic plate or the like, thus imparting a unique appearance design, tactile impression or texture to the artificial leather base material.
  • Decorative molded bodies for which an artificial leather is used as a surface decorating sheet are also known as the exterior member, including, for example, the casing of a mobile device such as a mobile phone, a home electrical appliance, and a sanitary product, the interior member of a vehicle, a vessel, an aircraft and the like, and the exterior member of a building material, an article of furniture and the like.
  • a decorating sheet which is an artificial leather integrated with a resin molded body by in-molding, and a decorative molded body using the same.
  • an artificial leather base material is produced by coloring a fiber base material including a non-woven fabric and an elastic polymer such as polyurethane.
  • a fiber base material including a non-woven fabric and an elastic polymer such as polyurethane As the fibers included in the artificial leather base material, polyester fibers can be preferably used because of the excellent heat resistance and moldability.
  • a disperse dye As the dye for dyeing the artificial leather base material including polyester fibers, a disperse dye is widely used because of the excellent color development.
  • an artificial leather base material dyed with a disperse dye is problematic in that the disperse dye may contaminate another member and a molded body to be decorated, and such contamination can be prominent when the ambient temperature or the pressure applied to the member is high, or when the adhesive or the like contains an organic solvent.
  • PTL 2 discloses an ultrafine fiber napped non-woven fabric including polyester ultrafine fibers that can be dyed with a cationic dye and an elastomeric matrix, and a UV stabilizer composition.
  • PTL 3 discloses a technique relating to a synthetic leather, namely, a synthetic leather obtained by forming a resin layer on the surface of a double-raschel knitted fabric.
  • the double-raschel knitted fabric includes a front knitted fabric, a back knitted fabric, and a pile layer connecting the front knitted fabric and the back knitted fabric.
  • the fibers constituting the front knitted fabric are polyester fibers dyed with a cationic dye, and a resin layer is formed on the front knitted fabric side.
  • the polyester fibers include a dicarboxylic acid component composed mainly of terephthalic acid, and a polyester including a glycol component composed mainly of ethylene glycol, wherein the dicarboxylic acid component includes a component represented by the following formula (III):
  • X represents a metal ion, a quaternary phosphonium ion, or a quaternary ammonium ion.
  • PTL 4 discloses a deodorizing fabric that has been subjected to a deodorizing treatment, wherein the deodorizing fabric includes, as a copolymer component, copolymerized polyester fibers a containing, in an acid component, a metal salt (A) of a sulfoisophthalic acid or a quaternary phosphonium salt or a quaternary ammonium salt (B) of a sulfoisophthalic acid such that 3.0 ⁇ A+B ⁇ 5.0 (mol %) and 0.2 ⁇ B/(A+B) ⁇ 0.7, and the deodorizing fabric has been dyed with a cationic dye.
  • A metal salt
  • B quaternary ammonium salt
  • the color of the artificial leather base material covered by the resin layer is not visible from the surface side. Accordingly, there is no need to color the artificial leather base material.
  • the decorative molded body is produced, for example, by primary decorative molding such as in-molding in which, in a state in which a decorating sheet or a preform molded body obtained by shaping the decorating sheet into a three-dimensional shape is disposed in advance in a cavity of a mold, molten resin is injected into the cavity, and then solidified, thus molding a decorative molded body in which the decorating sheet is integrated with the surface of a resin molded body.
  • primary decorative molding such as in-molding in which, in a state in which a decorating sheet or a preform molded body obtained by shaping the decorating sheet into a three-dimensional shape is disposed in advance in a cavity of a mold, molten resin is injected into the cavity, and then solidified, thus molding a decorative molded body in which the decorating sheet is integrated with the surface of a resin molded body.
  • the decorative molded body can be produced by secondary decorative molding such as overlaying in which a decorating sheet is integrated with a resin molded body by being attached to the resin molded body with an adhesive while shaped by heating so as to follow the surface thereof.
  • a decorating sheet dyed with a disperse dye the dye may be sublimated by heat or pressure or may be liberated by an organic solvent contained in the adhesive, when the decorating sheet is integrated with the molded body to be decorated.
  • the disperse dye that has migrated from the decorating sheet contaminates the molded body to be decorated, which is a resin molded body.
  • the molded body to be decorated is white or light color, the contamination caused by the disperse dye becomes even more conspicuous, thus significantly compromising the commercial value.
  • the artificial leather base material is covered by the dark color resin layer, so that the color of the artificial leather base material is not visible from the surface side.
  • the cross section of the decorating sheet is exposed.
  • an after treatment such as a skiving treatment is not performed on an end face of the decorating sheet at an end face of a decorative molded body, the cross section of the decorating sheet is also exposed.
  • An aspect of the present invention is directed to an artificial leather base material including a fiber base material that includes cationic dye-dyeable polyester fibers and an elastic polymer, the artificial leather base material being dyed with at least one cationic dye and having a surface with a lightness L* value of ⁇ 50.
  • a fiber base material that includes cationic dye-dyeable polyester fibers and an elastic polymer, the artificial leather base material being dyed with at least one cationic dye and having a surface with a lightness L* value of ⁇ 50.
  • Such an artificial leather base material is less likely to cause migration of the dye to another member in contact therewith even though it is colored in a dark color.
  • the artificial leather base material is less likely to contaminate the resin layer or the resin molded body.
  • the fiber base material includes, for example, a non-woven fabric of cationic dye-dyeable polyester fibers and an elastic polymer.
  • the artificial leather base material has a grade of color difference, determined in an evaluation of color migration to a white polyvinyl chloride film with a thickness of 0.8 mm under a load of 750 g/cm 2 at 50° C. for 16 hours, of 4 or more, because even a dark colored artificial leather base material is less likely to contaminate a white or light-color resin layer, a resin molded body, or another member in contact therewith.
  • a grade of color difference, determined in an evaluation of color migration to a white polyvinyl chloride film, of 4 or more means that color difference ⁇ E* ⁇ 2.0 is achieved in the evaluation of color migration.
  • the artificial leather base material it is preferable that, after a white polyurethane film with a thickness of 250 ⁇ m is pressure-bonded under heating to a surface of the artificial leather base material via a polyurethane adhesive under 5 Kg/cm 2 at 130° C. for 1 minute to form a resin layer-equipped artificial leather, and the resin layer-equipped artificial leather is pressurized under heating under 20 Kg/cm 2 at 150° C. for 1 minute, the artificial leather has a grade of color difference, determined in an evaluation of color migration to the white polyurethane film, of 3 or more. This is because even when a resin layer-equipped artificial leather including a white or light-color resin layer is formed, the artificial leather base material is less likely to contaminate the resin layer. Note that “a grade of color difference, determined in an evaluation of color migration to the white polyurethane film, of 3 or more” means that a color difference ⁇ E* of ⁇ 3.8 is achieved in the evaluation of color migration.
  • the artificial leather base material has a grade of color difference, determined in an evaluation of color migration using methyl ethyl ketone (MEK), of 2 or more, because the artificial leather base material is less likely to be contaminate the resin layer when the artificial leather base material is bonded to a white or light-color resin layer with an adhesive containing a solvent.
  • a grade of color difference, determined in an evaluation of color migration using methyl ethyl ketone (MEK), of 2 or more means that a grade of color difference, determined in an evaluation of color migration to a white polyurethane film in accordance with the JIS gray-scale standard, of 2 or more.
  • a product of a softness and a thickness of the artificial leather base material is 2 or more, because a flexible texture can be achieved.
  • the artificial leather base material contains 0.5 to 20 parts by mass of the cationic dye, per 100 parts by mass of the fiber base material, because even a dark colored artificial leather base material is less likely to cause migration of the dye.
  • the artificial leather base material has a grade, determined in a water fastness test for a cotton cloth in accordance with JIS L 0846, of 4-5 or more, because the migration of the dye is sufficiently suppressed since the cationic dye that is not ionically bonded, which is likely to be detached by coming into contact with water, has been removed.
  • Another aspect of the present invention is directed to a resin layer-equipped artificial leather including: any one of the above-described artificial leather base materials; and a resin layer stacked on at least one surface of the artificial leather base material.
  • the resin layer has a surface with a lightness L* value of >50.
  • a lightness difference ⁇ L* between the artificial leather base material and the resin layer is 10 or more, because a high-contrast end face or appearance with a color difference and excellent design quality can be obtained, and the effects of the present invention become prominent.
  • Another aspect of the present invention is directed to a napped artificial leather obtained by napping at least one surface of any one of the above-described artificial leather base materials, the artificial leather base material having a surface with a lightness L* value of ⁇ 50.
  • Another aspect of the present invention is directed to a shoe including: the above-described napped artificial leather as an upper material; and an outsole bonded to the upper material, the outsole having a lightness L* value of >50.
  • Another aspect of the present invention is directed to a decorating sheet for being integrated with a molded body to be decorated, including any one of the above-described artificial leather base materials.
