WO2020044911A1 - 人工皮革基材、その製造方法及び立毛人工皮革 - Google Patents
人工皮革基材、その製造方法及び立毛人工皮革 Download PDFInfo
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- WO2020044911A1 WO2020044911A1 PCT/JP2019/029718 JP2019029718W WO2020044911A1 WO 2020044911 A1 WO2020044911 A1 WO 2020044911A1 JP 2019029718 W JP2019029718 W JP 2019029718W WO 2020044911 A1 WO2020044911 A1 WO 2020044911A1
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- fiber
- artificial leather
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- fibers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/004—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 flocked webs or pile fabrics upon which a resin is applied; Teasing, raising web before resin application
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Definitions
- the present invention relates to an artificial leather substrate excellent in stretchability and nap artificial leather.
- Patent Literature 1 discloses a base layer composed of ultrafine fibers having an average single fiber diameter of 0.1 to 10 ⁇ m and a porous elastic polymer, a resin layer formed on at least one surface of the base layer, A synthetic leather with silver consisting of: a base layer having a structure in which fiber bundles made of ultrafine fibers are entangled with each other, and a cross section perpendicular to the thickness direction of a surface of the base layer in contact with the resin layer.
- Patent Literature 1 discloses that such artificial leather with silver retains high peel strength and a high elongation rate and a high elongation recovery rate, which are indicators of stretchability.
- Patent Literature 2 is an artificial leather having a fiber entangled body containing a fine fiber having a single fiber fineness of 1.1 dtex or less and a polymer elastic body, and having a raised surface, and the fine fiber is
- An artificial fiber with excellent stretchability which is a latently crimp-expressing polyester composite fiber in which two types of polytrimethylene terephthalate having an intrinsic viscosity difference of 0.05 to 0.40 (dl / g) are composited with each other in a side-by-side type.
- Disclose leather is a latently crimp-expressing polyester composite fiber in which two types of polytrimethylene terephthalate having an intrinsic viscosity difference of 0.05 to 0.40 (dl / g) are composited with each other in a side-by-side type.
- Patent Document 3 discloses a woven or knitted fabric containing a yarn comprising a side-by-side type or eccentric core-sheath type composite fiber formed from two or more types of polyethylene terephthalate-based polymers having a difference in intrinsic viscosity (IV), Disclosed is a sheet material excellent in stretchability, characterized by being composed of ultrafine fibers having an average single fiber fineness of 0.001 dtex or more and 0.5 dtex or less and containing a self-emulsifying polyurethane.
- Patent Document 4 shows a strength elongation curve in the vertical direction measured by a method described in JIS L 1096 (1999) 8.14.1 A method, and (1) strength F 5 at an elongation of 5%. % Is 0.1 to 10 N / 2.5 cm, and (2) F20 % / F5 % is 5 or more in the relationship between the strength F20% at an elongation of 20 % and the above F5 % .
- a sheet-like material which is an artificial leather having excellent stretchability.
- Patent Document 5 is not a technique relating to artificial leather, but includes a short fiber layer made of short fibers having fiber ends and a filament fiber main layer mainly composed of filament fibers having almost no fiber ends.
- the fiber ends of the short fibers are entangled with the short fibers, and the entangled fiber ends are intertwined by penetrating the filament fiber main component layer.
- a multi-layer nonwoven fabric having an exposed fiber end penetrating a filament fiber main component layer and being exposed from a surface of the filament fiber main component layer is disclosed.
- the present invention provides an artificial leather substrate for obtaining artificial leather having a high balance between stretchability, high mechanical properties, and a feeling of napped when napped, a method for producing the same, and an artificial leather substrate obtained using the artificial leather substrate.
- An object of the present invention is to provide a raised artificial leather.
- One aspect of the present invention includes a nonwoven fabric that is an entangled body of the fiber (A) and the fiber (B), and a polymer elastic body provided inside the nonwoven fabric.
- a nonwoven fabric that is an entangled body of the fiber (A) and the fiber (B), and a polymer elastic body provided inside the nonwoven fabric.
- the fiber (B) is an ultrafine fiber having an average fineness of less than 0.6 dtex. It is an artificial leather substrate.
- the average fineness is also simply referred to as fineness.
- the fiber (A) which is a crimped fiber formed from two kinds of resins having different intrinsic viscosities, exhibits strong crimp.
- the nonwoven fabric formed from such crimped fibers becomes bulky.
- crimped fibers having strong crimps allow the artificial leather substrate to exhibit excellent stretchability.
- the long-fiber fiber (A) is hard to pull out and hardly deteriorates stretchability.
- a nonwoven fabric formed only of crimped fibers when used, it was difficult to obtain an artificial leather substrate having both mechanical properties and excellent stretchability.
- a nonwoven fabric containing only fiber (A) has high mechanical properties but low stretchability if the degree of entanglement of the fibers is too high, and high stretchability if the degree of entanglement is too low, but has poor mechanical properties. descend.
- an artificial leather base material having both high stretchability and high mechanical properties cannot be obtained.
- the fiber (B) which is an ultrafine fiber having an average fineness of less than 0.6 dtex, is a crimped fiber and a long fiber crimped fiber having an average fineness of 0.6 dtex or more.
- the nonwoven fabric formed by being entangled with the fiber (A) an artificial leather substrate having both high stretchability and high mechanical properties can be obtained.
- the fiber (A) which is a crimped fiber having a strong crimp the fiber (A) and the fiber (B) are easily entangled by the crimp. As a result, an artificial leather base material having both high stretchability and high mechanical properties is realized.
- the fiber (B) which is an ultrafine fiber, gives an excellent nap appearance by densifying the fiber on the surface of the artificial leather substrate. Furthermore, in a nonwoven fabric in which the fiber (A) which is a crimped fiber and the fiber (B) which is a microfiber are entangled, the fiber (B) is hard to return because the yarn is gradually stretched when the stretching is repeated. It also has the effect of keeping the fiber (A), which is a crimped fiber that tends to be easily formed, within a certain elongation range.
- the fiber (A) preferably has an average curvature of 10% or more, more preferably 15% or more, from the viewpoint of maintaining high stretchability. In particular, it is preferable that the average curvature of the fiber (A) is 15% or more and the average curvature of the fiber (B) is less than 15%.
- ⁇ ⁇ Fiber (B) is preferably a short fiber having an average fiber length of less than 100 mm from the viewpoint of excellent card passability.
- the fiber (A) is preferably a side-by-side fiber or an eccentric core-sheath fiber in which the difference in intrinsic viscosity between the two resins is 0.05 (dl / g) or more. This is preferable because it is easy to obtain a compressed fiber.
- polyester is preferable as the two kinds of resins forming the fiber (A).
- the mixing ratio ((A) / (B)) of the fiber (A) and the fiber (B) is from 10/90 to 90/10, because of the balance between high stretchability and high mechanical properties. It is preferable because an excellent artificial leather substrate can be obtained.
- the average elongation when applying a load of 1 kg for 5 minutes is 10% or more from the viewpoint that an artificial leather base material having high stretchability can be obtained.
- the polymer elastic body is water-based polyurethane
- the content of the water-based polyurethane is 8 to 15% by mass
- the average area of the voids in the cross section in the thickness direction is particularly 300 to 1000 ⁇ m 2. preferable.
- Such an artificial leather substrate hardly reduces the stretchability even after repeated elongation.
- the artificial leather base material When the content of the water-based polyurethane is 8 to 15% by mass, the artificial leather base material is not hardened to rubber-like, and the fibers are appropriately restrained to maintain stretchability. Then, the fiber (A) and the fiber (B) are sufficiently entangled to adjust the average area of the voids in the cross section in the thickness direction to 300 to 1000 ⁇ m 2 , so that each void has an appropriate size. By doing so, even after repeated elongation, an artificial leather base material having excellent stretchability and having an elongation rate and an elongation recovery rate that are equal to or more than a certain value can be obtained.
- ⁇ ⁇ Another aspect of the present invention is a raised artificial leather including any of the artificial leather base materials described above, one surface of which is subjected to a raised processing.
- a raised artificial leather has an excellent balance between stretchability and mechanical properties, and can have a raised surface with dense raised hair.
- Another aspect of the present invention is the method for producing an artificial leather substrate, wherein 0.6 dtex or more formed from two resins having different intrinsic viscosities for forming the fiber (A).
- a step of laminating a second fibrous web on at least one surface of the first fibrous web to form a laminated web, and forming a crimped fiber (A1) and an ultrafine fiber generating fiber ( B1) a step of forming an entangled fiber sheet by entanglement processing; a step of heat-shrinking the entangled fiber sheet to form a heat-shrinkable fiber sheet; and a microfiber-generating fiber forming a heat-shrinkable fiber sheet.
- crimped fiber (A1) A step of forming the Wei (B) and the nonwoven fabric is entangled body of a step of impregnating imparting elastic polymer to the heat shrinkable fiber sheet or nonwoven, is at least provided process for producing an artificial leather substrate.
- the crimped fiber is a fiber that forms the fiber (A) that is a crimped fiber, and is an actual crimped fiber having a crimp when it is formed into a web, and a crimped fiber when it is formed into a web.
- latently crimped fibers which do not exhibit the following properties and are crimped by heat treatment in a later step. According to such a method, as described above, an artificial leather base material having both high stretchability, high mechanical properties, and an excellent feeling of napped when napped is obtained.
- the laminated web is a laminate in which the second fiber web is laminated on both sides of the first fiber web, from the viewpoint that an artificial leather base material having an excellent balance between high stretchability and mechanical properties can be obtained. preferable.
- the step of impregnating the elastic polymer is a step of impregnating the heat-shrinkable fiber sheet or the nonwoven fabric with the aqueous polyurethane emulsion and then drying the resultant to form the aqueous polyurethane.
- the amount of solvent used can be reduced.
- the water-based polyurethane tends to restrain the fiber, and when the blending ratio is too high, the stretchability tends to decrease. Therefore, the content ratio of the aqueous polyurethane is preferably less than 20%.
- the crimped fiber (A1) is a crimped fiber spun with a spinning draft of 400 or more and has an average fineness of 0.6 dtex or more, has a water-based polyurethane content of 8 to 15% by mass, and has a thickness in the thickness direction. It is preferable to produce an artificial leather base material having an average area of voids in a cross section of 300 to 1000 ⁇ m 2 , because an artificial leather base material that does not excessively reduce stretchability even after repeated elongation is easily obtained.
