WO2020138029A1 - Knitting string and knitted product - Google Patents

Knitting string and knitted product Download PDF

Info

Publication number
WO2020138029A1
WO2020138029A1 PCT/JP2019/050496 JP2019050496W WO2020138029A1 WO 2020138029 A1 WO2020138029 A1 WO 2020138029A1 JP 2019050496 W JP2019050496 W JP 2019050496W WO 2020138029 A1 WO2020138029 A1 WO 2020138029A1
Authority
WO
WIPO (PCT)
Prior art keywords
knitting
string
artificial leather
fibers
nonwoven fabric
Prior art date
Application number
PCT/JP2019/050496
Other languages
French (fr)
Japanese (ja)
Inventor
真人 割田
道憲 藤澤
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to JP2020563282A priority Critical patent/JP7356457B2/en
Publication of WO2020138029A1 publication Critical patent/WO2020138029A1/en

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • 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

Definitions

  • the present invention relates to a knitting cord including an artificial leather substrate and a knit product manufactured using the same.
  • artificial leather including an artificial leather substrate including a nonwoven fabric and a polymeric elastic body impregnated into the nonwoven fabric has been known.
  • Artificial leather is widely used as a surface material for footwear, bags, clothes, furniture and the like.
  • Patent Document 2 discloses an artificial leather having a silver-tone resin layer on one surface of an artificial leather substrate including a nonwoven fabric containing fibers having a denier of 0.3 or less and a polymeric elastic body impregnated into the nonwoven fabric.
  • a woven or knitted fabric using a leather-like yarn that is cut into a thickness of 0.5 to 1 mm and a width of 1 to 5 mm.
  • knit has been widely used as a material for uppers such as sports shoes.
  • Materials for uppers for sports shoes are required to have a high degree of functionality depending on their use.
  • the material for the upper using a knit can partially exhibit the functionality required by partially changing the structure of the knitted fabric.
  • Patent Document 6 discloses a leather-like yarn having a silver surface on one surface of a substrate composed of ultrafine fibers and an elastic polymer.
  • the string having such a silver surface has a large frictional resistance when the strings rub against each other at the time of knitting, so that the string is likely to be cut, and its practicality is low.
  • the string obtained by shredding the artificial leather substrate has been known.
  • knitting operation by forming a new loop on the preformed loop and passing through it, or hooking the string on the hook of the knitting needle in inlay knitting
  • the cords were sometimes rubbed and cut.
  • Another aspect of the present invention is a knit product including any one of the above knitting strings.
  • Such a knit product has a novel design that retains fullness and suppleness.
  • a knitting cord including an artificial leather substrate that is unlikely to cause cutting in the knitting process, and a knit product manufactured using the same.
  • FIG. 1 is a schematic view of a knit product including the knitting cord of the embodiment.
  • FIG. 2 is a schematic diagram of a knit product using the knitting cord of the embodiment as an inlay knitting element.
  • FIG. 3 is a graph in which the results of Examples and Comparative Examples are plotted.
  • Polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate resin and other aliphatic polyesters nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 6 and 12 nylon; polypropylene, polyethylene, Fibers such as polybutene, polymethylpentene, and polyolefin such as chlorine-based polyolefin can be used. These may be used alone or in combination of two or more.
  • the ultrafine fibers forming the non-woven fabric may contain a colorant such as a dye or a pigment, an ultraviolet absorber, a heat stabilizer, a deodorant, a fungicide, and various stabilizers, if necessary.
  • the average fineness of the ultrafine fibers forming the non-woven fabric is 0.5 dtex or less, 0.0001 to 0.5 dtex, and further 0.001 to 0.2 dtex, which is knit knitting having both flexibility and fullness. It is preferable in that a cord can be obtained.
  • the ultrafine fibers forming the non-woven fabric form a fiber bundle of ultrafine fibers derived from the ultrafine fiber generation type fibers from the viewpoint of obtaining a knitting cord excellent in breaking strength.
  • the number of ultrafine fibers forming the fiber bundle is not particularly limited, but it is preferably 5 to 70, and more preferably 10 to 50 from the viewpoint of excellent balance between flexibility and breaking strength.