  • a decorating sheet for being integrated with a molded body to be decorated, including any one of the above-described artificial leather base materials.
  • the decorating sheet is a preform molded body shaped into a three-dimensional shape.
  • the migration of the dye to another member can also be suppressed in preform molding.
  • Another aspect of the present invention is directed to a decorative molded body including: a molded body to be decorated; and the decorating sheet as described above that is stacked and integrated on the molded body to be decorated.
  • a decorative molded body is less likely to be contaminated by the dye migrating from the artificial leather base material even when the molded body to be decorated is white or light colored, or transparent, such as a molded body to be decorated having a lightness L* value of >50.
  • the molded body to be decorated has a lightness L* value of >50, such as a white, light-color, or transparent one, or when the lightness difference ⁇ L* between the molded body to be decorated and the decorating sheet is 10 or more, because the contamination by the dye is less conspicuous.
  • FIG. 1 is a schematic cross-sectional view of a resin layer-equipped artificial leather 10 including an artificial leather base material 1 according to an embodiment.
  • FIG. 2A is a schematic diagram of a shoe 20 that uses the artificial leather base material 1 according to the embodiment as an upper material.
  • FIG. 2B is a schematic cross-sectional view of the shoe 20 .
  • FIG. 3A is an explanatory diagram for illustrating a step for molding a preform molded body 15 by vacuum molding using a decorating sheet 11 including the artificial leather base material.
  • FIG. 3B is an explanatory diagram for illustrating a step for molding a preform molded body 15 by vacuum molding using the decorating sheet 11 including the artificial leather base material.
  • FIG. 3C is an explanatory diagram for illustrating a step for molding a preform molded body 15 by vacuum molding using the decorating sheet 11 including the artificial leather base material.
  • FIG. 3D is an explanatory diagram for illustrating a step for molding a preform molded body 15 by vacuum molding using the decorating sheet 11 including the artificial leather base material.
  • FIG. 3E is an explanatory diagram for illustrating a step for molding a preform molded body 15 by vacuum molding using the decorating sheet 11 including the artificial leather base material.
  • FIG. 3F is an explanatory diagram for illustrating a step for molding a preform molded body 15 by vacuum molding using the decorating sheet 11 including the artificial leather base material.
  • FIG. 4A is an explanatory diagram for illustrating a step for molding a decorative molded body 30 by in-molding using the preform molded body 15 .
  • FIG. 4B is an explanatory diagram for illustrating a step for molding a decorative molded body 30 by in-molding using the preform molded body 15 .
  • FIG. 4C is an explanatory diagram for illustrating a step for molding the decorative molded body 30 by in-molding using the preform molded body 15 .
  • FIG. 4D is an explanatory diagram for illustrating a step for molding the decorative molded body 30 by in-molding using the preform molded body 15 .
  • FIG. 5 is a schematic cross-sectional view of a decorative molded body 50 produced by bonding a resin layer-equipped artificial leather 40 to a molded body 43 to be decorated.
  • FIG. 6 is a schematic perspective view showing the shape and the dimensions of a preform molded body according to examples.
  • an embodiment of an artificial leather base material according to the present invention will be described in detail, in conjunction with an exemplary production method thereof.
  • the artificial leather base material may be used as a resin layer-equipped artificial leather by forming a resin layer on the surface thereof, may be used as a napped artificial leather formed by napping the surface thereof into a suede-like or nubuck-like surface, or may be directly used as an artificial leather.
  • a fiber base material that includes a fiber fabric including cationic dye-dyeable polyester fibers and an elastic polymer applied to the fiber fabric is prepared.
  • the “cationic dye-dyeable polyester fibers” refer to polyester fibers, as will be described below, that include dye sites for a cationic dye in the molecule.
  • the fineness of the dyeable polyester fibers is not particularly limited.
  • the fineness is preferably 0.05 to 5 dtex, more preferably 0.09 to 4 dtex, particularly preferably 0.1 to 3 dtex, quite particularly preferably 0.14 to 2.5 dtex. With such a fineness, good color development can also be achieved with a small amount of the cationic dye, so that the migration of the cationic dye can be suppressed, and the flexible texture can be maintained.
  • the surface area of the fibers becomes too large, so that it becomes difficult to develop a dark color unless the cationic dye is used at a high concentration. As a result, the cationic dye tends to migrate to another member.
  • the fineness is too high, the surface area of the fibers becomes small. Accordingly, dyeing can be achieved with a smaller dye content in the case of developing the same color, so that the dye is less likely to migrate.
  • the writing effect and the napped feel are reduced, the texture tends to be hard, and the appearance and the surface touch are degraded.
  • a fineness that is too high tends to result in reduced stretchability during softening by heating, thus making it difficult to shape an accurate shape during molding.
  • the fiber fabric it is possible to use a non-woven fabric, a woven fabric, a knitted fabric, and the like without any particular limitation.
  • a non-woven fabric in particular, an entangled non-woven fabric obtained by entangling ultrafine fibers are preferable.
  • the non-woven fabric obtained by entangling ultrafine fibers can be easily stretched during molding.
  • the non-woven fabric makes it difficult for molten resin to permeate the artificial leather base material, thus retaining a high fiber-like texture.
  • an entangled non-woven fabric obtained by entangling ultrafine fibers of cationic dye-dyeable polyester fibers through an entangling treatment of ultrafine fiber-generating fibers
  • a method for producing, as an example of the fiber fabric, an entangled non-woven fabric (hereinafter also simply referred to as a “non-woven fabric”) obtained by entangling ultrafine fibers of cationic dye-dyeable polyester fibers through an entangling treatment of ultrafine fiber-generating fibers will be described in detail as a representative example.
  • the type of the non-woven fabric obtained by entangling ultrafine fibers is not particularly limited, and a non-woven fabric that uses direct spun ultrafine fibers may be used.
  • an entangled non-woven fabric made of ultrafine fibers of a cationic dye-dyeable polyester first, an entangled non-woven fabric of ultrafine fiber-generating fibers is produced.
  • the production method of the entangled non-woven fabric of ultrafine fiber-generating fibers include a method involving melt-spinning ultrafine fiber-generating fibers and directly collecting the resultant fibers as long fibers without intentionally cutting them, thus forming a fiber web, and a method involving forming a fiber web by carding or the like using staples obtained by cutting ultrafine fiber-generating fibers into a predetermined length, and thereafter subjecting them to a known entangling treatment.
  • long fibers refer to fibers that are continuous in the length direction other than staples, and are also referred to as “filaments”. From the viewpoint of sufficiently increasing the fiber density, the length of the long fibers is, for example, preferably 100 mm or more, more preferably 200 mm or more. The upper limit of the length of the long fibers is not particularly limited, and may be several meters, several hundred meters, several kilometers or longer, and be continuously spun. In the present embodiment, the production of a long fiber-web will be described in detail as a representative example.
  • Ultrafine fiber-generating fibers refer to fibers that generate ultrafine fibers having a small fineness as a result of performing a chemical or physical post-treatment on the spun fibers.
  • a production method using island-in-the-sea composite fibers as the ultrafine fiber-generating fibers will be described; however, known ultrafine fiber-generating fibers such as strip/division-type composite fibers may be used in place of the island-in-the-sea composite fibers.
  • An island-in-the-sea composite fiber is a multicomponent composite fiber composed of at least two polymers, and has a cross section on which an island component polymer is dispersed in a matrix composed of a sea component polymer.
  • a long-fiber web of the island-in-the-sea composite fibers is formed by melt-spinning the island-in-the-sea composite fibers and directly collecting the resultant fibers as long fibers on a net without cutting them.
  • a cationic dye-dyeable polyester obtained by copolymerization of a copolymerizable monomer including a dicarboxylic acid component composed mainly of terephthalic acid and including 1.5 to 3 mol % of a component represented by the following formula (I), and a glycol component composed mainly of ethylene glycol.
  • R represents hydrogen, or an alkyl group or a 2-hydroxyethyl group having 1 to 10 carbon atoms
  • X represents a metal ion, a quaternary phosphonium ion, or a quaternary ammonium ion.
  • Examples of the compound represented by the formula (I) include: alkali metal salts (lithium salt, sodium salt, potassium salt, rubidium salt, and cesium salt) of 5-sulfoisophthalic acid; 5-tetraalkyl phosphonium sulfoisophthalic acid such as 5-tetrabutyl phosphonium sulfoisophthalic acid, and 5-ethyl tributyl phosphonium sulfoisophthalic acid; and 5-tetraalkyl ammonium sulfoisophthalic acid such as 5-tetrabutyl ammonium sulfoisophthalic acid and 5-ethyl tributyl ammonium sulfoisophthalic acid.