- an artificial leather base material having a good balance between high stretchability, mechanical properties, and napped feeling when napped.
- FIG. 1 is an explanatory diagram illustrating the average curvature.
- FIG. 2 is an explanatory diagram illustrating an average area of a void in a cross section in a thickness direction.
- the artificial leather substrate of the present embodiment includes a nonwoven fabric which is an entangled body of the fiber (A) and the fiber (B), and a polymer elastic body provided inside the nonwoven fabric, and the fiber (A) It is a crimped fiber formed from two resins having different intrinsic viscosities, and is a long fiber having an average fineness of 0.6 dtex or more (hereinafter, also simply referred to as fineness). It is an artificial leather substrate which is an ultrafine fiber having an average fineness of less than 6 dtex.
- the artificial leather substrate of the present embodiment will be described in detail along with an example of a method for producing the artificial leather substrate.
- the artificial leather substrate described above can be manufactured by, for example, a manufacturing method including at least the following steps.
- Step (1) a step of preparing a first fibrous web containing a long fiber crimped fiber (A1) of 0.6 dtex or longer formed from two kinds of resins having different intrinsic viscosities.
- Step (2) a step of preparing a second fibrous web of microfiber-generating fibers (B1) for forming fibers (B) that are microfibers of less than 0.6 dtex.
- Step (3) a step of laminating the second fiber web on at least one surface of the first fiber web to form a laminated web.
- Step (4) a step of forming an entangled fiber sheet in which the crimped fibers (A1) and the ultrafine fiber-generating fibers (B1) forming the laminated web are entangled.
- Step (5) a step of heat-shrinking the entangled fiber sheet to form a heat-shrinkable fiber sheet.
- Step (6) forming a nonwoven fabric which is an entangled body of the crimped fiber (A1) and the fiber (B) by subjecting the ultrafine fiber generating fiber (B1) forming the heat shrinkable fiber sheet to the ultrafine fiber treatment Process to make it.
- Step (7) a step of impregnating the heat-shrinkable fiber sheet or nonwoven fabric with the polymer elastic body.
- (1) First Fiber Web Preparing Step In the production of the artificial leather base material of the present embodiment, a long fiber having an average fineness of 0.6 dtex or more, which is formed from two kinds of resins having different intrinsic viscosities, is used. A first fibrous web containing crimped fibers (A1) is produced.
- a crimped fiber (A1) is spun using a so-called spunbond method using a melt spinning method, and collected on a net without cutting.
- a method of forming a continuous fiber long fiber web, or crimping type fiber (A1) is spun using a melt spinning method and stretched, and then crimped if necessary, and the average fiber length is 100 mm or more.
- the raw cotton cut into a web is made into a web by passing through a card machine.
- the crimped fiber (A1) is a fiber that forms a fiber (A) that is a crimped fiber formed from two kinds of resins having different intrinsic viscosities.
- a method of forming a web of continuous fibers using a spunbond method is preferable because mechanical properties are more easily improved. Note that a method in which the cut raw cotton is made into a web by passing through a card machine tends to be difficult to pass through the card machine.
- the crimped fiber (A1) is a long fiber.
- the long fiber in the present embodiment has an average fiber length of 100 mm or more, preferably 200 mm or more, and further produced by a spun bond method and continuously spun, for example, several meters, and furthermore, several meters in length.
- the crimped fiber (A1) is a long fiber, the crimped fiber hardly comes off and exhibits high stretchability.
- the fiber (A) is a short fiber having an average fiber length of less than 100 mm, the fiber (A) easily escapes and the stretchability of the artificial leather base material tends to decrease.
- a method for manufacturing the first fibrous web using a spunbond method as a representative example will be described in detail.
- Examples of the resin for forming the crimped fiber (A1) formed from two resins having different intrinsic viscosities include polyethylene terephthalate (PET), which is a copolymer of terephthalic acid units and ethylene glycol units, Modification of polyester resin such as polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyester elastomer, or a modified product thereof, which is a copolymer of terephthalic acid unit and 1,4-butanediol unit Examples include polyester-based resins, polyamide-based resins such as polyamide 6, polyamide 66, polyamide 610, aromatic polyamide, and polyamide elastomer, and modified polyamide-based resins such as modified products thereof. Among these, a polyester resin is preferable because a fiber exhibiting high crimp is easily obtained.
- the modified product means a polymer in which a part of the main polymer-forming unit is replaced by a small amount of another monomer unit for the purpose of adjusting the intrinsic viscosity, melting point and crystallinity of the resin.
- a small amount of a monomer unit for modifying a polyester includes, for example, an asymmetric aromatic carboxylic acid such as isophthalic acid, phthalic acid and 5-sodium sulfoisophthalic acid; an aliphatic dicarboxylic acid such as adipic acid; Examples thereof include diols such as butanediol, neopentyl glycol, cyclohexanedimethanol, polyethylene glycol, and polypropylene glycol.
- Examples of the crimped fibers (A1) formed from two kinds of resins having different intrinsic viscosities include side-by-side fibers and eccentric core-sheath fibers having an eccentric core-sheath cross section.
- the side-by-side type fiber is a fiber formed by bonding two kinds of resins having different intrinsic viscosities along the length direction of the fiber during melt spinning.
- the eccentric core-sheath fiber has a core-sheath cross-section in which one of the two resins having different intrinsic viscosities during melt spinning has one resin as a core and the other resin as a sheath. It is a fiber in which the core is shifted asymmetrically from the center in the core-sheath type cross section and asymmetrically arranged.
- Such crimped fibers exhibit strong crimp after spinning or after heat treatment.
- the combination of the two resins forming the crimped fiber is appropriately selected according to the degree of stretch property to be exhibited and the requirement of the entangled state of the nonwoven fabric according to the application.
- PET and PBT, PET and PET, PBT and PBT, PBT and PTT, and the like are appropriately selected according to required characteristics.
- at least one of these may be a modified product.
- a combination of PET and PBT is preferable because the fiber (A) expresses a strong crimp so that an artificial leather base material having excellent stretchability is easily obtained.
- the difference between the intrinsic viscosities of the two resins is 0.05 dl / g or more, and more preferably 0.1 to 0.6 dl / g, because the fiber (A) has a strong crimp that contributes to the development of stretchability. Is preferred from the viewpoint of expressing If the difference in the intrinsic viscosity is too small, it becomes difficult to develop a strong crimp, and if the difference in the intrinsic viscosity is too large, the melt spinnability tends to decrease because the oblique direction on the nozzle surface becomes severe after discharging from the nozzle. There is.
- the intrinsic viscosity of the two resins having different intrinsic viscosities is 0.6 to 1.2 dl / g, more preferably 0.62 to 1.1 dl / g, for the resin having a high intrinsic viscosity. Is preferred from the viewpoint of excellent melt spinnability and mechanical properties.
- the proportion of the high-viscosity resin of the two types of resins is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass, since strong crimp is easily developed.
- Each of the two resins may contain additives such as organic particles, inorganic particles, a flame retardant and an antistatic agent as required.
- the first fibrous web is brought into contact with the two kinds of melted resins discharged from the individual nozzle holes of the melt composite spinneret in which the two kinds of resins are arranged, and further continuously from the spinning nozzle at a predetermined discharge speed. , And stretched while cooling using a high-speed airflow, and then deposited on a conveyor-belt-shaped movable net by a spunbonding method. Also, the web of long fibers deposited on the net may be hot pressed to impart morphological stability.
- Melt spinning conditions are not particularly limited. For example, when the following conditions are satisfied, a fiber (A) expressing high crimp is obtained, and an artificial leather base material that easily maintains stretchability after repeated elongation is obtained. It is preferable in that it can be obtained.
- the discharge speed of the molten resin discharged from one hole of the spinning nozzle is A (g / min)
- the melt density of the resin is B (g / cm 3 )
- the area of one hole is C (mm 2 )
- the spinning speed is
- D (m / min) is set
- the melt spinning is performed under the conditions set so that the spinning draft calculated by the following equation is 400 or more, and further, 400 to 1600, particularly 700 to 1600. It is mentioned.
- ⁇ Spinning draft D / (A / B / C)
- the average fineness of the crimped fiber (A1) and the fiber (A) which is a crimped fiber is 0.6 dtex or more, 0.6 to 2.5 dtex, further 0.6 to 2 dtex, especially 0.6 to 2 dtex. It is preferably 1.5 dtex.
- the average fineness of the crimped fiber (A1) and the fiber (A) which is a crimped fiber is less than 0.6 dtex, the entanglement becomes insufficient and the mechanical properties are likely to be reduced.
- a first fibrous web containing a long fiber crimped fiber (A1) having a fineness of 0.6 dtex or more, formed from two kinds of resins having different intrinsic viscosities can be obtained.
- the crimped fiber (A1) is an actual crimped fiber that is a crimped fiber in this step or a fiber that is a latent crimped fiber that develops a crimp by a subsequent heat treatment, and has an average fineness of 0.6 dtex or more. Is a long fiber having
- Second fiber web A second fiber web containing microfiber-generating fibers (B1) for forming fibers (B), which are microfibers of less than 0.6 dtex, is prepared.
- the second fibrous web for example, after spinning ultrafine fiber-generating fibers using a melt spinning method and stretching, crimping is further applied as necessary, and the cut raw cotton is passed through a carding machine.
- Microfiber-generating fibers are spun using a melt spinning method using a method such as web forming or a spunbond method, and are collected on a net without cutting, and continuous fiber long fibers are formed.
- the ultrafine fiber-generating fiber may be either a short fiber or a long fiber.Since it is easy to obtain an artificial leather base material which has excellent card passing properties, and has particularly excellent mechanical properties and a feeling of napped when napped, short fibers are used. Webs are particularly preferred. In the present embodiment, a case where a short fiber web is manufactured will be described in detail as a representative example.
- the ultrafine fiber-generating fiber (B1) is a fiber that forms an ultrafine fiber having a small fineness by subjecting a spun fiber to a chemical post-treatment or a physical post-treatment.
- Specific examples include, for example, sea-island type conjugate fibers and exfoliated split type conjugate fibers.
- the resin of the island component serving as a different type of domain from the resin of the sea component is dispersed in the resin of the sea component serving as the matrix.
- This is a conjugate fiber that generates a fiber bundle-like ultrafine fiber mainly composed of the above resin.