  • the fiber length of the ultrafine fibers forming the non-woven fabric is intentionally cut after spinning, for example, even if the short fibers have a fiber length of about 3 to 100 mm, long fibers that are not intentionally cut after spinning (continuous Although it may be a fiber), a long fiber is preferable because the breaking strength of the string is likely to be high due to the high degree of entanglement and a high fullness is obtained.
  • the fiber length of the long fiber before it is made into an ultrafine fiber is preferably 100 mm or more, and can be technically manufactured, and unless it is inevitably cut in the manufacturing process, it is several meters or several meters.
  • the fiber length may be 100 m, several km or more.
  • polyurethane examples include polyurethane, (meth)acrylic polymer elastic body, acrylonitrile polymer elastic body, olefin polymer elastic body, polyester elastic body, and the like. Can be mentioned. Of these, polyurethane is particularly preferable because it has excellent abrasion resistance.
  • a polymer elastic material is, as described later, in a state of emulsion or solution, a nonwoven fabric which is an entangled body of ultrafine fibers, or a nonwoven fabric which is an entangled body of ultrafine fiber generating fibers for forming ultrafine fibers. After impregnation, it is applied by drying or by wet coagulation with a poor solvent.
  • nonwoven fabric/polymer elastic body of the nonwoven fabric, which is an entangled body of ultrafine fibers, and the polymer elastic body is 99/1 to 55/45, and further 95/5 to 60/40. It is preferable because it is excellent in balance with softness.
  • the artificial leather substrate of the present embodiment preferably contains a lubricant for imparting lubricity to the surface of the knitting cord and reducing frictional resistance against a knitting needle when knitting.
  • a lubricant for imparting lubricity to the surface of the knitting cord and reducing frictional resistance against a knitting needle when knitting.
  • the lubricant include, for example, silicone-based softeners such as amino-modified silicone-based, alkyl silicone-based, amide-modified silicone-based, and epoxy-modified silicone-based softeners, and vegetable waxes such as persimmon wax, carnauba wax, and candelilla wax; Animal waxes such as beeswax and wool wax; mineral waxes such as montan wax; petroleum waxes such as paraffin wax and microstarine wax; polyethylene wax, Fischer-Tropsch wax; synthetic waxes such as fatty acid ester waxes Silk protein etc. are mentioned.
  • silicone-based softeners are preferable because they can easily balance the friction
  • the content ratio of the lubricant contained in the string for knitting is 0.01 to 3% by mass, and further 0.1 to 2% by mass, so that the friction resistance of the surface during knitting is sufficient. It is preferable from the standpoint that the stepability of knitting is improved by reducing If the content of the lubricant contained in the knitting cord is too high, the breaking strength tends to be low and the processability tends to be low.
  • the artificial leather substrate of the present embodiment may include a reinforcing material for a polymeric elastic body that is provided as a finishing agent after the application of the polymeric elastic body described above in order to improve the strength as a knitting cord.
  • a reinforcing agent include polyurethane, (meth)acrylic polymer elastic body, acrylonitrile polymer elastic body, olefin polymer elastic body, polyester elastic body and the like.
  • the acrylic polymer elastic body is particularly preferable because it has excellent reinforcing properties and flexibility.
  • Such a reinforcing agent is added in the form of an emulsion or a solution by impregnating a non-woven fabric which is an entangled body of ultrafine fibers, and then drying or wet coagulating with a poor solvent.
  • the reinforcing agent is preferably impregnated between the fiber bundles of the ultrafine fibers to enhance the reinforcing effect.
  • the content ratio of the reinforcing agent contained in the knitting braid is 0.01 to 5% by mass, and further 0.5 to 3% by mass, so that the strength of the knitting braid is increased. It is preferable from the viewpoint of improving the processability of the coating. If the content of the reinforcing agent contained in the knitting cord is too high, the flexibility tends to decrease and the processability tends to decrease.
  • a nonwoven fabric that is an entangled body of ultrafine fibers first manufacture a web of sea-island fibers.
  • a web can be produced, for example, by the spunbond method.
  • the molten polymer for forming the sea-island type fibers discharged from the spinneret is drawn and drawn by a suction device such as an air jet nozzle at a speed of 2000 to 5000 m/min, and then opened. It is manufactured by depositing it on a moving collection surface while making it fine.