  • alkali metal salts lithium salt, sodium salt, potassium salt, rubidium salt, and cesium salt
  • the compounds represented by the formula (I) may be used alone or in a combination of two or more. Among these, it is preferable to include a compound represented by the formula (I) where X is a quaternary phosphonium ion or a quaternary ammonium ion, because a cationic dye-dyeable polyester having excellent mechanical properties and high-speed spinnability can be obtained.
  • a cationic dye-dyeable polyester obtained by polymerization of a copolymerizable monomer that includes a dicarboxylic acid component including 1.5 to 3 mol % of the compound represented by the formula (I), in particular, the compound represented by the formula (I) where X is a quaternary phosphonium ion or a quaternary ammonium ion and composed mainly of terephthalic acid, and a glycol component composed mainly of ethylene glycol, because color migration can be easily suppressed even when the artificial leather base material is dyed in a dark a color.
  • X represents a metal ion, a quaternary phosphonium ion, or a quaternary ammonium ion.
  • X represents a metal ion, a quaternary phosphonium ion, or a quaternary ammonium ion.
  • the ratio of the unit represented by the formula (II) When the ratio of the unit represented by the formula (II) is less than 1.5 mol %, the dyeing fastness when the artificial leather base material is dyed with a cationic dye tends to be reduced. On the other hand, when the ratio of the unit represented by the formula (II) exceeds 3 mol %, the high-speed spinnability is reduced, thus making it difficult to obtain ultrafine fibers. Also, the mechanical properties, such as tear strength, of the resulting artificial leather base material tend to be significantly reduced.
  • terephthalic acid constitutes 50 mol % or more of the dicarboxylic acid component in the copolymerizable monomer.
  • the terephthalic acid content of the dicarboxylic acid component is preferably 75 mol % or more.
  • another dicarboxylic acid excluding the compound represented by the formula (I), may be included as the dicarboxylic acid component in order to lower the glass transition temperature.
  • another dicarboxylic acid component may include other dicarboxylic acids, including, for example, aromatic dicarboxylic acid such as isophthalic acid, cyclohexane dicarboxylic acid such as 1,4-cyclohexane dicarboxylic acid, and aliphatic dicarboxylic acid such as adipic acid, and derivatives thereof.
  • aromatic dicarboxylic acid such as isophthalic acid
  • cyclohexane dicarboxylic acid such as 1,4-cyclohexane dicarboxylic acid
  • aliphatic dicarboxylic acid such as adipic acid
  • the copolymerization ratio of another dicarboxylic acid is preferably 2 to 12 mol %, more preferably 3 to 10 mol %.
  • the glass transition temperature is not sufficiently lowered, and the degree of orientation of amorphous sites inside the fibers increases, so that dyeability tends to be reduced.
  • the copolymerization ratio of another dicarboxylic acid exceeds 12 mol %, the glass transition temperature is excessively lowered, and the degree of orientation of the amorphous sites inside the fibers is reduced, so that the fiber strength tends to be reduced.
  • an isophthalic acid unit is contained as another dicarboxylic acid unit, it is preferable to contain, as the dicarboxylic acid unit, preferably 1 to 6 mol %, more preferably 2 to 5 mol % of the isophthalic acid unit, because of the excellent mechanical properties and high-speed spinnability.
  • a 1,4-cyclohexane dicarboxylic acid unit and an adipic acid unit it is preferable to include, preferably 1 to 6 mol %, more preferably 2 to 5 mol % of each of the 1,4-cyclohexane dicarboxylic acid unit and the adipic acid unit, because a cationic dye-dyeable polyester having excellent mechanical properties and high-speed spinnability can be obtained.
  • “Composed mainly of ethylene glycol” means that ethylene glycol constitutes 50 mol % or more of the glycol component of the copolymerizable monomer.
  • the ethylene glycol content of the glycol component is preferably 75 mol % or more, more preferably 90 mol % or more.
  • Examples of other components include diethylene glycol and polyethylene glycol.
  • the glass transition temperature (Tg) of the cationic dye-dyeable polyester is not particularly limited, and is preferably 60 to 70° C., more preferably 60 to 65° C. When Tg is too high, the high-speed stretchability is reduced, and the shaping properties tend to be reduced when heat-molding the artificial leather base material for use.
  • a colorant such as carbon black, a weathering agent, an antifungal agent, and the like may be added to the cationic dye-dyeable polyester, so long as the effects of the present invention are not impaired.
  • sea component polymer a polymer having higher solubility in a solvent or higher decomposability by a decomposition agent than those of the cationic dye-dyeable polyester is selected.
  • the sea component polymer include a water-soluble polyvinyl alcohol resin (water-soluble PVA), polyethylene, polypropylene, polystyrene, an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer, a styrene-ethylene copolymer, and a styrene-acrylic copolymer.
  • the island-in-the-sea composite fibers can be produced by melt spinning in which the sea component polymer and the cationic dye-dyeable polyester serving as the island component polymer are melt-extruded from a multicomponent fiber spinning spinneret.
  • the fineness of the island-in-the-sea composite fibers is not particularly limited, and is preferably 0.5 to 10 dtex, more preferably 0.7 to 5 dtex.
  • the molten island-in-the-sea composite fibers discharged from the spinneret are cooled by a cooling apparatus, and are further drawn out and attenuated by a suction apparatus such as an air jet nozzle so as to have a desired fineness. Then, the drawn and attenuated long fibers are piled on a collection surface of a movable net or the like, thereby obtaining a long-fiber web. Note that, in order to stabilize the shape, a part of the long-fiber web may be further pressure-bonded by pressing the long-fiber web if necessary.
  • the obtained long-fiber web is subjected to an entangling treatment, thereby producing an entangled non-woven fabric of long fibers.
  • the entangling treatment for the long-fiber web include a treatment in which a plurality of layers of long-fiber webs are superposed in the thickness direction by using a cross lapper or the like, and subsequently needle-punched simultaneously or alternately from both sides such that at least one barb penetrates the web.
  • an oil solution, an antistatic agent, or the like may be added to the long fiber-web in any stage from the spinning step to the entangling treatment of the island-in-the-sea composite fiber.
  • the fiber density of the long fiber-web may be further increased in advance by performing a shrinking treatment in which the long-fiber web is immersed in hot water at about 70 to 150° C., thus imparting uniformity.
  • the fiber density may be further increased by performing hot pressing after the entangling treatment so as to impart shape stability.
  • the basis weight of the entangled non-woven fabric is preferably in the range of about 100 to 2000 g/m 2 .
  • a treatment to further increase the fiber density and the degree of entanglement may be performed by heat-shrinking the entangled non-woven fabric of the island-in-the-sea composite fibers.
  • a further densification of and the fixation of the shape of the entangled non-woven fabric, and the smoothing of the surface thereof may be performed by further hot-pressing the heat shrunk entangled non-woven fabric.
  • an entangled non-woven fabric composed of ultrafine fibers of the cationic dye-dyeable polyester is obtained.
  • a conventionally known ultrafine fiber formation method such as a method involving immersing the entangled non-woven fabric in a solvent or decomposition agent capable of selectively removing only the sea component polymer can be used without any particular limitation.
  • the water-soluble PVA as the sea component polymer, it is preferable to use hot water as the solvent.
  • the water-soluble PVA as the sea component polymer, it is preferable to remove the water-soluble PVA by extraction until the removal rate of the water-soluble PVA becomes about 95 to 100% by immersing the web in hot water at 85 to 100° C. for 100 to 600 seconds. Note that the water-soluble PVA can be more efficiently removed by extraction by repeating a dip-nipping treatment in the immersing.
  • the basis weight of the entangled non-woven fabric composed of ultrafine fibers of the cationic dye-dyeable polyester thus obtained is preferably 140 to 3000 g/m 2 , more preferably 200 to 2000 g/m 2 .
  • an elastic polymer such as polyurethane is impregnated into the internal voids of the entangled non-woven fabric before or after, or both before and after generating ultrafine fibers from ultrafine fiber-generating fibers such as island-in-the-sea composite fibers in order to impart shape stability and fullness to the entangled non-woven fabric of the cationic dye-dyeable polyester.
  • the elastic polymer examples include polyurethanes, acrylonitrile elastomers, olefin elastomers, polyester elastomers, polyamide elastomers, and acrylic elastomers. Among these, polyurethanes are preferable.
  • the elastic polymer may further contain a colorant such as a pigment (e.g., carbon black) or a dye, a coagulation regulator, an antioxidant, an ultraviolet absorber, a fluorescent agent, an antifungal agent, a penetrant, an antifoaming agent, a lubricant, a water-repellent agent, an oil-repellent agent, a thickener, a filler, a curing accelerator, a foaming agent, a water-soluble polymer compound such as polyvinyl alcohol or carboxymethyl cellulose, inorganic fine particles, and a conductive agent, so long as the effects of the present invention are not impaired.