- the split-split composite fiber has a petal shape or a superimposed shape in which a plurality of different resins are alternately arranged on the outer periphery of the fiber, and is separated and bundled by peeling each resin by a physical treatment. It is a conjugate fiber that forms an ultrafine fiber.
- the sea-island composite fiber since a fiber bundle of ultrafine fibers holding voids is formed therein, a flexible artificial leather base material is easily obtained, and high mechanical properties are easily obtained.
- an ultrafine fiber is formed using a sea-island composite fiber will be described in detail as a representative example.
- the sea-island type composite fiber is a multi-component type composite fiber composed of at least two kinds of polymers. By extracting or decomposing and removing the sea component at an appropriate later stage, the fiber bundle-shaped ultrafine fiber composed of the island component is removed. Let it form.
- thermoplastic resin of the island component of the sea-island composite fiber examples include polyester resins such as PET, PBT, PTT, and polyester elastomer; polyamide 6, polyamide 66, polyamide 610, aromatic polyamide, and polyamide elastomer. Polyamide resins; acrylic resins; olefin resins and the like. These may be modified. These may be used alone or in combination of two or more.
- thermoplastic resin of the sea component examples include polyvinyl alcohol resin, polyethylene, polypropylene, polystyrene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, styrene ethylene copolymer, and styrene acrylic copolymer. Coalescence, and the like.
- a water-soluble polyvinyl alcohol-based resin particularly an ethylene-modified polyvinyl alcohol resin, is preferable because it is easily shrunk by wet heat treatment or hot water treatment.
- the web of the sea-island type composite fiber specifically, a large number of nozzle holes, using a composite spinneret arranged in a predetermined pattern, spun the sea-island type composite fiber using a melt spinning method, and stretched. Then, crimping is further provided as necessary, and the cut raw cotton is passed through a carding machine to form a web. If necessary, the web of sea-island composite fibers may be hot-pressed in order to impart form stability.
- the fiber (B) is formed from a sea-island composite fiber, it is preferable that, for example, 5 to 200, more preferably 10 to 50, particularly 10 to 30 ultrafine fibers form a fiber bundle.
- the ultrafine fiber-generating fiber (B1) in the web is converted into a fiber (B) which is an ultrafine fiber having an average fineness of less than 0.6 dtex by being subjected to an ultrafine fiber treatment.
- the average fiber length of the fiber (B) is not particularly limited, and even if the short fiber is less than 100 mm, the fiber is continuously manufactured from spinning to continuous web by 100 mm or more, furthermore, 200 mm or more, particularly by spunbonding.
- the fiber length may be several meters, further several hundred meters, particularly several kilometers or more.
- the fiber (B) is a short fiber having an average fiber length of less than 100 mm, it is preferably 40 to 75 mm from the viewpoint of excellent card passability. Further, it is preferable that the fiber (B) is drawn after spinning from the viewpoint that an artificial leather base material having more excellent mechanical properties can be obtained.
- a method for producing a laminated web for example, cross wrapping in which about 4 to 100 sheets are stacked using a cross wrapper so that the second fiber web is disposed on at least one surface, preferably both surfaces of the first fiber web.
- a woven fabric, a knitted fabric, another nonwoven fabric, or the like may be stacked as needed.
- a needle break prevention oil or a charge is applied to the surface of the fiber used or the surface of the fiber web. It is preferable to add an inhibitor or the like.
- the ratio between the first fiber web and the second fiber web is not particularly limited, but the ratio ((A) / ((A) / (F)) of the fiber (A) and the fiber (B), which is an ultrafine fiber, in the finally obtained nonwoven fabric.
- B)) is preferably in such a ratio as to be 10/90 to 90/10, more preferably 15/85 to 85/15.
- a step of forming the entangled fiber sheet by entanglement of the crimped fiber (A1) and the ultrafine fiber-generating fiber (B1) of the laminated web Next, the first fiber web forming the laminated web
- the entangled fiber sheet is formed by intertwining the crimped fiber (A1) and the ultrafine fiber-generating fiber (B1) of the second fiber web.
- the entangled fiber sheet is formed by subjecting the laminated web to an entanglement process using a known nonwoven fabric manufacturing method such as needle punching or high-pressure water flow treatment.
- a known nonwoven fabric manufacturing method such as needle punching or high-pressure water flow treatment.
- the entanglement process by needle punch will be described in detail as a representative example.
- ⁇ ⁇ Apply a silicone oil or mineral oil such as a needle break prevention oil agent, an antistatic oil agent, or an entanglement improvement oil agent to the laminated web. Thereafter, an entanglement treatment is performed to entangle the crimped fiber (A1) and the ultrafine fiber generating fiber (B1) three-dimensionally by needle punch.
- a silicone oil or mineral oil such as a needle break prevention oil agent, an antistatic oil agent, or an entanglement improvement oil agent
- needle punching is performed under the condition that at least one or more barbs penetrate simultaneously or alternately from one side or both sides.
- the punching density depends on the basis weight of the laminated web, the fiber density, etc., but is preferably 1000 to 3000 fibers / cm 2 , and more preferably 1200 to 2500 fibers / cm 2 , and the fibers are moderately entangled and have high stretchability. Is maintained, and high mechanical properties are also maintained.
- the fiber (B) which is an ultrafine fiber having an average fineness of less than 0.6 dtex and formed from the ultrafine fiber-generating fiber (B1), achieves both high mechanical properties and high stretchability of the obtained artificial leather base material.
- the basis weight of the entangled fiber sheet in which the fiber (A1) of the laminated web and the microfiber-generating fiber (B1) thus produced are entangled is not particularly limited, but may be 100 to 1000 g / m 2 , Further, it is preferably 200 to 900 g / m 2 from the viewpoint that an artificial leather base material having both high mechanical properties and high stretchability can be obtained, and an appropriate process passability can be obtained.
- the fiber density and the degree of entanglement of the entangled fiber sheet are increased by heat-shrinking the entangled fiber sheet.
- the crimp is expressed in (A1) or the already expressed crimp is strengthened.
- the heat shrinking treatment for example, a method of continuously contacting the entangled fiber sheet with water vapor, a method of applying water to the entangled fiber sheet, and then heating the water with electromagnetic waves such as heating air or infrared rays And the like. Further, for the purpose of further densifying and fixing the form and further smoothing the surface while further densifying the entangled fiber sheet densified by the heat shrinkage treatment, if necessary, further hot press treatment may be performed. Good.
- the basis weight before the heat shrinkage treatment is 1.1 times (mass ratio) or more, further 1.3 times or more and 2 times or less, More preferably, it is 1.6 times or less.
- the weight per unit area of the heat-shrinkable fiber sheet produced in this way is not particularly limited, but is preferably 200 to 2000 g / m 2 , and more preferably 400 to 1800 g / m 2 , to satisfy the mechanical properties and stretchability. It is preferable because an artificial leather base material having an excellent balance can be obtained, and an appropriate process passability can be obtained.
- Step of forming a nonwoven fabric that is an entangled body by processing the ultrafine fiber-generating fibers in the heat-shrinkable fiber sheet into ultrafine fibers, 0.6 dtex or more formed from two types of resins having different intrinsic viscosities from each other A non-woven fabric which is an entangled body of a long fiber crimped fiber (A1) and an ultrafine fiber (B) having an average fineness of less than 0.6 dtex is formed.
- the ultrafine fiber-generating fiber is a sea-island composite fiber will be described in detail as a representative example.
- the sea component is extracted or decomposed and removed with water or a solvent from the sea-island type conjugate fiber contained in the heat-shrinkable fiber sheet to convert it into a fiber bundle-like ultrafine fiber.
- a nonwoven fabric which is an entangled body with the fiber (B) is formed.
- the water-soluble polyvinyl alcohol-based sea component is obtained by heating with water, an alkaline aqueous solution, an acidic aqueous solution, or the like. The resin is removed.
- the fiber (B) which is an ultrafine fiber is an ultrafine fiber having an average fineness of less than 0.6 dtex, and preferably has an average fineness of 0.01 to 0.55 dtex, more preferably 0.05 to 0.5 dtex.
- the fibers (B), which are such ultrafine fibers, exhibit a napped feeling of the fine fibers when the surface of the artificial leather substrate is napped.
- the fibers (B), which are ultrafine fibers formed from sea-island composite fibers, are, for example, 5 to 200, more preferably 10 to 50, and especially 10 to 30 ultrafine fibers forming a fiber bundle. Preferably it is present.
- the fiber (B) exists as a fiber bundle of ultrafine fibers, higher mechanical strength is exhibited.
- the basis weight of the non-woven fabric which is an entangled body of the crimped fiber (A1) and the fiber (B) thus formed, is not particularly limited, but is, for example, 100 to 1000 g / m 2 , and more preferably 200 to 600 g. / M 2 .
- Step of impregnating a heat-shrinkable fiber sheet or a nonwoven fabric with a polymer elastic body In the production of an artificial leather base material, a process for imparting form stability to the artificial leather base material and enhancing the sense of fulfillment is carried out.
- the polymer elastic body is impregnated into the heat-shrinkable fiber sheet obtained in (5) or the nonwoven fabric obtained in step (6).
- the heat-shrinkable fiber sheet obtained in the step (5) is impregnated with a polymer elastic body, after the polymer elastic body has been applied, in the step (6), the ultrafine fiber-generating fiber is subjected to ultrafine fiber treatment.
- the fibers (B) of the ultrafine fibers to be formed are not restricted by the elastic polymer, and are preferred in that an artificial leather base material having higher stretchability can be obtained.
- the polymer elastic body include, for example, a polyamide elastic body such as a polyurethane, an acrylic elastic body, and a polyamide elastomer, a polyester elastic body such as a polyester elastomer, a polystyrene elastic body, and a polyolefin elastic body.
- the content ratio of the polymer elastic body is 5 to 50% by mass, more preferably 5 to 40% by mass, and especially 5 to 40% by mass with respect to the total amount of the nonwoven fabric which is the entangled body of the fiber (A) and the fiber (B).
- the content of 10 to 30% by mass is preferred from the viewpoint that an artificial leather base material having excellent form stability and a sense of fulfillment and excellent stretchability can be obtained. If the content ratio of the polymer elastic body is too low, the morphological stability tends to decrease, and the stretchability tends to decrease due to the tendency of the fibers to easily pass through. On the other hand, when the content ratio of the elastic polymer is too high, the rubber-like texture tends to be obtained, and the stretchability tends to be reduced. When the content ratio of the polymer elastic body is 8 to 15% by mass with respect to the total amount of the nonwoven fabric which is the entangled body of the fiber (A) and the fiber (B), The elongation recovery rate is particularly excellent.