  • the drawn sea-island type fiber preferably has a fineness of 1 to 4 dtex, more preferably 2 to 3 dtex.
  • the web thus obtained is laminated in a plurality of layers using a known web laminating apparatus (for example, a cross lap equipment) to form a stacked web, and the stacked web is three-dimensionally entangled to form sea-island type fibers.
  • a web entangled sheet is obtained.
  • the three-dimensional entanglement treatment of the stacked webs is performed by a needle punching treatment, a high-pressure water stream, or the like.
  • the needle punching treatment for example, it is preferable to perform the needle punching treatment under the condition that at least one barb penetrates from both sides simultaneously or alternately.
  • the punching density is not particularly limited, but is preferably in the range of 300 to 5000 punch/cm 2 , and more preferably in the range of 500 to 3500 punch/cm 2 . In this way, the web entangled sheet is obtained.
  • the artificial leather substrate In the production of the artificial leather substrate, either before or after the sea-island type fibers are made into ultrafine fibers, or both, for the purpose of preventing the fine fibers from slipping off, improving peeling strength, and imparting morphological stability and solidity.
  • a polymeric elastic body is impregnated into the internal voids of a web entangled sheet or a nonwoven fabric which is an entangled body of ultrafine fibers after being made into ultrafine fibers.
  • a method of applying an emulsion or solution of a polymer elastic body to a nonwoven fabric which is a entangled body of web entangled sheets or ultrafine fibers after ultrafine fiber formation, by a dip nip, and then coagulating by a dry or wet coagulation method.
  • a nonwoven fabric which is a entangled body of web entangled sheets or ultrafine fibers after ultrafine fiber formation, by a dip nip, and then coagulating by a dry or wet coagulation method.
  • the ultrafine fiber treatment is an entangled body of ultrafine fibers obtained by dissolving or decomposing and removing the resin forming the sea component by subjecting the web entangled sheet to hot water heating with water, an alkaline aqueous solution, an acidic aqueous solution, or the like. This is a step of forming a non-woven fabric.
  • the thickness of the artificial leather substrate is adjusted by slicing into multiple pieces in a direction perpendicular to the thickness direction or grinding as necessary. Further, by buffing the surface, a suede-like surface which is a napped surface may be formed.
  • the buffing is preferably performed using, for example, sandpaper or emery paper having a count of 120 to 600. It is preferable to have a suede-like surface because the frictional resistance to the knitting needle is particularly low in the knitting process.
  • the thickness of the artificial leather substrate thus obtained is, for example, 0.4 to 3.0 mm, and particularly preferably 0.5 to 2.0 mm.
  • the apparent density of the artificial leather substrate is 0.2 to 0.7 g/cm 3 , and further 0.3 to 0.6 g/cm 3, which is excellent in balance between fullness and supple texture. It is preferable from the point of view.
  • the lubricant can be applied to the entire artificial leather substrate.
  • the lubricant dispersion is preferably prepared so that the lubricant dispersion has a predetermined concentration, for example, about 0.1 to 20% by mass as the solid content of the dispersion.
  • the artificial leather substrate thus obtained is cut into a string with a slitting machine having a slit width of, for example, 0.5 to 3 mm, preferably 0.8 to 2 mm.
  • a string for knitting which is a string including the artificial leather substrate, is manufactured.
  • the breaking elongation (%) of the knitting cord is preferably 50 to 300%, and more preferably 60 to 250% from the viewpoint that it becomes difficult to cut in the knitting process.
  • the knitting cord of the present embodiment is a cord that retains a sense of fulfillment and suppleness and is excellent in knitting processability. By manufacturing a knitted product using such a knitting cord, it is possible to obtain a knit product having a new design while maintaining a sense of fulfillment and suppleness.
  • Examples 1 to 6, 9 to 13 and Comparative Examples 1 to 6 Water-soluble PVA as the sea component, PET with an isophthalic acid modification degree of 6 mol% as the island component, and the number of islands per fiber is 25 islands, so that the sea component/island component is 25/75 (mass ratio)
  • a melt-composite spinning die a sea-island type filament was discharged from the die at 260°C. Then, the ejector pressure was adjusted so that the spinning speed was 4000 m/min, the sea-island type continuous fibers having an average fineness of 2.5 dtex were collected on the net, and the continuous fiber web having a basis weight of 30 to 40 g/m 2 was collected.