  • a colorant such as a pigment (e.g., carbon black) or a dye, a coagulation regulator, an antioxidant, an ultraviolet absorber, a fluorescent agent, an antifungal agent, a penetrant, an antifoaming agent, a lubricant, a water-repellent agent, an oil-repellent agent,
  • the content ratio of the elastic polymer is preferably 0.1 to 50 mass %, more preferably 3 to 40 mass %, particularly preferably 5 to 25 mass %, quite particularly preferably 10 to 15 mass %, relative to the total amount of the elastic polymer and the cationic dye-dyeable polyester fibers, because color migration to the resin layer in contact with the artificial leather base material dyed with a cationic dye, the molded body to be decorated and other members is less likely to occur, and an artificial leather base material having well-balanced fullness and suppleness or the like can be obtained.
  • a raw fabric of the fiber base material which is an entangled non-woven fabric of the cationic dye-dyeable polyester that has been impregnated with the elastic polymer is obtained.
  • the raw fabric of the fiber base material is finished by being sliced into a plurality of pieces in a direction perpendicular to the thickness direction or ground as needed so as to adjust the thickness.
  • the raw fabric may be finished into a napped fiber base material that has been napped by being buffed on at least on one surface by using sand paper or emery paper with a grit number of preferably about 120 to 600, more preferably about 320 to 600.
  • the napped fiber base material becomes a suede-like or nubuck-like artificial leather.
  • the fiber base material is dyed with a cationic dye, thereby obtaining an artificial leather base material dyed with a cationic dye.
  • a cationic dye By dyeing the fiber base material with a cationic dye, excellent dyeing fastness is exerted as a result of the cationic dye being fixed by ionic bonding to the sulfonium ions that serve as the dye sites of the cationic dye of the cationic dye-dyeable polyester and are contained in the unit represented by the following formula (I a ):
  • any conventionally known cationic dye may be used without any particular limitation.
  • the cationic dye is dissolved in a dye liquid to become a dye ion exhibiting cationic properties, for example, a dye ion including a quaternary ammonium group or the like, and is conically bonded to the cationic dye-dyeable polyester fibers.
  • a cationic dye forms a salt with an anion such as a chlorine ion. This anion such as a chlorine ion is contained in the cationic dye, but will be washed off by washing performed after dyeing.
  • Specific examples of the cationic dye include: azo-based blue cationic dyes such as a C.I.
  • Basic Blue 54 and C.I. Basic Blue 159 oxazine-based blue cationic dyes such as C.I. Basic Blue 3, C.I. Basic Blue 6, C.I. Basic Blue 10, C.I. Basic Blue 12, C.I. Basic Blue 75, and C.I. Basic Blue 96; coumarin-based dyes such as C.I. Basic Yellow 40; methine-based dyes such as C.I. Basic Yellow 21; azomethine-based dyes such as C.I. Basic Yellow 28; azo-based red dyes such as C.I. Basic Red 29 and C.I. Basic Red 46; and xanthene-based dyes such as C.I. Basic Violet 11. These may be used alone or in a combination of two or more.
  • the dyeing method is not particularly limited, and examples thereof include methods in which dyeing is performed using a dyeing machine such as a jet dyeing machine, a beam dyeing machine, or a jigger.
  • a dyeing machine such as a jet dyeing machine, a beam dyeing machine, or a jigger.
  • the conditions for dyeing processing dyeing may be performed at a high pressure, but it is preferable to perform dyeing at normal pressure, because the environmental load is low, and the dyeing cost can be reduced.
  • the dyeing temperature is preferably 60 to 100° C., more preferably 80 to 100° C.
  • a dyeing assistant such as acetic acid or mirabilite may be used.
  • the concentration of the cationic dye in a dye liquid is in the range of preferably 0.05 to 20% owf, more preferably 0.1 to 15% owf, particularly preferably 0.5 to 20% owf, quite particularly preferably 1.0 to 15% owf, relative to the fiber base material to be dyed, because the color of the cationic dye-dyeable polyester fibers is sufficiently developed in a dark color, and the cationic dye becomes less likely to migrate to other members.
  • the concentration of the cationic dye in the dye liquid is too high, a large amount of the cationic dye that is not fixed to the dye sites of the cationic dye-dyeable polyester fibers is contained, so that the cationic dye tends to migrate to other members.
  • the concentration of the cationic dye is too low, it tends to be difficult to color the fiber base material in a dark color such as a color with a lightness L* value of ⁇ 50.
  • the fiber base material dyed with a cationic dye is subjected to a washing treatment in a hot water bath containing an anionic surfactant, thereby removing a cationic dye having a low bonding strength.
  • a washing treatment the cationic dye having a low bonding strength is sufficiently removed, and other members such as a resin layer that is stacked and a molded body to be decorated are less likely to be contaminated with the cationic dye contained in the artificial leather base material.
  • the anionic surfactant include Sordine R manufactured by NISSEI KASEI CO. LTD., SENKANOL A-900 manufactured by SENKA corporation, and Meisanol KHM manufactured by Meisei Chemical Works, Ltd.
  • the washing treatment in the hot water bath containing an anionic surfactant is performed in a hot water bath at preferably 50 to 100° C., more preferably 60 to 80° C.
  • a hot water bath it is preferable to use the dyeing machine with which the dyeing treatment has been performed, because the production process can be simplified.
  • the washing is performed for preferably about 10 to 30 minutes, more preferably about 15 to 20 minutes. Also, the washing is repeated once or more, preferably twice or more.
  • the fiber base material dyed with a cationic dye is dried after being washed.
  • the fiber base material dyed with a cationic dye may be further subjected to various finishing treatments as needed.
  • the finishing treatment include a flexibilizing treatment by crumpling, a reverse seal brushing treatment, an antifouling treatment, a hydrophilization treatment, a lubricant treatment, a softener treatment, an antioxidant treatment, an ultraviolet absorber treatment, a fluorescent agent treatment, and a flame retardant treatment.
  • the fiber base material dyed with a cationic dye is sufficiently washed by the above-described washing such that the washable chlorine in the cationic dye is about 90 ppm or less, relative to the weight of the resulting artificial leather base material, because the cationic dye becomes less likely to migrate to other members.
  • the artificial leather base material dyed with a cationic dye contains preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, particularly preferably 0.5 to 10 parts by mass, quite particularly preferably 1.0 to 10 parts by mass of the cationic dye, per 100 parts by mass of the fiber base material.
  • the cationic dye content per 100 parts by mass of the fiber base material is too large, the amount of the dye that is not bonded to the dye sites of the cationic dye-dyeable polyester fibers increases, so that the cationic dye tends to be likely to migrate to other members.
  • the cationic dye content is too small, it becomes difficult to color the fiber base material in preferably a dark color with a lightness L* value of ⁇ 50, more preferably a dark color with an L* value of ⁇ 35.
  • the artificial leather base material dyed with a cationic dye has the following properties. Specifically, it is preferable that the cotton stain in a water fastness test in accordance with a JIS method (JIS L 0846) is determined to be grade 4-5 or more. When the cotton stain of the artificial leather base material in the water fastness test is determined to be grade 4-5 or more, the artificial leather base material contains a small amount of the cationic dye that is not conically bonded, which is likely to be detached by coming into contact with water, so that the cationic dye is inhibited from migrating to other members.
  • JIS L 0846 JIS L 0846
  • the artificial leather base material dyed with a cationic dye according to the present embodiment has a grade of color difference, determined in an evaluation of color migration to a white polyvinyl chloride film with a thickness of 0.8 mm under a load of 750 g/cm 2 at 50° C. for 16 hours, of preferably 4 or more, more preferably 5 or more. Furthermore, in the artificial leather base material dyed with a cationic dye according to the present embodiment, when a white polyurethane film with a thickness of 250 ⁇ m is pressure-bonded under heating to a surface of the artificial leather base material via a polyurethane adhesive under 5 Kg/cm 2 at 130° C.
  • the artificial leather has a grade of color difference of the white polyurethane film, of preferably 3 or more, more preferably 4 or more.
  • the artificial leather base material dyed with a cationic dye according to the present embodiment has a grade of color difference, determined in an evaluation of color migration using methyl ethyl ketone (MEK), of preferably 2 or more, more preferably 3 or more, because the cationic dye is less likely to be isolated when it comes into contact with a solvent, so that high dyeing fastness that makes the cationic dye less likely to contaminate other members even in an application in which the artificial leather base material is integrated with a resin layer using an adhesive or the like.
  • MEK methyl ethyl ketone
  • the thickness of the artificial leather base material dyed with a cationic dye is not particularly limited, and is preferably 0.2 to 4 mm, more preferably 0.3 to 1.8 mm, because a flexible texture can be achieved.
  • the softness of the artificial leather base material which is measured in the manner described below, is preferably 2.0 to 6.0 mm, more preferably 2.5 to 5.0 mm, because a flexible texture can be achieved.
  • the product of the softness and the thickness is preferably 2 or more, more preferably 2.5 or more, because well-balanced thickness and texture can be achieved, resulting in an elegant texture suitable for an artificial leather product.