- polyurethane is particularly preferred because of its excellent flexibility and fullness.
- properties of the polyurethane include an aqueous polyurethane prepared as an aqueous emulsion and a solvent-based polyurethane prepared as a solution by being dissolved in a solvent containing N, ⁇ N-dimethylformamide (DMF).
- DMF N, ⁇ N-dimethylformamide
- a method of impregnating the polymer elastic body a method of impregnating the heat-shrinkable fiber sheet or the nonwoven fabric with the solvent-based polyurethane and then wet-solidifying the resultant to give the sponge-like polyurethane is given.
- a polymer elastic body having excellent elasticity can be provided in the artificial leather substrate. Since the solvent-based polyurethane hardly restrains the fiber, an artificial leather substrate having both high stretchability and high mechanical properties can be easily obtained even if the polyurethane is contained, for example, in an amount of 20% or more.
- the elastic polymer there is also a method of impregnating a heat-shrinkable fiber sheet or nonwoven fabric with a water-based polyurethane emulsion, followed by drying to give a water-based polyurethane.
- a method for impregnating a heat-shrinkable fiber sheet or nonwoven fabric with a water-based polyurethane emulsion followed by drying to give a water-based polyurethane.
- the amount of solvent used can be reduced.
- the water-based polyurethane tends to restrain the fiber, and when the blending ratio is too high, the stretchability tends to decrease. Therefore, the content ratio of the aqueous polyurethane is preferably less than 20%.
- Aqueous polyurethane is prepared as an aqueous emulsion or an aqueous suspension. Further, the water-based polyurethane may be crosslinked for the purpose of improving water resistance, abrasion resistance and hydrolysis resistance.
- the cross-linking agent for cross-linking the water-based polyurethane may be an external cross-linking agent added as a third component to the water-based polyurethane, or an internal cross-linking agent that introduces a reaction point to a cross-linked structure in advance in the molecular structure of the water-based polyurethane. There may be.
- the crosslinking agent include compounds having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, and a silanol group.
- the content ratio of the water-based polyurethane is 8 to 15% by mass based on the total amount of the nonwoven fabric which is the entangled body of the fiber (A) and the fiber (B).
- An artificial leather base material having an excellent elongation recovery rate after repeated elongation is obtained.
- the content of the water-based polyurethane is less than 8% by mass, the morphological stability tends to decrease, and the fiber tends to be easily pulled out, and the elongation recovery rate after repeated elongation tends to decrease.
- the content of the water-based polyurethane is too high, the rubber-like texture tends to be obtained.
- a dip nip method in which a process of squeezing with a press roll or the like so as to obtain a predetermined impregnation state is performed once or plural times is preferably used.
- a bar coating method, a knife coating method, a roll coating method, a comma coating method, a spray coating method, or the like may be used.
- pigments such as carbon black, dyes, fungicides and antioxidants, ultraviolet absorbers, light stabilizers such as light stabilizers, flame retardants, penetrants and lubricants, silica Anti-blocking agents such as titanium oxide, water repellents, viscosity modifiers, surfactants such as antistatic agents, defoamers such as silicones, fillers such as cellulose, and coagulation regulators, and silica and titanium oxide It may contain inorganic particles and the like.
- the artificial leather substrate is obtained by the above steps.
- the obtained artificial leather base material is dried and then sliced or ground in a direction perpendicular to the thickness direction to adjust the thickness and adjust the surface state to finish. Further, a raised surface obtained by raising the surface of at least one surface of the artificial leather base material or a resin layer with a tone of silver may be formed.
- the artificial leather substrate of the present embodiment is preferably used in the manufacture of napped artificial leather in which at least one surface is napped, in particular, because the napped surface formed by performing the napped treatment has excellent napped feeling. .
- a suede-like or nubuck-like texture can be obtained by buffing the surface layer of the artificial leather base material using sandpaper or the like to perform the napping treatment.
- a softening treatment by massaging, a brushing treatment of a reverse seal, an antifouling treatment, a hydrophilic treatment, a lubricant treatment, a softener treatment, an antioxidant treatment, an ultraviolet absorber treatment, and a fluorescent light
- a finishing treatment such as a chemical treatment or a flame retardant treatment may be performed.
- the artificial leather substrate thus obtained is preferably further dyed.
- Dyeing is performed by appropriately selecting a dye mainly comprising a disperse dye, a reactive dye, an acid dye, a metal complex dye, a sulfur dye, a sulfur vat dye, etc. according to the type of the fiber, and using a padder, a jigger, a circular, a wind, etc. This is performed using a known dyeing machine usually used for dyeing.
- a disperse dye to perform high-temperature and high-pressure dyeing.
- the artificial leather substrate obtained by the production method of the present embodiment as described above or the artificial leather using the same is provided inside a nonwoven fabric that is an entangled body of the fiber (A) and the fiber (B), and is provided inside the nonwoven fabric.
- the fiber (A) is a crimped fiber formed from two kinds of resins having different intrinsic viscosities, and is a long fiber having an average fineness of 0.6 dtex or more
- Fiber (B) is an artificial leather substrate which is an ultrafine fiber having an average fineness of less than 0.6 dtex.
- the fiber (A) is strongly crimped, and exhibits a stretch property by strong crimping.
- the crimped fiber means a fiber having an average curvature rate of 10% or more measured as described later.
- the crimp of the fiber (A) preferably has an average curvature of 14% or more, particularly 15% or more, and more preferably 20% or more from the viewpoint of exhibiting high stretchability.
- ⁇ ⁇ Fiber (B) is preferably a weakly crimped ultrafine fiber.
- weakly crimped means that the average curvature measured as described below is less than 14%, further less than 13.5%, and particularly less than 11%.
- the elongation of the fiber (A) is kept within a certain range.
- an artificial leather having a good balance of stretchability, mechanical properties, and napped feeling when napped can be obtained.
- the average elongation when applying a load of 1 kg for 5 minutes is 10% or more, more preferably 15% or more, especially 20% or more. It is preferable because it becomes an artificial leather base material or artificial leather having excellent properties.
- the average elongation when a load of 1 kg is applied for 5 minutes means the average of the elongation in the vertical direction corresponding to the direction along the production line direction and the horizontal direction perpendicular to the vertical direction.
- the stretchability of the artificial leather base material or the artificial leather using the same is as follows.
- the elongation percentage in both the vertical direction and the horizontal direction when a load of 1 kg is applied for 5 minutes is 10% or more, It is preferable from the viewpoint of maintaining a low stretch property.
- the artificial leather substrate of the present embodiment includes a nonwoven fabric that is an entangled body of the fiber (A) and the fiber (B), and an aqueous polyurethane provided inside the nonwoven fabric, and the fiber (A) is A crimped fiber formed of two resins having different intrinsic viscosities and having an average curvature of 15% or more, and a long fiber having an average fineness of 0.6 to 2.5 dtex; ) Is an ultrafine fiber having an average fineness of less than 0.6 dtex, an artificial leather having a water-based polyurethane content of 8 to 15% by mass, and an average area of voids in a cross section in the thickness direction of 300 to 1000 ⁇ m 2.
- a base material it is particularly preferable since an artificial leather base material having excellent stretchability and having a certain or more elongation rate and elongation recovery rate can be obtained even after repeated elongation.
- the fiber (B) which is an ultrafine fiber repeats elongation. It has an effect of keeping the fiber (A), which is a crimped fiber, in which the yarn is sometimes gradually stretched out and hard to return, within a certain elongation range.
- the fiber (B), which is an ultrafine fiber moves the fiber (A), which is a crimped fiber, within a certain range of elongation. The fastening action tends to decrease.
- the fiber (A) which is a crimped fiber having an average curvature ratio of 15% or more
- the fiber (A) and the fiber (B) are easily entangled sufficiently by the crimp.
- the crimped fiber is a long fiber, it is difficult for the fiber to come off easily and the stretchability is hardly reduced.
- the fiber (B), which is an ultrafine fiber gives an excellent nap appearance by making the appearance state dense.
- the content of the water-based polyurethane is 8 to 15% by mass, the artificial leather base material is not too hard to be rubber-like, and the fibers are appropriately restrained to maintain the stretchability.
- the fiber (A) and the fiber (B) are sufficiently entangled to adjust the average area of the voids in the cross section in the thickness direction to 300 to 1000 ⁇ m 2 , so that each void has an appropriate size.
- an artificial leather base material having excellent stretchability and having an elongation rate and an elongation recovery rate that are equal to or more than a certain value can be obtained.
- Average area of the voids in the thickness direction of the cross section 300 ⁇ 1000 ⁇ m 2, further, 350 ⁇ 950 ⁇ m 2, particularly preferably in 400 ⁇ 900 ⁇ m 2.
- the average area of the voids in the cross section in the thickness direction is an average of the areas of the voids per one in the thickness direction calculated as described later.
- the fibers are bulky and are entangled so that the voids become small even if the fibers (A), which are crimped fibers having a high average curvature tend to be coarse, are included. ing.
- the entanglement of the nonwoven fabric which is the entangled body of the fiber (A) and the fiber (B)
- the entanglement of the nonwoven fabric is insufficient and the voids are large, so that the stretchability after repeated elongation is maintained. Properties tend to be low.
- the average area of the voids is less than 300 ⁇ m 2
- the entanglement of the nonwoven fabric, which is the entangled body of the fiber (A) and the fiber (B) is too strong or the amount of the aqueous polyurethane is too large, so that the fiber becomes difficult to move.
- the stretchability tends to decrease.
- Such an artificial leather substrate is excellent in the persistence of stretchability after repeated elongation.
- the average elongation rate after 20 times elongation measured as described below is 18% or more
- the average elongation recovery rate is 55% or more
- the average elongation rate after 20 times elongation is 20%.
- an artificial leather base material having an average elongation recovery rate of 60% or more can be realized.
- the apparent density of the artificial leather substrate or artificial leather obtained in the present embodiment is 0.20 to 0.7 g / cm 3 , and more preferably 0.25 to 0.5 g / cm 3 . It is preferable because artificial leather having particularly excellent properties and high stretchability can be obtained.