  • Friction resistance of string (S) The friction resistance (S) of the obtained string was measured as follows. A test piece was prepared by cutting the string to be measured into 10 cm and 30 cm in the longitudinal direction. Then, a 10 cm string was bent at the central portion and both ends of the string were aligned, and the string was set on the upper chuck of a tensile tester in which the chuck distance was set to 200 mm so that a string loop having a length of about 3 cm was formed. Next, one end of a 30 cm string was set on the lower chuck, the other end was passed through the string loop set on the upper chuck, and then a 10 g weight was hung.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Knitting Of Fabric (AREA)
  • Braiding, Manufacturing Of Bobbin-Net Or Lace, And Manufacturing Of Nets By Knotting (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Provided is a knitting string and a knitted product manufactured using the same. This knitting string contains an artificial leather substrate, and also includes: a nonwoven fabric that is an entangled body of ultra-fine fibers having an average fineness of 0.5 dtex or smaller; and a polymer elastic body impregnated into the nonwoven fabric. The knitting string satisfies 10 ≥ T ≥ 4.6S + 0.5 and S < 0.18, where T is a breaking strength (kg/cm) of the string and S is a frictional resistance (kg) between strings. The string is preferably used in an inlay knitted element or a stocking-stitch knitted element of a knitted item.

Description

ニット編み用紐及びニット製品Knitting strings and knit products
　本発明は、人工皮革基体を含むニット編み用紐及びそれを用いて製造されるニット製品に関する。 The present invention relates to a knitting cord including an artificial leather substrate and a knit product manufactured using the same.
　従来から、不織布と不織布に含浸付与された高分子弾性体を含む人工皮革基体を含む人工皮革が知られている。人工皮革は、履物、鞄、衣類、家具等の表面素材として広く用いられている。 Conventionally, artificial leather including an artificial leather substrate including a nonwoven fabric and a polymeric elastic body impregnated into the nonwoven fabric has been known. Artificial leather is widely used as a surface material for footwear, bags, clothes, furniture and the like.
　人工皮革基体を細断して得られる紐も知られている。例えば、下記特許文献１は、人工皮革基体を幅２～１０ｍｍに細断した紐であり、靴紐や野球グローブの紐等の製造に用いられる紐を開示する。 Also known are strings obtained by shredding artificial leather substrates. For example, Patent Document 1 below discloses a string obtained by chopping an artificial leather base into a width of 2 to 10 mm, and discloses a string used for manufacturing shoelaces, baseball glove strings, and the like.
　また、例えば、下記特許文献２は、０．３デニール以下の繊維を含む不織布と不織布に含浸付与された高分子弾性体とを含む人工皮革基体の一面に銀面調の樹脂層を有する人工皮革を厚さ０．５～１ｍｍ、幅１～５ｍｍに細断した皮革状ヤーンを用いた織編物を開示する。 In addition, for example, Patent Document 2 below discloses an artificial leather having a silver-tone resin layer on one surface of an artificial leather substrate including a nonwoven fabric containing fibers having a denier of 0.3 or less and a polymeric elastic body impregnated into the nonwoven fabric. Disclosed is a woven or knitted fabric using a leather-like yarn that is cut into a thickness of 0.5 to 1 mm and a width of 1 to 5 mm.
　また、下記特許文献３は、平均繊度０．００１～２ｄｔｅｘの極細長繊維の不織布と不織布に含浸付与された高分子弾性体とを含む人工皮革基体の一面に銀面調の樹脂層を有する人工皮革を巾２～１０ｍｍに細断して得られた、インテリア製品用の織編物の製造に用いられる、紐状人工皮革製品を開示している。しかし、特許文献３に開示された紐状人工皮革製品は高強度であるが、しなやかさと紐同士の摩擦抵抗が大きい。そのために、目の細かい織編物を製造することには適していなかった。また、特許文献３に開示された紐状人工皮革製品は過度に高強度であるために、編み機の針に強い負荷がかかることにより、設備が破損してしまうこともあった。 In addition, Patent Document 3 below discloses an artificial leather substrate having a silver-tone resin layer on one surface of an artificial leather substrate including a nonwoven fabric of ultrafine long fibers having an average fineness of 0.001 to 2 dtex and a polymeric elastic body impregnated into the nonwoven fabric. Disclosed is a string-like artificial leather product obtained by cutting leather into a width of 2 to 10 mm and used for manufacturing a woven or knitted fabric for interior products. However, although the string-shaped artificial leather product disclosed in Patent Document 3 has high strength, it is supple and has a large friction resistance between strings. Therefore, it was not suitable for producing finely woven or knitted fabrics. Further, since the string-shaped artificial leather product disclosed in Patent Document 3 has an excessively high strength, a heavy load is applied to the needles of the knitting machine, which may damage the equipment.