  • the apparent density of the artificial leather base material is preferably 0.3 to 0.6 g/cm 3 or more, particularly preferably 0.45 to 0.55 g/cm 3 or more, because a flexible texture can be achieved.
  • the artificial leather base material dyed with a cationic dye according to the present embodiment is less likely to cause contamination of the resin layer and a molded body to be decorated, which will be described below, with a cationic dye even when the artificial leather base material is colored in a dark color such as a color with an L* value of 50.
  • the artificial leather base material dyed with a cationic dye has an L* value of ⁇ 50, the effects of the present invention become prominent particularly when the artificial leather base material is colored in a dark color such as a color with an L* value of ⁇ 35.
  • the cationic dye-dyeable polyester fibers and the elastic polymer may be colored with a pigment such as carbon black, in addition to being dyed with a cationic dye so as to have an L* value of ⁇ 35.
  • a pigment such as carbon black
  • the artificial leather base material dyed with a cationic dye according to the present embodiment described thus may be finished into a suede-like or nubuck-like napped artificial leather by napping the fibers on the surface thereof, or may be finished into a resin layer-equipped artificial leather by providing a resin layer on the surface thereof.
  • the artificial leather base material may be used as an artificial leather product such as shoes for which the artificial leather base material is integrated with a resin molded body such as an outsole, or may be used as a decorating sheet that is to be integrated with a molded body to be decorated used for production of a decorative molded body such as a casing of a mobile device.
  • a resin layer-equipped artificial leather in which a resin layer is stacked and integrated on at least one surface of an artificial leather base material dyed with a cationic dye.
  • FIG. 1 is a schematic cross-sectional view of a resin layer-equipped artificial leather 10 including an artificial leather base material 1 .
  • the resin layer-equipped artificial leather 10 includes an artificial leather base material 1 , and a resin layer 2 stacked on one surface of the artificial leather base material 1 .
  • the artificial leather base material 1 is an artificial leather base material as described above that includes a surface with a lightness L* value of ⁇ 50, and a fiber base material including cationic dye-dyeable polyester fibers and an elastic polymer, the artificial leather base material 1 being dyed with at least one cationic dye.
  • Examples of the resin layer 2 include layers that have been used for forming the resin layers of the conventionally known resin layer-equipped artificial leathers, namely, layers composed mainly of polyurethane, an acrylonitrile elastomer, an olefin elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer or the like.
  • the resin layer-equipped artificial leather 10 even when a white or light-color resin layer 2 such as the one having an L* value of >50, preferably an L* value>70, is formed, the resin layer 2 is less likely to be contaminated by the cationic dye included in the artificial leather base material 1 .
  • the lightness difference ⁇ L* in L* value between the artificial leather base material 1 and the resin layer 2 is preferably 10 or more, more preferably 20 or more, particularly preferably 30 or more, because a high-contrast appearance having an excellent design quality can be achieved.
  • FIG. 2A is a schematic diagram showing the appearance of an upper portion of a shoe 20 that uses the artificial leather base material 1 as an upper material.
  • FIG. 2B is a schematic cross-sectional view of the upper portion of the shoe 20 .
  • end portions of the artificial leather base material 1 are bonded to and integrated with a rubber sole 3 made of a rubber, which is a light-color resin layer with an L* value of >50, with adhesive layers 3 a , to form a resin layer-equipped artificial leather 7 .
  • a patch 5 which is a light-color resin layer with an L* value of >50, is bonded to the surface of the artificial leather base material 1 with an adhesive layer 5 a , to form a resin layer-equipped artificial leather 8 .
  • the resin layer-equipped artificial leather 7 refers to a region having a structure that includes the artificial leather base material 1 dyed with a cationic dye that has a lightness L* value of ⁇ 50, the light-color or white rubber sole 3 made of a rubber that has an L* value of >50 and is integrated with the end portions of the artificial leather base material 1 with the adhesive layers 3 a .
  • the resin layer-equipped artificial leather 8 refers to a region including the artificial leather base material 1 , and the patch 5 , which is a light-color or white resin layer that has an L* value of >50 and is bonded to and integrated with the surface of the artificial leather base material 1 with the adhesive layer 5 a .
  • Such resin layer-equipped artificial leathers 7 and 8 even when they are bonded to and integrated with the white or light-color rubber sole 3 or patch 5 , such as those having an L* value of >50, preferably an L* value>70, the cationic dye included in the dark-color artificial leather base material 1 is less likely to contaminate the rubber sole 3 and the patch 5 .
  • ⁇ L* which is a difference in L* value between the artificial leather base material 1 and the rubber sole 3 or the patch 5 , is preferably 10 or more, more preferably 20 or more, particularly preferably 30 or more, because of the excellent design quality due to a color with an excellent contrast.
  • a preform molded body obtained by molding a decorating sheet into a three-dimensional shape by preform molding is produced in advance.
  • a method for molding a preform molded body using vacuum molding will be described in detail with reference to FIGS. 3A to 3F .
  • a molding method such as vacuum pressure molding, pressure molding, or hot-press molding may be used in place of vacuum molding.
  • a non-air-permeable thermoplastic resin sheet 12 is placed on a decorating sheet 11 , which is a napped artificial leather including an artificial leather base material dyed with a cationic dye, to form a superposed body 13 .
  • the decorating sheet 11 which is a napped artificial leather, is air-permeable, and thus cannot be directly subjected to vacuum molding.
  • the thermoplastic resin sheet 12 is placed on the decorating sheet 11 in order to temporarily impart airtightness to the decorating sheet 11 in vacuum molding.
  • thermoplastic resin sheet it is possible to use any sheet or film that is softened by heating during vacuum molding so as to be provided with a shape, is capable of maintaining airtightness without a pinhole or the like, and can be selectively detached in a later step, without any particular limitation.
  • thermoplastic resin for fouling such a thermoplastic resin sheet include amorphous thermoplastic resins such as a (meth)acrylic resin, and crystalline thermoplastic resins having a low melting point, including, for example, polyolefin resins such as polyethylene and polypropylene.
  • the thickness of the thermoplastic resin sheet is preferably about 10 to 300 ⁇ m, more preferably about 15 to 200 ⁇ m, particularly preferably about 30 to 100 ⁇ m. When the thermoplastic resin sheet is too thick, the shaping properties of the decorating sheet 11 tend to be reduced. When the thermoplastic resin sheet is too thin, it tends to be difficult to detach the thermoplastic resin sheet 12 from the decorating sheet 11 after preform molding.
  • the superposed body 13 is softened by being heated with heaters H.
  • the heating temperature with the heaters H is a temperature that allows the shape of the superposed body 13 to be changed so as to follow the shape of a mold M 1 of a vacuum molding machine M shown in FIG. 3B , without causing complete melting, and can be selected from the range of 100 to 180° C., for example.
  • the heated and softened superposed body 13 is subjected to vacuum molding. Specifically, the heated and softened superposed body 13 is disposed so as to cover the mold M 1 of the vacuum molding machine M shown in FIG. 3B . Then, as shown in FIG. 3C , the softened superposed body 13 is brought into close contact with the mold M 1 of the vacuum molding machine M, and the air between the superposed body 13 and the mold M 1 is discharged by a vacuum pump P from vacuum holes v formed in the mold M 1 , thereby causing the superposed body 13 to be adsorbed by the mold M 1 so as to be tightly attached thereto with atmospheric pressure. Then, the shaped superposed body 13 is cooled and solidified.
  • a preform molded body 14 is released from the mold M 1 .
  • unnecessary portions N of the preform molded body 14 are trimmed as needed.
  • thermoplastic resin sheet 12 is detached, to give a preform molded body 15 .
  • the preform molded body 15 thus obtained is integrated with a molded body to be decorated, to form a decorative molded body.
  • Examples of the method for integrating the preform molded body with a molded body to be decorated include in-molding in which the preform molded body is integrated with a molded body to be decorated, which is a resin molded body molded by injection molding, and a method in which a molded body to be decorated that is molded in advance is bonded to one surface of the preform molded body via an adhesive.
  • thermoplastic resin sheet 12 A method for producing a decorative molded body by in-molding will be described with reference to FIGS. 4A to 4D .
  • a method for performing in-molding using a preform molded body 15 from which the thermoplastic resin sheet 12 has been detached will be described in the present embodiment, a preform molded body 15 with the thermoplastic resin sheet 12 attached thereto may be subjected to in-molding, and, thereafter, the thermoplastic resin sheet 12 may be detached.
  • a mold 17 includes a movable mold 17 a having a cavity C, and a fixed mold 17 b .
  • a stripper plate 17 c is disposed between the movable mold 17 a and the fixed mold 17 b .
  • the preform molded body 15 is disposed in the cavity C.