- the average fineness was measured as follows. A scanning electron microscope (SEM) photograph of a cross section of the artificial leather substrate was taken at a magnification of 3000 times. Then, ten cross sections of the fiber were randomly selected from the SEM photograph, the cross sectional areas were measured, and the average value of the cross sectional areas was calculated. Then, the average value of the cross-sectional area was converted into an average fineness using the density of each resin.
- SEM scanning electron microscope
- the polyester fiber of the side-by-side type was defined as the fiber (A), and the others were measured as the fiber (B).
- ⁇ Apparent density> The thickness (mm) and the basis weight (g / cm 2 ) were measured according to JIS L1913, and the apparent density (g / cm 3 ) was calculated from these values.
- the elongation percentage indicates the elongation percentage when elongating at a constant load.
- the elongation recovery rate indicates the recovery rate after elongation at a constant load and removal of the load.
- the artificial leather base material was cut out to a width of 2.5 cm, a reference line at intervals of 3 cm was inserted between 5 cm in length, and a length L1 where the reference line was extended after applying a load of 1 kg for 5 minutes was measured. The elongation rate was measured.
- ⁇ Standing feeling> The appearance of the obtained raised artificial leather was visually and visually evaluated according to the following criteria.
- ⁇ Texture> The obtained raised artificial leather was bent, and the feeling of waist and flexibility was determined according to the following criteria.
- ⁇ Tear strength> A test piece of 10 cm in length and 4 cm in width was cut out from the raw material of artificial leather. Then, a cut of 5 cm was made in the center of the short side of the test piece in parallel with the long side. Then, using a tensile tester, each section was sandwiched between chucks of a jig, and an ss curve was measured at a tensile speed of 10 cm / min. Three test pieces were measured in the longitudinal direction of the raw material and in the lateral direction perpendicular to the longitudinal direction, and the average value was determined.
- Example 1 Melting at 275 ° C. using polybutylene terephthalate (PBT) having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g) and polyethylene terephthalate (PET) having an intrinsic viscosity [ ⁇ ] of 0.585 (dl / g)
- PBT polybutylene terephthalate
- PET polyethylene terephthalate
- the first is discharged from the spinneret for composite spinning, the ejector pressure is adjusted so that the spinning speed becomes 4000 m / min, the long fibers are collected on the net, and the first fibers containing side-by-side polyester fibers having an average fineness of 1.5 dtex. A fibrous web was obtained.
- a water-soluble thermoplastic polyvinyl alcohol-based resin (PVA; sea component) and isophthalic acid-modified polyethylene terephthalate (island component) having a modification degree of 6 mol% were mixed at a sea component / island component ratio of 50/50 (mass ratio).
- PVA thermoplastic polyvinyl alcohol-based resin
- isophthalic acid-modified polyethylene terephthalate island component having a modification degree of 6 mol%
- the stacked web was subjected to a needle punching process using a 1 barb needle at a punching density of 1840 P / cm 2 to form an entangled fiber sheet having a basis weight of 220 g / m 2 .
- the entangled fiber sheet was subjected to steam treatment at 110 ° C. and 23.5% RH. Then, after drying in an oven at 90 to 110 ° C., it is further heat-pressed at 115 ° C. to be subjected to heat shrinkage treatment with a basis weight of 312 g / m 2 , an apparent density of 0.52 g / cm 3 and a thickness of 0.60 mm. A heat-shrinkable fiber sheet was obtained.
- the heat-shrinkable fiber sheet was impregnated with an aqueous polyurethane emulsion (solid content: 18%) at a pick of up 50%.
- the water-based polyurethane was a polycarbonate-based non-yellowing polyurethane. Further, 4.9 parts by mass of a carbodiimide-based crosslinking agent and 6.4 parts of ammonium sulfate were added to 100 parts by mass of the polyurethane to adjust the solid content of the polyurethane to 10%. Then, the heat-shrinkable fiber sheet impregnated with the emulsion was dried at 115 ° C. in a 25% RH atmosphere, and further dried at 150 ° C.
- the heat-shrinkable fiber sheet provided with the polyurethane is immersed in hot water at 95 ° C. for 10 minutes while being subjected to a nip treatment and a high-pressure water flow treatment to dissolve and remove the PVA, thereby obtaining an ultrafine PET having an average fineness of 0.3 dtex.
- a fiber was formed.
- an artificial leather substrate was obtained.
- the artificial leather substrate having a raised surface was formed by grinding the both surfaces using # 120 paper on the back surface and # 240 and # 320 paper on the main surface of the artificial leather substrate. Then, the artificial leather base material having the raised surface formed thereon was subjected to high-pressure dyeing at 120 ° C. using a disperse dye to obtain a raised artificial leather having a suede-like raised surface.
- the obtained raised artificial leather had a basis weight of 240 g / m 2 , an apparent density of 0.282 g / cm 3 , and a thickness of 0.85 mm.
- Example 2 As shown in Table 1, in Example 1, a PET having an intrinsic viscosity [ ⁇ ] of 0.775 (dl / g) was used instead of a PBT having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g). In the same manner as above, except that PET having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) was used instead of PET having an intrinsic viscosity [ ⁇ ] of 0.585 (dl / g), Obtained and evaluated. Table 1 shows the results.
- Example 3 As shown in Table 1, in Example 1, PET having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) was used instead of PET having an intrinsic viscosity [ ⁇ ] of 0.585 (dl / g). In addition, except that the content ratio of the water-based polyurethane was changed, the napped artificial leather was obtained and evaluated in the same manner. Table 1 shows the results.
- Example 4 As shown in Table 1, in Example 1, instead of forming ultrafine fibers of PET having an average fineness of 0.3 dtex, ultrafine fibers of PET having an average fineness of 0.5 dtex were formed. An artificially raised artificial leather was obtained and evaluated in the same manner except that the ratio was changed. Table 1 shows the results.
- Example 5 Same as Example 1 except that the second fiber web of Example 3 was changed to a second fiber web manufactured as follows, and changed to ultrafine fibers of long fibers as shown in Table 1. To obtain artificially raised artificial leather and evaluated. Table 1 shows the results.
- PVA thermoplastic polyvinyl alcohol-based resin
- isophthalic acid-modified polyethylene terephthalate island component having a modification degree of 6 mol%, with a sea component / island component ratio of 25/25 (mass ratio).
- Example 6 As shown in Table 1, in Example 3, instead of the first fiber web containing the side-by-side type polyester fiber having an average fineness of 1.5 dtex, the first fiber web containing the side-by-side type polyester fiber having an average fineness of 0.6 dtex was used. In the same manner except that the fiber web was used, napped artificial leather was obtained and evaluated. Table 1 shows the results.
- Example 4 As shown in Table 1, the napped artificial hair was prepared in the same manner as in Example 1 except that PET microfibers having an average fineness of 0.6 dtex were formed instead of forming PET ultrafine fibers having an average fineness of 0.3 dtex. Leather was obtained and evaluated. Table 1 shows the results.
- the nap-artificial leathers obtained in Examples 1 to 6 according to the present invention all have a stretch showing an elongation of 10% or more in both the vertical and horizontal directions and an average elongation of 10% or more. Also, the tear strength was 3 kg or more in both the vertical direction and the horizontal direction, and the nap was also excellent.
- the napped artificial leather of Comparative Example 1 which does not include the fiber (B) which is an ultrafine fiber having an average fineness of less than 0.6 dtex, has an elongation of 10% or more in both the vertical and horizontal directions and an average elongation of 10% or more , But the tear strength was low.
- Example 7 Polybutylene terephthalate (PBT) having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g) and polyethylene terephthalate (PET) having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) in a ratio of 50/50. It was discharged at a discharge speed A of 0.25 (g / min) from a melt composite spinneret having a hole area C of 0.08 mm 2 at 275 ° C. At this time, the melt density B of the resin was 1.21 (g / cm 3 ).
- the ejector pressure is adjusted so that the spinning speed D becomes 3987 m / min, the spinning is performed so that the spinning draft becomes 1544, and the long fibers are collected on a net, so that a side-by-side type having an average fineness of 0.63 dtex is obtained.
- a first fibrous web containing the polyester fibers of the above was obtained.
- a water-soluble thermoplastic polyvinyl alcohol-based resin (PVA; sea component) and isophthalic acid-modified polyethylene terephthalate (island component) having a modification degree of 6 mol% were mixed at a sea component / island component ratio of 50/50 (mass ratio).
- PVA thermoplastic polyvinyl alcohol-based resin
- isophthalic acid-modified polyethylene terephthalate island component having a modification degree of 6 mol%
- the laminated web was needle-punched at a punching density of 1840 P / cm 2 using a 1 barb needle to form an entangled fiber sheet having a basis weight of 410 g / m 2 .
- the entangled fiber sheet was subjected to steam treatment at 110 ° C. and 23.5% RH. Then, after drying in an oven at 90 to 110 ° C., it is further heat-pressed at 115 ° C. to be subjected to a heat shrink treatment with a basis weight of 511 g / m 2 , an apparent density of 0.63 g / cm 3 and a thickness of 0.81 mm. A heat-shrinkable fiber sheet was obtained.
- the heat-shrinkable fiber sheet was impregnated with an aqueous polyurethane emulsion (solid content: 10%) at a pick of up 50%.
- the aqueous polyurethane was a polycarbonate-based non-yellowing polyurethane.
- an emulsion prepared by mixing 1.5 parts by mass of a carbodiimide-based crosslinking agent and 7.5 parts by mass of ammonium sulfate with respect to 100 parts by mass of the aqueous polyurethane and adjusting the solid content of the aqueous polyurethane to 10% was used.
- the heat-shrinkable fiber sheet impregnated with the emulsion was dried at 115 ° C. in a 25% RH atmosphere, and further dried at 150 ° C.
- the heat-shrinkable fiber sheet provided with the polyurethane is immersed in hot water at 95 ° C. for 10 minutes while being subjected to a nip treatment and a high-pressure water flow treatment to dissolve and remove the PVA, thereby obtaining an ultrafine PET having an average fineness of 0.3 dtex.
- a fiber was formed.
- an artificial leather substrate was obtained.
- the artificial leather substrate having a raised surface was formed by grinding the both surfaces using # 120 paper on the back surface and # 240 and # 320 paper on the main surface of the artificial leather substrate. Then, the artificial leather base material having the raised surface formed thereon was subjected to high-pressure dyeing at 120 ° C. using a disperse dye to obtain a raised artificial leather having a suede-like raised surface.