　また、下記特許文献４は、弾性糸と、弾性糸よりも繊度が細い非弾性糸から成る弾性経編基布に、その弾性糸よりも見掛け繊度が太い人工皮革、又布をテープ状に裁断し、その裁断口から単糸繊度が３０ｄｔｅｘ以下の繊維が浮き出ているテープ糸条である非弾性嵩高糸がニットループを形成することなく編み込まれている弾性経編布帛を開示する。 Further, in Patent Document 4 below, an elastic warp knitted base fabric composed of an elastic yarn and a non-elastic yarn having a fineness smaller than that of the elastic yarn, artificial leather having an apparent fineness larger than that of the elastic yarn, or a cloth is cut into a tape shape. Then, an elastic warp knitted fabric is disclosed in which non-elastic bulky yarns, which are tape yarns in which fibers having a single yarn fineness of 30 dtex or less float out from the cut opening, do not form a knit loop.
　ところで、近年、スポーツ靴等のアッパー用素材としてニットが多く用いられている。スポーツ靴用のアッパー用素材は、その用途に応じて高度な機能性を要求される。ニットを用いたアッパー用素材は、編み地の構造を部分的に変えることで、部分的に要求に応じた機能性を発現させることが可能である。 By the way, in recent years, knit has been widely used as a material for uppers such as sports shoes. Materials for uppers for sports shoes are required to have a high degree of functionality depending on their use. The material for the upper using a knit can partially exhibit the functionality required by partially changing the structure of the knitted fabric.
　例えば、下記特許文献５は、履物製品のアッパーであって、ソール構造に接して配置されるように構成されたベース部を有するニット構成要素と、ベース部経路を通って延びるインレイ編みにより挿入される要素である伸張性ストランドとを有し、ベース部は、ニット構成要素の内側面および外側面を規定し、ベース部が、内側面と外側面との間にベース部経路を規定している、アッパーを開示する。そして、伸張性ストランドとして、ヤーン、ケーブル、ワイヤ、糸、より糸、フィラメント、繊維、スレッド、ロープ等を開示する。 For example, U.S. Pat. No. 6,037,049 is an upper for footwear products that is inserted by a knit component having a base portion configured to be placed in contact with a sole structure and an inlay knit extending through a base portion path. The base portion defines an inner surface and an outer surface of the knit component, and the base portion defines a base portion path between the inner surface and the outer surface. , Disclose uppers. Then, as the extensible strand, yarn, cable, wire, yarn, twisted yarn, filament, fiber, thread, rope, etc. are disclosed.
　また、下記特許文献６は、極細繊維と弾性重合体からなる基体の一面に銀面を有する皮革状ヤーンを開示する。このような銀面を有する紐は、ニッティング時に紐同士がこすれる際の摩擦抵抗が大きいために紐の切断が起こりやすくなり、実用性が低かった。 Further, Patent Document 6 below discloses a leather-like yarn having a silver surface on one surface of a substrate composed of ultrafine fibers and an elastic polymer. The string having such a silver surface has a large frictional resistance when the strings rub against each other at the time of knitting, so that the string is likely to be cut, and its practicality is low.