  • the method for disposing the preform molded body 15 in the cavity C is not particularly limited, it is preferable that the preform molded body 15 is fixed to the cavity C for the purpose of positioning.
  • the preform molded body 15 is not fixed to the cavity C, there is the possibility that the preform molded body 15 may be positionally displaced in the cavity C with the flowing of the injected resin during injection molding in the subsequent step.
  • the method for fixing the preform molded body 15 to the cavity C include a method in which the preform molded body 15 is fixed to the surface of the movable mold with a pressure-sensitive adhesive, and a method in which the preform molded body 15 is fixed by fitting a hole portion or a recess included in the shape of the preform molded body 4 to a core of the movable mold that matches the shape of the hole portion or the recess.
  • molten resin 16 a is injected into the cavity C by injection molding, thereby molding an in-molded body, which is a decorative molded body in which the preform molded body 15 is integrated on the surface thereof. More specifically, the movable mold 17 a and the fixed mold 17 b are closed, then a cylinder 18 a of an injection molding machine 18 is advanced until a nozzle 18 c comes into contact with a sprue bushing 17 f of the fixed mold 17 b , and the molten resin 16 a molten in the cylinder 18 a of the injection molding machine is injected with a screw 18 b , thereby injecting the molten resin 16 a into the cavity C of the mold 17 .
  • the injected molten resin 16 a flows into the cavity C through a resin flow path R inside the mold 17 , and is charged into the cavity C.
  • the molten resin 16 a appropriately permeates the preform molded body 15 , so that the injection-molded body, which is the molded body 16 to be decorated molded by injection molding, is integrated with the preform molded body 15 so as to maintain high adhesion due to an anchoring effect.
  • the resin for forming the injection-molded body molded by in-molding include various thermoplastic resins, including, for example, an ABS resin, a polycarbonate resin, polyolefin resins such as polypropylene, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate, and various polyamide resins can be used without any particular limitation, and these resins are appropriately selected according to the application.
  • resins having excellent impact resistance, such as an ABS resin, a polycarbonate resin, and a polyolefin resin such as polypropylene are suitably used as the resin for use in the casings of a mobile phone, a mobile device, a home electrical appliance and the like.
  • conditions for the injection molding conditions (resin temperature, mold temperature, injection pressure, injection speed, holding pressure after injection, cooling time) that allow the resin to flow to the flow terminal end may be selected as appropriate according to the melting point and the melt viscosity of the injected resin, the shape of the molded body, and the resin thickness.
  • the molten resin 16 a is cooled, to form an injection-molded body, which is the molded body 16 to be decorated, as shown in FIG. 4C .
  • a decorative molded body 30 in which the preform molded body 15 is integrated with the molded body 16 to be decorated is molded.
  • the movable mold 17 a and the fixed mold 17 b are separated from each other.
  • a decorative molded body 30 as shown in FIG. 4D is taken out.
  • the decorative molded body 30 in which the molded body 16 to be decorated, which is an injection-molded body, is integrated with one surface of the preform molded body 15 is obtained.
  • a napped artificial leather including an artificial leather base material dyed with a cationic dye is stacked and integrated on the surface layer.
  • the contamination by the cationic dye due to heating during production or use is suppressed even when a light-color or white, or transparent molded body to be decorated such as the one with a lightness L* value of >50, or even a lightness L* value of >70 is used.
  • ⁇ L* which is a difference in L* value between the decorating sheet and the molded body to be decorated, is preferably 10 or more, more preferably 20 or more, particularly preferably 30 or more, because of the excellent design quality due to a color with an excellent contrast.
  • Such a decorative molded body can be suitably used as the casings of a mobile phone, a smartphone, various mobile devices, a home electrical appliance and the like, the interior members of a vehicle, an aircraft and the like, and the exterior members of a building material, an article of furniture and the like.
  • FIG. 5 is a schematic cross-sectional view of a decorative molded body 50 including a resin layer-equipped artificial leather 40 that uses an artificial leather base material 41 including a surface with a lightness L* value of ⁇ 50, and a fiber base material including cationic dye-dyeable polyester fibers and an elastic polymer, the resin layer-equipped artificial leather 40 being dyed with a cationic dye.
  • the artificial leather base material 41 dyed with a cationic dye that has a lightness L* value of ⁇ 50 is finished into a resin layer-equipped artificial leather 40 by stacking and integrating a resin layer 42 on the surface thereof. Then, the artificial leather base material 41 is bonded to a resin molded body 43 via an adhesive layer 44 .
  • the decorative molded body 50 has an opening H.
  • a cross section E 1 of the opening H and an end face E 2 of the decorative molded body 50 are exposed to the outside, and constitute portions that can be visually recognized by the user.
  • the fiber base material included in the artificial leather base material 41 may be required to be colored, from the viewpoint of design quality.
  • the cationic dye is less likely to migrate from the dark-color artificial leather base material 41 to the resin layer 42 and the resin molded body 43 .
  • the non-woven fabric obtained by three-dimensionally entangling the island-in-the-sea composite fibers was impregnated with a polyurethane emulsion (emulsion composed mainly of polycarbonate/ether polyurethane with a polyurethane solid concentration of 30%), and was dried in a drying furnace at 150° C., thereby applying polyurethane to the non-woven fabric.
  • a polyurethane emulsion emulsion composed mainly of polycarbonate/ether polyurethane with a polyurethane solid concentration of 30%
  • the sea component included in the island-in-the-sea composite fibers was removed by extraction by immersing the non-woven fabric in which the island-in-the-sea composite fibers to which polyurethane had been applied were three-dimensionally entangled in hot water at 95° C.
  • the non-woven fabric was dried in a drying furnace at 120° C., thereby obtaining a fiber base material including the non-woven fabric of the cationic dye-dyeable polyester fibers with a fineness of 0.2 dtex that had been impregnated with polyurethane.
  • the obtained fiber base material had a mass ratio of non-woven fabric/polyurethane of 90/10.
  • the fiber base material was sliced into halves, and the surface thereof was napped by being buffed with sand paper with a grit number of 600.
  • the napped fiber base material had a fineness of 0.2 dtex, a polyurethane ratio of 10 mass %, a thickness of 0.78 mm, and an apparent density 0.51 g/cm 3 .
  • the napped fiber base material was dyed into red by being immersed in a dyeing bath storing a 90° C. dye liquid containing 19% owf of Nichilon Red-GL (manufactured by NISSEI KASEI CO., LTD.) as a cationic dye and 1 g/L of 90% acetic acid as a dyeing assistant at a bath ratio of 1:30 for 40 minutes.
  • the step of soaping the napped fiber base material in the same dyeing bath at 70° C. using a hot water bath containing 2 g/L of Sordine R as an anionic surfactant was repeated twice.
  • the napped fiber base material was dried, thereby obtaining a dyed suede-like artificial leather.
  • a dark-red suede-like artificial leather (suede-like artificial leather base material) including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.2 dtex was obtained.
  • the obtained suede-like artificial leather had a thickness of 0.83 mm and an apparent density of 0.47 g/cm 3 .
  • various properties of the suede-like artificial leather were evaluated as follows.
  • the cationic dye content of the suede-like artificial leather was quantitatively determined by the following method.
  • the prepared dye liquid was collected, and five diluted dye liquids at different concentrations with dilution ratios of 10 to 100 were prepared. Then, the absorbance for the region with a wavelength of 380 to 780 nm of each of the five diluted dye liquids was measured with a spectrophotometer (U-3010 manufactured by Hitachi High-Tech Science Corporation) for every 1 nm, and the measured values were added up, thereby creating a calibration curve of the absorbance with respect to the dye concentration (g/L).
  • a spectrophotometer U-3010 manufactured by Hitachi High-Tech Science Corporation
  • the dye liquid (residual dye liquid) in the dyeing bath after dyeing was collected, and the absorbance for the region with a wavelength of 380 to 780 nm was measured for every 1 nm, and the measured values were added up, thereby determining the dye concentration C (g/L) of the residual dye liquid from the calibration curve.
  • the dye concentration C1 (g/L) in the cleaning solution after the first soaping and the dye concentration C2 (g/L) in the cleaning solution after the second soaping were determined in the same manner.
  • the mass of the dyed napped fiber base material is represented as S (g)
  • the amount of the dye dissolved in the dye liquid to achieve the target owf % is represented as P (g)
  • the amount of the liquid used when the bath ratio to the napped fiber base material was adjusted is represented as W(L).
  • W1 (L) the amount of the liquid used for the first soaping
  • the dye removal amount P2 (g) by the second soaping was also calculated in the same manner.
  • the lightness L* was determined in accordance with JIS Z 8729 from the coordinate values of the L*a*b* color system on the surface of a cut-out piece of the suede-like artificial leather. The value was an average of the values for three points evenly selected from average positions of the test piece.