- the obtained raised artificial leather had a basis weight of 352 g / m 2 , an apparent density of 0.314 g / cm 3 , and a thickness of 1.12 mm.
- the polyurethane content was 10% by mass.
- the “spun draft of the crimped fiber (A1)” was calculated as follows.
- the melt densities B (g / cm 3 ) of the resins are defined as discharge volumes (cc / rpm) E1 and E2 when two types of resins having different intrinsic viscosities are discharged during melt spinning.
- FIG. 2 shows an example of an image obtained in the first embodiment. Each of the black portions is a void.
- Example 8 napped artificial leather was obtained and evaluated in the same manner except that the first fibrous web produced as follows was used.
- Polybutylene terephthalate (PBT) having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g) and polyethylene terephthalate (PET) having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) in a ratio of 50/50. It was discharged at a discharge speed A of 0.51 (g / min) from a melt composite spinning die having an area C of one hole of 0.08 mm 2 at 275 ° C.
- Example 9 In Example 7, napped artificial leather was obtained and evaluated in the same manner except that the first fibrous web produced as follows was used.
- Polybutylene terephthalate (PBT) having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g) and polyethylene terephthalate (PET) having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) in a ratio of 50/50.
- the mixture was discharged at a discharge speed of A1.0 (g / min) from a melt spinning die having a hole area C of 0.08 mm 2 at 275 ° C.
- Example 10 In Example 7, instead of using the second fiber web produced as follows to form PET microfine fibers having an average fineness of 0.3 dtex, forming PET microfine fibers having an average fineness of 0.5 dtex An artificially raised artificial leather was obtained in the same manner as described above, and evaluated.
- PVA thermoplastic polyvinyl alcohol-based resin
- isophthalic acid-modified polyethylene terephthalate island component
- Example 11 In Example 7, the second fibrous web / first fibrous web / second fibrous web was laminated at a mass ratio of 1/2/1, and instead of forming a laminated web, 1 / 8.5 / 1. Were obtained in the same manner as above except that a laminated web was obtained and evaluated. Table 2 shows the results.
- Example 12 In Example 7, the second fiber web / the first fiber web / the second fiber web were laminated at a mass ratio of 1/2/1, and instead of forming a laminated web, 0.7 / 1/0 was used. Laminated artificial leather was obtained and evaluated in the same manner except that the laminated web was obtained at a mass ratio of 0.7. Table 2 shows the results.
- Example 13 In Example 8, instead of impregnating the heat-shrinkable fiber sheet with the water-based polyurethane emulsion (solid content 10%) with pick up 50%, the water-based polyurethane emulsion (solid content 11%) was impregnated with pick up 50%. In the same manner as above, except that the content of polyurethane was changed to 8.5% by mass instead of 10% by mass, nap artificial leather was obtained and evaluated. Table 2 shows the results.
- Example 14 In Example 8, instead of impregnating the heat-shrinkable fiber sheet with an aqueous polyurethane emulsion (solid content: 10%) at a pick up of 50%, an aqueous polyurethane emulsion (18.8% solid content) was impregnated with a pick up of 50%. An artificially raised artificial leather was obtained and evaluated in the same manner except that the polyurethane content was changed to 13% by mass instead of 10% by mass. Table 2 shows the results.
- Example 15 the napped artificial leather was obtained and evaluated in the same manner except that the first fiber web manufactured as follows was used.
- Polybutylene terephthalate (PBT) having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g) and polyethylene terephthalate (PET) having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) in a ratio of 50/50.
- the mixture was discharged at a discharge speed of A1.0 (g / min) from a melt composite spinning die having an area C of one hole of 0.08 mm 2 at 275 ° C.
- Example 7 the laminated web was formed only with the first fibrous web manufactured as described below, and the napped hair was similarly raised except that the water-based polyurethane content was changed to 6% by mass instead of 10% by mass. Artificial leather was obtained and evaluated.
- Polybutylene terephthalate (PBT) having an intrinsic viscosity [ ⁇ ] of 1.025 (dl / g) and polyethylene terephthalate (PET) having an intrinsic viscosity [ ⁇ ] of 0.52 (dl / g) in a ratio of 50/50.
- the mixture was discharged at a discharge speed A of 0.51 (g / min) from a melt composite spinning die having an area C of one hole of 0.08 mm 2 at 275 ° C.
- Example 7 instead of the first fiber web containing the side-by-side type polyester fiber, the first fiber web containing the regular polyester fiber having an average fineness of 1.32 dtex was used, and the first fiber web was laminated only with the first fiber web. A web was formed, and the napped artificial leather was obtained and evaluated in the same manner except that the water-based polyurethane content was changed to 6% by mass instead of 10% by mass. Table 3 shows the results.
- Example 16 In Example 8, instead of impregnating the heat-shrinkable fiber sheet with an aqueous polyurethane emulsion (solid content: 10%) at a pick up of 50%, an aqueous polyurethane emulsion (solid content of 6.6%) was impregnated with a pick up of 50%. An artificially raised artificial leather was obtained and evaluated in the same manner except that the polyurethane content was changed to 5% by mass instead of 10% by mass. Table 3 shows the results.
- Example 17 In Example 8, instead of impregnating the heat-shrinkable fiber sheet with the aqueous polyurethane emulsion (solid content: 10%) with pick up 50%, the aqueous polyurethane emulsion (solid content 10.2%) was impregnated with pick up 50%. An artificially raised artificial leather was obtained and evaluated in the same manner except that the polyurethane content was changed to 7.5% by mass instead of 10% by mass. Table 3 shows the results.