特開２０１２‐２０７３５３号公報JP, 2012-207353, A 特開昭５９－１５０１３３号公報JP-A-59-150133 国際公開２００８／１２０７０２号パンフレットInternational publication 2008/120702 pamphlet 特開２００６-１７６９０８号公報JP, 2006-176908, A 特開２０１８-１１８１５３号公報JP, 2018-118153, A 特開昭５９-１５０１３３号公報JP-A-59-150133
　上述したように、人工皮革基体を細断して得られた紐は従来から知られていた。人工皮革基体を細断して得られた紐を編むニッティングを行う場合、予め形成されたループに新たなループを形成させてくぐらせる編成動作や、インレイ編みにおいて、編み針のフックに紐を引っかけて引っ張ることによりループを形成する際に、紐同士が擦れて切断されることがあった。 As mentioned above, the string obtained by shredding the artificial leather substrate has been known. When knitting the string obtained by shredding the artificial leather base, knitting operation by forming a new loop on the preformed loop and passing through it, or hooking the string on the hook of the knitting needle in inlay knitting When forming a loop by pulling the cord, the cords were sometimes rubbed and cut.
　本発明は、人工皮革基体を細断して得られた紐をニット編み用紐として用いた場合、ニッティング工程において切断を生じさせにくい人工皮革基体を含むニット編み用紐及びそれを用いて製造されるニット製品を提供することを目的とする。 The present invention, when a string obtained by shredding an artificial leather substrate is used as a knitting string, a knitting string containing an artificial leather substrate that is unlikely to cause cutting in a knitting step, and a production using the same The purpose is to provide knit products that are manufactured.
　本発明の一局面は、人工皮革基体を含む紐であって、人工皮革基体は、平均繊度０．５ｄｔｅｘ以下の極細繊維の絡合体である不織布と、不織布に含浸付与された高分子弾性体とを含み、該紐の破断強力（ｋｇ/ｃｍ）をＴ，該紐同士の摩擦抵抗（ｋｇ）をＳとした場合、１０≧Ｔ≧４．６Ｓ+０．５，Ｓ＜０．１８を満たす、ニット編み物のインレイ編み要素又はメリヤス編み要素に好ましく用いられる、ニット編み用紐である。このようなニット編み用紐は、ニッティング工程において切断を生じさせにくいために、インレイ編み要素又はメリヤス編み要素に好適に用いることができる。 One aspect of the present invention is a string including an artificial leather substrate, wherein the artificial leather substrate is a nonwoven fabric that is an entangled body of ultrafine fibers having an average fineness of 0.5 dtex or less, and a polymeric elastic body impregnated into the nonwoven fabric. Where T is the breaking strength (kg/cm) of the cord and S is the frictional resistance (kg) between the cords, 10≧T≧4.6S+0.5, S<0.18 are satisfied. A cord for knitting, which is preferably used for an inlay knitting element or a knitting element of a knit knitting. Since such a knitting cord hardly causes cutting in the knitting step, it can be suitably used for an inlay knitting element or a knitting element.
　また、ニット編み用紐は、Ｔ≧１２Ｓ+０．５をさらに満たす場合には、インレイ編み要素としてもメリヤス編み要素としてもニッティング工程においてとくに切断を生じさせにくい点から好ましい。 Further, if the string for knitting is further satisfied with T≧12S+0.5, it is preferable as an inlay knitting element or a knitting element because it is particularly unlikely to cause cutting in the knitting process.
　また、ニット編み用紐は、滑剤を０．１～２質量％含むことが、ニッティング工程において摩擦抵抗を低下させて、より切断されにくくなる点から好ましい。 Further, it is preferable that the knit knitting cord contains 0.1 to 2% by mass of a lubricant, because friction resistance is lowered in the knitting process and it becomes more difficult to cut.
　また、ニット編み用紐は、スエード調表面を有することがニッティング工程において摩擦抵抗がより低くなる点から好ましい。 Also, it is preferable that the knitting cord has a suede-like surface because the frictional resistance in the knitting process becomes lower.
　また、本発明の他の一局面は、上記何れかのニット編み用紐を含むニット製品である。このようなニット製品は、充実感としなやかさを保持した、新規な意匠を有する。 Another aspect of the present invention is a knit product including any one of the above knitting strings. Such a knit product has a novel design that retains fullness and suppleness.
　本発明によれば、ニッティング工程において切断を生じさせにくい人工皮革基体を含むニット編み用紐及びそれを用いて製造されるニット製品を得ることができる。 According to the present invention, it is possible to obtain a knitting cord including an artificial leather substrate that is unlikely to cause cutting in the knitting process, and a knit product manufactured using the same.