  • the thickness of the suede-like artificial leather was measured in accordance with a JIS method. Using a thickness measurement instrument, the thicknesses of five different portions of the sample were measured under the pressurization condition of a load of 23.5 KPa for 10 seconds, and an average value of the measured thicknesses was calculated, after which the value was rounded at the third decimal place.
  • the bending resistance of the suede-like artificial leather was measured using a softness tester (leather softness measuring instrument ST 300: manufactured by the United Kingdom, MSA Engineering Systems Limited). Specifically, a predetermined ring with a diameter of 25 mm was set on a lower holder of the device, and thereafter, the suede-like artificial leather was set on the lower holder. Then, a metal pin (diameter: 5 mm) fixed to an upper lever was pressed down toward the suede-like artificial leather. Then, the upper lever was pressed down, and the value at the time when the upper lever was locked was read. Note that the value indicated the penetration depth, and the larger the value, the suppler the leather was.
  • the suede-like artificial leather is cut out into a piece of 2.45 cm long by 2.45 cm wide, and the cut-out piece was sandwiched between the surfaces of measurement white cloths, and the cut-out piece and the measurement white cloth were stapled together at four locations on the upper, lower, left and right sides, to produce a test base material. Then, the test base material is immersed in MEK placed in a glass container for 20 seconds, and thereafter taken out, and air-dried. After the drying, the state of contamination to the measurement white cloth was evaluated. As for the evaluation, the most contaminated portion, regardless of whether it was located on the front or the back, was visually evaluated according to the JIS gray-scale standard, and rated using degrees 1 to 5.
  • the color difference ⁇ E* of the urethane film before and after the heat treatment of the resin layer-equipped artificial leather was measured using a spectrophotometer, and evaluated according to the following criteria:
  • the suede-like artificial leather was cut-out into a piece of 30 cm long by 20 cm wide, to prepare a sample. Then, the tactile impression of the surface when rubbed by the palm of a hand was evaluated according to the following criteria:
  • the suede-like artificial leather was cut-out into a piece of 30 cm long by 20 cm wide, to prepare a sample. Then, the tactile impression of the sample when grabbed was evaluated according to the following criteria:
  • a napped fiber base material was obtained in the same manner as in Example 1, except that the napped fiber base material included a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 2.0 dtex, and had a polyurethane ratio of 5 mass %, a thickness of 0.82 mm, and an apparent density of 0.46 g/cm 3 . Then, the obtained napped fiber base material was dyed into red by being immersed in a 90° C.
  • a dyed dark-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 2.0 dtex was obtained.
  • the obtained suede-like artificial leather had a thickness of 1.19 mm and an apparent density of 0.40 g/cm 3 .
  • various properties of the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a napped fiber base material was obtained in the same manner as in Example 1, except that the napped fiber base material included a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 3.3 dtex, and had a polyurethane ratio of 5 mass %, a thickness of 0.75 mm, and an apparent density of 0.46 g/cm 3 . Then, the obtained napped fiber base material was dyed into red by being immersed in a 90° C.
  • a dyed dark-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 3.3 dtex was obtained.
  • the obtained suede-like artificial leather had a thickness of 1.02 mm and an apparent density of 0.40 g/cm 3 .
  • various properties of the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a napped fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 4.2 dtex, and having a polyurethane ratio of 5 mass %, a thickness of 0.75 mm, and an apparent density 0.45 g/cm 3 was produced. Then, the obtained napped fiber base material was dyed into red by being immersed in a 90° C.
  • a dyed dark-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 4.2 dtex was obtained.
  • the obtained suede-like artificial leather had a thickness of 1.06 mm and an apparent density of 0.39 g/cm 3 .
  • various properties of the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a napped fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.08 dtex, and having a polyurethane ratio of 10 mass %, a thickness of 0.75 mm, and an apparent density 0.52 g/cm 3 was produced. Then, the obtained napped fiber base material was dyed into red by being immersed in a 90° C.
  • a dyed suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.08 dtex was obtained.
  • the obtained suede-like artificial leather had a thickness of 0.82 mm and an apparent density of 0.48 g/cm 3 .
  • various properties of the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a napped fiber base material obtained in the same manner as in Example 1 was dyed in the same manner as in Example 1 except that dye concentration was changed from 19% owf to 6% owf, to obtain a dyed dark-red suede-like artificial leather. Then, various properties of the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a napped fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 5.1 dtex, and having a polyurethane ratio of 5 mass %, a thickness of 0.78 mm, and an apparent density 0.44 g/cm 3 was produced. Then, the obtained napped fiber base material was dyed into red by being immersed in a 90° C.
  • a dyed dark-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 5.1 dtex was obtained.
  • the obtained suede-like artificial leather had a thickness of 1.05 mm and an apparent density of 0.38 g/cm 3 .
  • the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a dyed dark-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers was obtained in the same manner as in Example 1, except that the napped fiber base material was washed with water at 70° C., instead of repeating twice the step of soaping the napped fiber base material at 70° C. using a hot water bath containing 2 g/L of Sordine R as an anionic surfactant in Example 1. Then, the suede-like artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a dyed dark-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers was obtained in the same manner as in Example 6, except that the napped fiber base material was washed with water at 70° C., instead of repeating twice the step of soaping the napped fiber base material at 70° C. using a hot water bath containing 2 g/L of Sordine R as an anionic surfactant in Example 6. Then, the suede-like artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the fiber base material was jet-dyed with D. Red-W, Kiwalon Rubin 2GW, and Kiwalon Yellow 6GF serving as disperse dyes at 130° C. for 1 hour, and reductively cleaned in the same dyeing bath, to obtain a dyed dark-red suede-like artificial leather.
  • the suede-like artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a napped fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.14 dtex, and having a polyurethane ratio of 10 mass %, a thickness of 0.78 mm, and an apparent density 0.51 g/cm 3 was produced. Then, the obtained fiber base material was dyed into red by being immersed in a 90° C. dyeing bath containing 3.8% owf of Nichilon Red-GL (manufactured by NISSEI KASEI CO., LTD.) serving as a cationic dye, and 1 g/L of 90% acetic acid as a dyeing assistant at a bath ratio of 1:30 for 40 minutes.
  • Nichilon Red-GL manufactured by NISSEI KASEI CO., LTD.
  • the step of soaping the napped fiber base material in the same dyeing bath at 70° C. using a hot water bath containing 2 g/L of Sordine R as an anionic surfactant was repeated twice.
  • the fiber base material was dried, thereby obtaining a dyed light-red suede-like artificial leather including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.14 dtex.
  • the obtained suede-like artificial leather had a thickness of 0.82 mm and an apparent density of 0.48 g/cm 3 .
  • the suede-like artificial leather were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the non-woven fabric obtained by three-dimensionally entangling the island-in-the-sea composite fibers was impregnated with a polyurethane emulsion (emulsion composed mainly of polycarbonate/ether polyurethane with a polyurethane solid concentration of 30%), and was dried in a drying furnace at 150° C., thereby applying polyurethane to the non-woven fabric.
  • the sea component was removed by extraction by immersing the non-woven fabric of the island-in-the-sea composite fibers to which polyurethane had been applied in hot water at 95° C.
  • the non-woven fabric to which polyurethane had been applied was sliced into halves, then the surface thereof was buffed with sand paper with a grit number of 600, and the non-woven fabric was thereby finished into a suede-like fiber base material.
  • the fiber base material had a fineness of 0.08 dtex, a polyurethane content ratio of 10 mass %, a thickness of 0.5 mm, and an apparent density 0.55 g/cm 3 .
  • the fiber base material was dyed into red by being immersed in a 90° C. dye liquid containing 18% owf of Nichilon Red-GL (manufactured by NISSEI KASEI CO., LTD.) as a cationic dye and 1 g/L of 90% acetic acid as a dyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the step of soaping the fiber base material in the same dyeing bath at 70° C. using a hot water bath containing 2 g/L of Sordine R as an anionic surfactant was repeated twice. Then, after the soaping, the fiber base material was dried, thereby obtaining a dark-red suede-like artificial leather dyed with a cationic dye.
  • Nichilon Red-GL manufactured by NISSEI KASEI CO., LTD.
  • a decorating sheet which was a dyed dark-red suede-like artificial leather dyed with a cationic dye that included a fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with 0.08 dtex and polyurethane was obtained.
  • the suede-like artificial leather had a thickness of 0.55 mm and an apparent density of 0.50 g/cm 3 .
  • the L* value was 36. Then, various properties of the suede-like artificial leather were evaluated as follows.
  • the lightness L* was determined in accordance with JIS Z 8729 from the coordinate values of the L*a*b* color system on the surface of a cut-out piece of the suede-like artificial leather. The value was an average of the values for three points evenly selected from average positions of the test piece.