- Example 18 In Example 8, instead of impregnating the heat-shrinkable fiber sheet with the aqueous polyurethane emulsion (solid content 10%) with pick up 50%, the aqueous polyurethane emulsion (solid content 24%) was impregnated with pick up 50%. In the same manner as above, except that the content ratio of polyurethane was changed to 16% by mass instead of 10% by mass, nap artificial leather was obtained and evaluated. Table 3 shows the results.
- any of the napped artificial leathers obtained in Examples 7 to 14 in which the average area of the voids in the cross section in the thickness direction is 300 to 1000 ⁇ m 2 has stretchability with high resilience after repeated elongation. , And maintained high stretchability even after repeated elongation.
- the artificial leather of Example 15 manufactured by the spinning draft 393, in which the average curvature of the fiber (A) is slightly low has an average area of the voids in the cross section in the thickness direction of 1000 ⁇ m 2 .
- the elongation recovery rate after repeated elongation was slightly lower.
- Comparative Example 5 in which the laminated web was formed only with the first fiber web, the average area of the voids in the cross section in the thickness direction exceeded 1000 ⁇ m 2 , the elongation recovery rate after repeated elongation was low, and the tear strength was low. It was low. Further, instead of the first fiber web containing the side-by-side type polyester fiber, the first fiber web containing the regular polyester fiber having an average fineness of 1.32 dtex is used, and the laminated web is formed only with the first fiber web. Comparative Example 6, which was performed, had poor stretchability. In Example 16 in which the content ratio of polyurethane was 5%, the elongation recovery rate after repeated elongation was low. Example 17 in which the polyurethane content was 7.5% also had a low elongation recovery rate after repeated elongation. Example 18 having a polyurethane content of 16% had a low elongation.
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Abstract
Description
工程(1):互いに固有粘度の異なる2種の樹脂から形成された0.6dtex以上の長繊維の捲縮型繊維(A1)を含む第1の繊維ウェブを準備する工程。
工程(2):0.6dtex未満の極細繊維である繊維(B)を形成するための極細繊維発生型繊維(B1)の第2の繊維ウェブを準備する工程。
工程(3):第1の繊維ウェブの少なくとも1面に第2の繊維ウェブを積層して積層ウェブを形成する工程。
工程(4):積層ウェブを形成する捲縮型繊維(A1)と極細繊維発生型繊維(B1)とを絡合処理させた絡合繊維シートを形成する工程。
工程(5):絡合繊維シートを熱収縮させて熱収縮繊維シートを形成する工程。
工程(6):熱収縮繊維シートを形成する極細繊維発生型繊維(B1)に極細繊維化処理することにより、捲縮型繊維(A1)と繊維(B)との絡合体である不織布を形成させる工程。
工程(7):熱収縮繊維シートまたは不織布に高分子弾性体を含浸付与する工程。
本実施形態の人工皮革基材の製造においては、互いに固有粘度の異なる2種の樹脂から形成された、0.6dtex以上の平均繊度を有する長繊維の捲縮型繊維(A1)を含む第1の繊維ウェブを製造する。
・紡糸ドラフト=D/(A/B/C)
0.6dtex未満の極細繊維である繊維(B)を形成するための極細繊維発生型繊維(B1)を含む第2の繊維ウェブを準備する。
次に、第1の繊維ウェブと第2の繊維ウェブとを重ねて積層することにより積層ウェブを形成する。
次に、積層ウェブを形成する第1の繊維ウェブの捲縮型繊維(A1)と第2の繊維ウェブの極細繊維発生型繊維(B1)とを絡合させることにより絡合繊維シートを形成する。絡合繊維シートは、ニードルパンチや高圧水流処理等の公知の不織布製造方法を用いて、積層ウェブに絡合処理を施すことにより形成される。本実施形態では、ニードルパンチによる絡合処理について代表例として詳しく説明する。
次に、絡合繊維シートを熱収縮させることにより、絡合繊維シートの繊維密度および絡合度合を高めるとともに、繊維(A1)にクリンプを発現させたり、既に発現しているクリンプを強めたりする。熱収縮処理の具体例としては、例えば、絡合繊維シートを水蒸気に連続的に接触させる方法や、絡合繊維シートに水を付与した後、加熱エアーや赤外線などの電磁波で水を加熱する方法等が挙げられる。また、熱収縮処理により緻密化された絡合繊維シートをさらに緻密化するとともに形態を固定化したり、表面を平滑化したりすることを目的として、必要に応じて、さらに熱プレス処理を行ってもよい。
本工程では、熱収縮繊維シート中の極細繊維発生型繊維を極細繊維化処理することにより、互いに固有粘度の異なる2種の樹脂から形成された0.6dtex以上の長繊維の捲縮型繊維(A1)と、0.6dtex未満の平均繊度を有する極細繊維である繊維(B)、との絡合体である不織布を形成させる。本実施形態では、極細繊維発生型繊維が海島型複合繊維である場合について、代表例として詳しく説明する。
人工皮革基材の製造においては、人工皮革基材に形態安定性を付与し、また、充実感を高めるために、工程(5)で得られた熱収縮繊維シートまたは工程(6)で得られた不織布に高分子弾性体を含浸付与する。工程(5)で得られた熱収縮繊維シートに高分子弾性体を含浸付与した場合、高分子弾性体が付与された後に、工程(6)において極細繊維発生型繊維に極細繊維化処理するために、形成される極細繊維の繊維(B)が高分子弾性体で拘束されず、ストレッチ性のより高い人工皮革基材が得られる点から好ましい。
平均繊度は以下のように測定した。人工皮革基材の断面の走査型電子顕微鏡(SEM)写真を3000倍で撮影した。そして、SEM写真から繊維の断面をランダムに10個選んで断面積を測定し、その断面積の平均値を算出した。そして、断面積の平均値を各樹脂の密度を用いて平均繊度に換算した。なお、SEM写真においては、サイドバイサイド型のポリエステル繊維を繊維(A)とし、それ以外のものを繊維(B)として区別して測定した。
溶媒としてフェノール/テトラクロロエタン(体積比1/1)混合溶媒を用い30℃でウベローデ型粘度計(林製作所製HRK-3型)を用いて測定した。
人工皮革基材の厚み方向の中央部分をスライスした後、下層側表面を100倍の倍率で電子顕微鏡観察を行った。そして、図1に示すように、繊維1の湾曲部における100μmの長さの弦から垂線を下して交わる繊維までの距離Aを測定し、以下の式で湾曲率を算出した。そして、ランダムに10ヶ所で測定した湾曲率の平均を平均湾曲率とした。
平均湾曲率(%)=A(μm)/100(μm)×100
積層する繊維(A1)と繊維(B1)の目付けを測定し、その合計目付け量W(g/m2)とその中の繊維(A)と繊維(B)との各割合から繊維(A)と繊維(B)の目付けX(g/m2)を算出した。次に、水系ポリウレタン液濃度Y(%)、不織布へ含浸した時のピックアップZ(%)とした時、以下の式から水系ポリウレタンの割合を求めた。
水系ポリウレタン割合(%)=
[W×Z/100×Y/100]/[W×Z/100×Y/100+X]×100
JIS L1913に準じて、厚さ(mm)および目付け(g/cm2)を測定し、これらの値から見掛け密度(g/cm3)を算出した。
伸長率は、定荷重で伸張した際の伸び率を示す。また、伸長回復率は、定荷重で伸張し、荷重を除いた後の回復率を示す。人工皮革基材を2.5cm幅に切出し、長さ5cm間に3cm間隔の基準線を入れ、荷重1kgを5分間付加した後の基準線が伸びた長さL1を測定し、以下の式で伸長率を測定した。
・伸長率(%)=[L1(cm)-3(cm)]/3(cm)×100
また、荷重解放して5分間後、基準線間の長さL2を測定し、以下の式で伸長回復率を測定した。
・伸長回復率(%)=[L1(cm)-L2(cm)]/[L1(cm)-3(cm)]/×100
目視及び触感により、得られた立毛人工皮革の外観を以下の基準で判定した。
A:繊維が細かくばらけた均一な長さを有し、やわらかくスムースな感触の立毛面であった。
B:繊維が粗くばらけて不均一な長さを有し、粗い感触でライティングのない立毛感であった。
得られた立毛人工皮革を折り曲げて、腰や柔軟性の感触を以下の基準で判定した。
A:充実感があり、ボキ折れすることなく、柔軟性に優れた風合いであった。
B:充実感に欠ける、ボキ折れする、硬い、のいずれか1つ以上に該当する風合いであった。
得られた立毛人工皮革を引っ張り、その時の力の程度や戻りやすさの感触を以下の基準で判定した。
A:弱い力で伸びやすく力を解放した後の伸びの戻りが早い。
B:弱い力で伸びにくく力を解放した後の伸びの戻りが遅い、あるいは弱い力で伸びやすいが力を解放した後の伸びの戻りが遅い、あるいは弱い力で伸びにくく力を解放した後の伸びの戻りは早い、のいずれかに該当する。
人工皮革の原反から、たて10cm×よこ4cmの試験片を切りだした。そして、試験片の短辺の中央に、長辺に平行に5cmの切れ目を入れた。そして、引張試験機を用い、各切片を治具のチャックに挟み、10cm/minの引張速度でs-s曲線を測定した。原反の縦方向と縦方向に垂直な横方向について各試験片3個を測定し、それぞれ平均値を求めた。
固有粘度[η]=1.025(dl/g)のポリブチレンテレフタレート(PBT)と固有粘度[η]=0.585(dl/g)のポリエチレンテレフタレート(PET)とを用い、275℃で溶融複合紡糸用口金より吐出し、紡糸速度が4000m/minとなるようにエジェクター圧力を調整し、長繊維をネット上に捕集し、平均繊度1.5dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを得た。
表1に示したように、実施例1において、固有粘度[η]=1.025(dl/g)のPBTの代わりに、固有粘度[η]=0.775(dl/g)のPETを用い、固有粘度[η]=0.585(dl/g)のPETの代わりに、固有粘度[η]=0.52(dl/g)のPETを用いた以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
表1に示したように、実施例1において、固有粘度[η]=0.585(dl/g)のPETの代わりに、固有粘度[η]=0.52(dl/g)のPETを用い、さらに、水系ポリウレタンの含有割合を変更した以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
表1に示したように、実施例1において、平均繊度0.3dtexのPETの極細繊維を形成させた代わりに、平均繊度0.5dtexのPETの極細繊維を形成させ、さらに、水系ポリウレタンの含有割合を変更した以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
実施例3の第2の繊維ウェブを、次のようにして製造された第2の繊維ウェブに変更し、表1に示したような長繊維の極細繊維に変更した以外は実施例1と同様にして立毛人工皮革を得、評価した。結果を表1に示す。
(第2の繊維ウェブの製造)
水溶性熱可塑性ポリビニルアルコール系樹脂(PVA;海成分)と変性度6モル%のイソフタル酸変性ポリエチレンテレフタレ-ト(島成分)とを、海成分/島成分が25/25(質量比)となるように260℃で溶融複合紡糸用口金(島数:12島/繊維)より吐出し、紡糸速度が3500m/minとなるようにエジェクター圧力を調整し、長繊維をネット上に捕集し、長繊維の平均繊度3.0dtexの海島型複合繊維を含む第2の繊維ウェブを得た。
表1に示したように、実施例3において、平均繊度1.5dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブの代わりに、平均繊度0.6dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを用いた以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