図１は、実施形態のニット編み用紐を含むニット製品の模式図である。FIG. 1 is a schematic view of a knit product including the knitting cord of the embodiment. 図２は、実施形態のニット編み用紐をインレイ編み要素として用いたニット製品の模式図である。FIG. 2 is a schematic diagram of a knit product using the knitting cord of the embodiment as an inlay knitting element. 図３は、実施例及び比較例の結果をプロットしたグラフである。FIG. 3 is a graph in which the results of Examples and Comparative Examples are plotted.
　本発明に係る人工皮革基体を含むニット編み用紐及びそれを用いて製造されるニット製品の一実施形態を詳しく説明する。 An embodiment of a knitting cord including an artificial leather substrate according to the present invention and a knit product manufactured using the same will be described in detail.
　本実施形態のニット編み用紐は、人工皮革基体を含む紐であって、人工皮革基体は、平均繊度０．５ｄｔｅｘ以下の極細繊維の絡合体である不織布と、不織布に含浸付与された高分子弾性体とを含み、その紐の破断強力（ｋｇ/ｃｍ）をＴ，該紐同士の摩擦抵抗（ｋｇ）をＳとした場合、１０≧Ｔ≧４．６Ｓ+０．５，Ｓ＜０．１８を満たす、ニット編み物のインレイ編み要素又はメリヤス編み要素に好ましく用いられる、ニット編み用紐である。 The knitting cord of the present embodiment is a cord including an artificial leather base, and the artificial leather base is a nonwoven fabric which is an entangled body of ultrafine fibers having an average fineness of 0.5 dtex or less, and a polymer impregnated into the nonwoven fabric. When the breaking strength (kg/cm) of the string including an elastic body is T and the frictional resistance (kg) between the strings is S, 10≧T≧4.6S+0.5, S<0. A cord for knitting, which is preferably used for an inlay knitting element or a knitting element of a knit knitting, which satisfies 18.
　はじめに、ニット編み用紐を製造するための人工皮革基体について、詳しく説明する。 First, we will explain in detail the artificial leather substrate for manufacturing the knitting cord.
　人工皮革基体に含まれる不織布は、極細繊維が三次元的に絡合された絡合シートである。不織布を形成する極細繊維の種類は特に限定されない。その具体例としては、例えば、ポリエチレンテレフタレート（ＰＥＴ），イソフタル酸変性ＰＥＴ，スルホイソフタル酸変性ＰＥＴ，ポリブチレンテレフタレート，ポリヘキサメチレンテレフタレート等の芳香族ポリエステル；ポリ乳酸，ポリエチレンサクシネート，ポリブチレンサクシネート，ポリブチレンサクシネートアジペート，ポリヒドロキシブチレート－ポリヒドロキシバリレート樹脂等の脂肪族ポリエステル；ナイロン６，ナイロン６６，ナイロン１０，ナイロン１１，ナイロン１２，ナイロン６－１２等のナイロン；ポリプロピレン，ポリエチレン，ポリブテン，ポリメチルペンテン，塩素系ポリオレフィンなどのポリオレフィン等の繊維が挙げられる。これらは単独で用いても２種以上を組み合わせて用いてもよい。 The non-woven fabric included in the artificial leather substrate is an entangled sheet in which ultrafine fibers are entangled three-dimensionally. The type of ultrafine fibers forming the non-woven fabric is not particularly limited. Specific examples thereof include aromatic polyesters such as polyethylene terephthalate (PET), isophthalic acid modified PET, sulfoisophthalic acid modified PET, polybutylene terephthalate, polyhexamethylene terephthalate; polylactic acid, polyethylene succinate, polybutylene succinate. , Polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalerate resin and other aliphatic polyesters; nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 6 and 12 nylon; polypropylene, polyethylene, Fibers such as polybutene, polymethylpentene, and polyolefin such as chlorine-based polyolefin can be used. These may be used alone or in combination of two or more.
　また、不織布を形成する極細繊維は、染料や顔料等の着色剤、紫外線吸収剤、熱安定剤、消臭剤、防かび剤、各種安定剤等を必要に応じて含有してもよい。 Further, the ultrafine fibers forming the non-woven fabric may contain a colorant such as a dye or a pigment, an ultraviolet absorber, a heat stabilizer, a deodorant, a fungicide, and various stabilizers, if necessary.