  • a water fastness test for a cotton cloth in accordance with a JIS method (JIS L 0846) was performed. Specifically, a test piece of 6 cm by 6 cm was cut out from the suede-like artificial leather. Then, the test piece was immersed in water at room temperature, and thereafter attached to a sweat testing machine. The test piece was held in a dryer machine at 37 ⁇ 2° C. for 4 hours under a load of about 45 N. Then, the fastness of the test piece was evaluated by making comparison with the contamination gray scale. Then, the grade at that time was determined.
  • JIS L 0846 JIS L 0846
  • the obtained decorating sheet was molded using a mold having a cavity for obtaining a preform molded body.
  • the preform molded body was a saucer-shaped molded body having a height of 7 mm from the bottom surface to the outer surface, which simulated a smartphone cover, as shown in FIG. 6 .
  • a transparent acrylic sheet with a thickness of 75 ⁇ m was placed on one surface of the decorating sheet, to form a superposed body. Then, the superposed body was heated to a temperature of 150° C. with an infrared heater, and was subjected to vacuum pressure molding at a predetermined air pressure using molds having various shapes. Through vacuum pressure molding, a preform molded body with a thermoplastic resin sheet in which the surface of the transparent acrylic sheet and the decorating sheet forming the superposed body were thermally compressed was obtained. Then, the transparent acrylic sheet was detached from the preform molded body with a thermoplastic resin sheet, to obtain a preform molded body.
  • in-molding was performed using the obtained preform molded body.
  • an in-molding mold having a shape corresponding to the shape of the preform molded body was prepared. Then, the mold was mounted on an injection molding machine, and the preform molded body was disposed in a cavity of the mold. Then, a milk-white ABS resin (TOYOLAC ABS700 manufactured by Toray Industries Inc.) was injection-molded at a resin temperature of 240° C. and a mold temperature of 50° C. A decorative molded body was obtained by performing in-mold in this manner. Note that the L* value of the injection-molded body to be decorated was 92.
  • Another decorative molded body was also produced in the same manner except that a clear-color polycarbonate (Iupilon 52000 manufactured by Mitsubishi Engineering-Plastics Corporation) was used in place of the ABS resin, and that the conditions were changed such that the resin temperature was 280° C. and the mold temperature was 80° C.
  • the L* value of the injection-molded decorated molded body was 93.
  • the decorative molded body thus molded was observed visually, and the dye migration of the decorated molded body was evaluated using the contamination gray scale, and rated using grades 1 (significant contamination) to 5 (no contamination).
  • a decorating sheet was placed on top of the surface of an ABS resin or polycarbonate rectangular plate of 30 mm ⁇ 50 mm having a thickness of 1.5 mm, and was uniformly pressurized so as to apply a load of 7.5 g/cm 2 thereto. Then, the whole was left under an atmosphere of 70° C. and 95% RH for 24 hours. Then, the color difference ⁇ E* between the rectangular plate before being left and the rectangular plate after being left was measured with a spectrophotometer, and was evaluated according to the following criteria.
  • a decorating sheet was obtained by dyeing the suede-like fiber base material in the same manner as in Example 10 except that dyeing was performed in Example 10 under the following dyeing conditions.
  • the fiber base material was dyed into blue by being immersed in a 90° C. dye liquid containing 5% owf of Nichilon Blue-AZN (manufactured by NISSEI KASEI CO., LTD.) as a cationic dye and 1 g/L of 90% acetic acid as a dyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, the step of soaping the fiber base material in the same dyeing bath at 70° C. using a hot water bath containing 2 g/L of Sordine R as an anionic surfactant was repeated twice. Then, after the soaping, the fiber base material was dried, thereby obtaining a dyed suede-like artificial leather.
  • Nichilon Blue-AZN manufactured by NISSEI KASEI CO., LTD.
  • a decorating sheet which was a dyed dark-blue suede-like artificial leather dyed with a cationic dye that included a fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with 0.08 dtex and polyurethane was obtained.
  • the suede-like artificial leather had a thickness of 0.83 mm and an apparent density of 0.47 g/cm 3 .
  • the L* value was 47.
  • Example 10 a preform molded body and a decorative molded body were molded in the same manner as in Example 10, except that the obtained decorating sheet was used in place of the decorating sheet obtained in Example 10, and the preform molded body and the decorative molded body were evaluated in the same manner as in Example 10. The results are shown in Table 2.
  • a suede-like fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.2 dtex, and having a polyurethane ratio of 10 mass %, a thickness of 0.82 mm, and an apparent density of 0.46 g/cm 3 was produced. Then, the obtained fiber base material was dyed into red by being immersed in a 90° C.
  • a decorating sheet which was a dark-red suede-like artificial leather dyed with a cationic dye that included a fiber base material including a non-woven fabric of cationic dye-dyeable polyester fibers with a fineness of 0.2 dtex and polyurethane was obtained.
  • the suede-like artificial leather had a thickness of 1.19 mm and an apparent density of 0.40 g/cm 3 .
  • the L* value was 42.
  • Example 10 a preform molded body and a decorative molded body were molded in the same manner as in Example 10, except that the obtained decorating sheet was used in place of the decorating sheet obtained in Example 10, and were evaluated in the same manner as in Example 10. The results are shown in Table 2.
  • a decorating sheet which was a suede-like artificial leather, was obtained by dyeing the suede-like fiber base material in the same manner as in Example 10, except that dyeing was performed under the following dyeing conditions in Example 10.
  • the suede-like fiber base material was dyed into blue by being immersed in a 90° C. dye liquid containing 5% owf of Nichilon Blue-AZN (manufactured by NISSEI KASEI CO., LTD.) as a cationic dye, and 1 g/L of 90% acetic acid as a dyeing assistant at a bath ratio of 1:30 for 40 minutes. Then, washing with water was performed once in the same dyeing bath at 70° C. Then, the suede-like fiber base material was dried, to obtain a decorating sheet, which was a dark-blue suede-like artificial leather dyed with a cationic dye.
  • Nichilon Blue-AZN manufactured by NISSEI KASEI CO., LTD.
  • the suede-like artificial leather had a thickness of 0.83 mm and an apparent density of 0.47 g/cm 3 .
  • the L* value was 33.
  • a preform molded body and a decorative molded body were molded in the same manner as in Example 10, except that the obtained decorating sheet was used in place of the decorating sheet obtained in Example 10, and were evaluated in the same manner as in Example 10. The results are shown in Table 2.
  • a suede-like fiber base material including a non-woven fabric to which polyurethane had been applied was obtained in the same manner as in Example 10, except that isophthalic acid-modified PET (containing 6 mol % of an isophthalic acid unit) was used as the thermoplastic resin serving as the island component. Then, the suede-like fiber base material was jet-dyed with D. Red-W, Kiwalon Rubin 2GW, and Kiwalon Yellow 6GF serving as disperse dyes at 130° C. for 1 hour, and reductively cleaned in the same dyeing bath, to obtain a decorating sheet, which was a dyed dark-red suede-like artificial leather. Then, the obtained decorating sheet was evaluated in the same manner as in Example 10. The results are shown in Table 2.
  • a suede-like fiber base material including a non-woven fabric to which polyurethane had been applied was obtained in the same manner as in Example 10, except that isophthalic acid-modified PET (containing 6 mol % of an isophthalic acid unit) was used as the thermoplastic resin serving as the island component. Then, the suede-like fiber base material was jet-dyed with D Blue HLA, D Red HLA, and D Yellow HLA serving as disperse dyes at 130° C. for 1 hour, and reductively cleaned in the same dyeing bath, to obtain a decorating sheet, which was a dyed dark-blue suede-like artificial leather. Then, the obtained decorating sheet was evaluated in the same manner as in Example 10. The results are shown in Table 2.
  • the surface of a resin molded body including, for example, a portable terminal body (smartphone, tablet PC) and accessories thereof such as a case and a cover, the casing of an electronic device, a vehicle interior material, and a cosmetics case, can be decorated like a dark-color artificial leather.
  • the artificial leather base material according to the present invention can be suitably used for skin members of clothing, shoes, articles of furniture, car seats, general merchandise and the like as a resin layer-equipped artificial leather and a napped artificial leather.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
US16/328,440 2016-09-14 2017-09-13 Dyed artificial leather base material, napped artificial leather, resin layer-equipped artificial leather, shoes, decorating sheet, and decorative molded body Abandoned US20200291571A1 (en)

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PCT/JP2017/033159 WO2018052052A1 (ja) 2016-09-14 2017-09-13 染色された人工皮革基材、立毛調人工皮革、樹脂層付人工皮革、靴、加飾用シート及び加飾成形体

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EP3739111A4 (en) * 2018-01-09 2021-11-17 Kuraray Co., Ltd. DECORATIVE SHAPED FILM, MOLDED BODY AND DECORATIVE SHAPED BODY
JP7128074B2 (ja) * 2018-10-05 2022-08-30 株式会社クラレ 靴成形体の製造方法
EP4223924A1 (en) * 2020-09-29 2023-08-09 Toray Industries, Inc. Artificial leather and light-transmitting device using same

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