表1に示したように、実施例2において、固有粘度[η]=0.775(dl/g)のPETの代わりに、固有粘度[η]=1.025(dl/g)のPBTを用い、第2の繊維ウェブ/第1の繊維ウェブ/第2の繊維ウェブ=1/2/1の重量比で積層して積重ウェブを形成した代わりに、第1の繊維ウェブのみで同じ目付の積重ウェブを形成し、さらに、水系ポリウレタンの含有割合を変更した以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
表1に示したように、比較例1において、積重ウェブを1840パンチ/cm2でニードルパンチングする代わりに、2760パンチ/cm2でニードルパンチングした等の変更をした以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
表1に示したように、実施例1において、平均繊度1.5dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブの代わりに、固有粘度[η]=0.615(dl/g)のPETからなるポリエステル繊維を含む第1の繊維ウェブを用い、積重ウェブを1840パンチ/cm2でニードルパンチングする代わりに、3680パンチ/cm2でニードルパンチングし、さらに、水系ポリウレタンの含有割合を変更した以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
表1に示したように、実施例1において、平均繊度0.3dtexのPETの極細繊維を形成させた代わりに、平均繊度0.6dtexのPETの繊維を形成させた以外は同様にして立毛人工皮革を得、評価した。結果を表1に示す。
固有粘度[η]=1.025(dl/g)のポリブチレンテレフタレート(PBT)と固有粘度[η]=0.52(dl/g)のポリエチレンテレフタレート(PET)とを50/50の比率で用い、275℃で1ホールの面積Cが0.08mm2である溶融複合紡糸用口金より、吐出速度A0.25(g/min)で吐出した。なお、このとき、樹脂の溶融密度Bは、1.21(g/cm3)であった。そして、紡糸速度Dが3987m/minとなるようにエジェクター圧力を調整し、紡糸ドラフトが1544になるように紡糸して長繊維をネット上に捕集することにより、平均繊度0.63dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを得た。
また、ポリウレタン含有割合は10質量%であった。
捲縮型繊維(A1)の溶融紡糸の際に、紡糸ノズル1ホールから吐出されるポリマーの吐出速度をA(g/min)、ポリマーの溶融密度をB(g/cm3)、1ホールの面積をC(mm2)、紡糸速度をD(m/min)として、以下の式により紡糸ドラフトを算出した。
・紡糸ドラフト=D/(A/B/C×104)
なお、樹脂の溶融密度B(g/cm3)は、溶融紡糸の際に固有粘度の異なる2種の樹脂がそれぞれ吐出されるときの吐出体積(cc/rpm)E1,E2とし、それらを吐出するときの各ギアポンプの回転数(rpm)をそれぞれF1とF2とし、吐出される1分間のポリマー吐出量(g/min)G1とG2を測定し、以下の式から算出した。
・溶融密度(g/cm3)=G1/E1/F1×G1/(G1+G2)+G2/E2/F2×G2/(G1+G2)
厚さ方向の断面の空隙の平均面積は以下のようにして測定した。
人工皮革基材の厚み方向の断面の全層を40倍の倍率で走査型電子顕微鏡で観察し、その画像を撮影した。そして、得られた画像を画像解析ソフトPopimaging(Digital being kids. Co製)を用い、動的閾値法で画像を二値化した。そして、二値化した画像をimage pro premier (日本ローパー社製)で読み込み、カウントツールで面積が5ドット以上の空隙部を抽出した。計測は万遍なく選択した3箇所の断面で行った。そして、計測ツールで抽出した各空隙部の面積を測定して平均値を求めた。図2に実施例1で得られた画像の一例を示す。黒い箇所のそれぞれが空隙部である。
実施例7において、次のように製造された第1の繊維ウェブを用いた以外は同様にして立毛人工皮革を得、評価した。
固有粘度[η]=1.025(dl/g)のポリブチレンテレフタレート(PBT)と固有粘度[η]=0.52(dl/g)のポリエチレンテレフタレート(PET)とを50/50の比率で用い、275℃で1ホールの面積Cが0.08mm2である溶融複合紡糸用口金より、吐出速度A0.51(g/min)で吐出した。そして、紡糸速度Dが4048m/minとなるようにエジェクター圧力を調整し、紡糸ドラフトが768になるように紡糸して長繊維をネット上に捕集することにより、平均繊度1.18dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを得た。
結果を表2に示す。
実施例7において、次のように製造された第1の繊維ウェブを用いた以外は同様にして立毛人工皮革を得、評価した。
固有粘度[η]=1.025(dl/g)のポリブチレンテレフタレート(PBT)と固有粘度[η]=0.52(dl/g)のポリエチレンテレフタレート(PET)とを50/50の比率で用い、275℃で1ホールの面積Cが0.08mm2である溶融複合紡糸用口金より、吐出速度A1.0(g/min)で吐出した。そして、紡糸速度Dが4132m/minとなるようにエジェクター圧力を調整し、紡糸ドラフトが400になるように紡糸して長繊維をネット上に捕集することにより、平均繊度2.42dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを得た。
結果を表2に示す。
実施例7において、次のように製造された第2の繊維ウェブを用いて、平均繊度0.3dtexのPETの極細繊維を形成させた代わりに、平均繊度0.5dtexのPETの極細繊維を形成させた以外は同様にして立毛人工皮革を得、評価した。
水溶性熱可塑性ポリビニルアルコール系樹脂(PVA;海成分)と変性度6モル%のイソフタル酸変性ポリエチレンテレフタレ-ト(島成分)とを、海成分/島成分が50/50(質量比)となるように260℃で溶融複合紡糸用口金(島数:12島/繊維)より吐出し、紡糸速度800m/minで紡糸を行った。次に、延伸し平均繊度11.8dtexの繊維を得た後、捲縮を付与した。得られた捲縮後繊維を51mmにカットし、カード機を通して第2の繊維ウェブを得た。
結果を表2に示す。
実施例7において、第2の繊維ウェブ/第1の繊維ウェブ/第2の繊維ウェブ=1/2/1の質量比で積層し、積層ウェブを形成した代わりに、1/8.5/1の質量比で積層し、積層ウェブを得た以外は同様にして立毛人工皮革を得、評価した。結果を表2に示す。
実施例7において、第2の繊維ウェブ/第1の繊維ウェブ/第2の繊維ウェブ=1/2/1の質量比で積層し、積層ウェブを形成した代わりに、0.7/1/0.7の質量比で積層し、積層ウェブを得た以外は同様にして立毛人工皮革を得、評価した。結果を表2に示す。
実施例8において、熱収縮繊維シートに、水系ポリウレタンのエマルジョン(固形分10%)をpick up50%で含浸させた代わりに、水系ポリウレタンのエマルジョン(固形分11%)をpick up50%で含浸させて、ポリウレタン含有割合を10質量%の代わりに8.5質量%に変更した以外は同様にして立毛人工皮革を得、評価した。
結果を表2に示す。
実施例8において、熱収縮繊維シートに、水系ポリウレタンのエマルジョン(固形分10%)をpick up50%で含浸させた代わりに、水系ポリウレタンのエマルジョン(固形分18.8%)をpick up50%で含浸させて、ポリウレタン含有割合を10質量%の代わりに13質量%に変更した以外は同様にして立毛人工皮革を得、評価した。結果を表2に示す。
実施例13において、次のように製造された第1の繊維ウェブを用いた以外は同様にして立毛人工皮革を得、評価した。
固有粘度[η]=1.025(dl/g)のポリブチレンテレフタレート(PBT)と固有粘度[η]=0.52(dl/g)のポリエチレンテレフタレート(PET)とを50/50の比率で用い、275℃で1ホールの面積Cが0.08mm2である溶融複合紡糸用口金より、吐出速度A1.0(g/min)で吐出した。そして、紡糸速度Dが4065m/minとなるようにエジェクター圧力を調整し、紡糸ドラフトが393になるように紡糸して長繊維をネット上に捕集することにより、平均繊度2.46dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを得た。
結果を下記表3に示す。
実施例7において、次のように製造された第1の繊維ウェブのみで積層ウェブを形成した、さらに、水系ポリウレタン含有割合を10質量%の代わりに6質量%に変更した以外は同様にして立毛人工皮革を得、評価した。
固有粘度[η]=1.025(dl/g)のポリブチレンテレフタレート(PBT)と固有粘度[η]=0.52(dl/g)のポリエチレンテレフタレート(PET)とを50/50の比率で用い、275℃で1ホールの面積Cが0.08mm2である溶融複合紡糸用口金より、吐出速度A0.51(g/min)で吐出した。そして、紡糸速度Dが3643m/minとなるようにエジェクター圧力を調整し、紡糸ドラフトが691になるように紡糸して長繊維をネット上に捕集することにより、平均繊度1.4dtexのサイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブを得た。
結果を表3に示す。
実施例7において、サイドバイサイド型のポリエステル繊維を含む第1の繊維ウェブの代わりに、平均繊度1.32dtexのレギュラー型のポリエステル繊維を含む第1の繊維ウェブを用い、第1の繊維ウェブのみで積層ウェブを形成し、さらに、水系ポリウレタン含有割合を10質量%の代わりに6質量%に変更した以外は同様にして立毛人工皮革を得、評価した。結果を表3に示す。
実施例8において、熱収縮繊維シートに、水系ポリウレタンのエマルジョン(固形分10%)をpick up50%で含浸させた代わりに、水系ポリウレタンのエマルジョン(固形分6.6%)をpick up50%で含浸させて、ポリウレタン含有割合を10質量%の代わりに5質量%に変更した以外は同様にして立毛人工皮革を得、評価した。結果を表3に示す。
実施例8において、熱収縮繊維シートに、水系ポリウレタンのエマルジョン(固形分10%)をpick up50%で含浸させた代わりに、水系ポリウレタンのエマルジョン(固形分10.2%)をpick up50%で含浸させて、ポリウレタン含有割合を10質量%の代わりに7.5質量%に変更した以外は同様にして立毛人工皮革を得、評価した。結果を表3に示す。
実施例8において、熱収縮繊維シートに、水系ポリウレタンのエマルジョン(固形分10%)をpick up50%で含浸させた代わりに、水系ポリウレタンのエマルジョン(固形分24%)をpick up50%で含浸させて、ポリウレタン含有割合を10質量%の代わりに16質量%に変更した以外は同様にして立毛人工皮革を得、評価した。結果を表3に示す。
Claims (15)
- 繊維(A)と繊維(B)との絡合体である不織布と、前記不織布の内部に付与された高分子弾性体と、を含み、
前記繊維(A)は、互いに固有粘度の異なる2種の樹脂から形成された捲縮繊維であって、0.6dtex以上の平均繊度を有する長繊維であり、
前記繊維(B)は、0.6dtex未満の平均繊度を有する極細繊維である人工皮革基材。 - 前記繊維(A)は、平均湾曲率が10%以上である請求項1に記載の人工皮革基材。
- 前記繊維(A)は、平均湾曲率が15%以上である請求項1に記載の人工皮革基材。
- 前記繊維(B)は、平均湾曲率が15%未満である請求項3に記載の人工皮革基材。
- 前記繊維(B)は、平均繊維長100mm未満の短繊維である請求項1~4の何れか1項に記載の人工皮革基材。
- 前記繊維(A)は、前記2種の樹脂の前記固有粘度の差が0.05(dl/g)以上であるサイドバイサイド型繊維または偏芯芯鞘型繊維である請求項1~5の何れか1項に記載の人工皮革基材。
- 前記2種の樹脂はポリエステルである請求項1~6の何れか1項に記載の人工皮革基材。
- 前記繊維(A)と前記繊維(B)との配合割合((A)/(B))が、10/90~90/10である請求項1~7の何れか1項に記載の人工皮革基材。
- 荷重1kgを5分間付加したときの平均伸長率が10%以上である請求項1~8の何れか1項に記載の人工皮革基材。
- 前記高分子弾性体は水系ポリウレタンであり、
前記水系ポリウレタンの含有割合が8~15質量%であり、
厚さ方向の断面の空隙の平均面積が300~1000μm2である請求項1~9の何れか1項に記載の人工皮革基材。 - 請求項1~10の何れか1項に記載の人工皮革基材を含み、その一面が立毛処理されていることを特徴とする立毛人工皮革。
- 請求項1に記載の人工皮革基材の製造方法であって、
前記繊維(A)を形成するための、互いに固有粘度の異なる2種の樹脂から形成された0.6dtex以上の長繊維の捲縮型繊維(A1)を含む第1の繊維ウェブを準備する工程と、
前記繊維(B)を形成するための、極細繊維発生型繊維(B1)の第2の繊維ウェブを準備する工程と、
前記第1の繊維ウェブの少なくとも1面に前記第2の繊維ウェブを積層して積層ウェブを形成する工程と、
前記積重ウェブを形成する前記捲縮型繊維(A1)と前記極細繊維発生型繊維(B1)とを絡合処理させた絡合繊維シートを形成する工程と、
前記絡合繊維シートを熱収縮させて熱収縮繊維シートを形成する工程と、
前記熱収縮繊維シートを形成する前記極細繊維発生型繊維(B1)に極細繊維化処理することにより、前記捲縮型繊維(A1)と前記繊維(B)との絡合体である不織布を形成させる工程と、
前記熱収縮繊維シートまたは前記不織布に高分子弾性体を含浸付与する工程と、を少なくとも備える人工皮革基材の製造方法。 - 前記積層ウェブは、前記第1の繊維ウェブの両面に前記第2の繊維ウェブを積層した積層体である請求項12に記載の人工皮革基材の製造方法。
- 前記高分子弾性体を含浸付与する工程が、前記熱収縮繊維シートまたは前記不織布に、ポリウレタン水系エマルジョンを含浸させた後、乾燥させることにより水系ポリウレタンを生成させる工程である請求項12または13に記載の人工皮革基材の製造方法。
- 前記捲縮型繊維(A1)が、紡糸ドラフト400以上で紡糸された繊度0.6dtex以上の捲縮型繊維であり、
前記水系ポリウレタンの含有割合が8~15質量%で、厚さ方向の断面の空隙の平均面積が300~1000μm2である人工皮革基材を製造する請求項14に記載の人工皮革基材の製造方法。
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