　不織布を形成する極細繊維の平均繊度は０．５ｄｔｅｘ以下であり、０．０００１～０．５ｄｔｅｘ、さらには０．００１～０．２ｄｔｅｘの範囲であることが、しなやかさと充実感とを兼ね備えるニット編み用紐が得られる点から好ましい。 The average fineness of the ultrafine fibers forming the non-woven fabric is 0.5 dtex or less, 0.0001 to 0.5 dtex, and further 0.001 to 0.2 dtex, which is knit knitting having both flexibility and fullness. It is preferable in that a cord can be obtained.
　また、不織布を形成する極細繊維は、極細繊維発生型繊維に由来する極細繊維の繊維束を形成していることが、破断強力に優れるニット編み用紐が得られる点から好ましい。繊維束を形成する極細繊維の本数はとくに限定されないが、５～７０本、さらには、１０～５０本であることが、しなやかさと破断強力とのバランスに優れる点から好ましい。 Further, it is preferable that the ultrafine fibers forming the non-woven fabric form a fiber bundle of ultrafine fibers derived from the ultrafine fiber generation type fibers from the viewpoint of obtaining a knitting cord excellent in breaking strength. The number of ultrafine fibers forming the fiber bundle is not particularly limited, but it is preferably 5 to 70, and more preferably 10 to 50 from the viewpoint of excellent balance between flexibility and breaking strength.
　不織布を形成する極細繊維の繊維長は、紡糸後に意図的にカットされた、例えば繊維長が３～１００ｍｍ程度になるような短繊維であっても、紡糸後に意図的にカットされない長繊維（連続繊維）であってもよいが、長繊維であることが絡合度が高くなることにより紐の破断強力が高くなりやすく、また、高い充実感が得られる点から好ましい。長繊維である場合、極細繊維化する前の長繊維の繊維長は１００ｍｍ以上であることが好ましく、技術的に製造可能であり、かつ、製造工程において不可避的に切断されない限り、数ｍ、数百ｍ、数ｋｍあるいはそれ以上の繊維長であってもよい。 The fiber length of the ultrafine fibers forming the non-woven fabric is intentionally cut after spinning, for example, even if the short fibers have a fiber length of about 3 to 100 mm, long fibers that are not intentionally cut after spinning (continuous Although it may be a fiber), a long fiber is preferable because the breaking strength of the string is likely to be high due to the high degree of entanglement and a high fullness is obtained. When it is a long fiber, the fiber length of the long fiber before it is made into an ultrafine fiber is preferably 100 mm or more, and can be technically manufactured, and unless it is inevitably cut in the manufacturing process, it is several meters or several meters. The fiber length may be 100 m, several km or more.
　不織布に含浸付与される高分子弾性体の具体例としては、例えば、ポリウレタン、（メタ）アクリル系高分子弾性体、アクリロニトリル系高分子弾性体、オレフィン系高分子弾性体、ポリエステル弾性体、などが挙げられる。これらの中では、ポリウレタンが耐摩耗性に優れる点からとくに好ましい。このような高分子弾性体は、後述するように、エマルジョンや溶液の状態で、極細繊維の絡合体である不織布、または極細繊維を形成するための極細繊維発生型繊維の絡合体である不織布に含浸されたのち、乾燥させたり、貧溶媒を用いて湿式凝固させたりすることにより付与される。 Specific examples of the polymer elastic body impregnated into the nonwoven fabric include polyurethane, (meth)acrylic polymer elastic body, acrylonitrile polymer elastic body, olefin polymer elastic body, polyester elastic body, and the like. Can be mentioned. Of these, polyurethane is particularly preferable because it has excellent abrasion resistance. Such a polymer elastic material is, as described later, in a state of emulsion or solution, a nonwoven fabric which is an entangled body of ultrafine fibers, or a nonwoven fabric which is an entangled body of ultrafine fiber generating fibers for forming ultrafine fibers. After impregnation, it is applied by drying or by wet coagulation with a poor solvent.
　極細繊維の絡合体である不織布と高分子弾性体との質量比（不織布／高分子弾性体）は、９９／１～５５／４５、さらには９５／５～６０／４０であることが充実感としなやかさとのバランスに優れる点から好ましい。 A sense of fulfillment that the mass ratio (nonwoven fabric/polymer elastic body) of the nonwoven fabric, which is an entangled body of ultrafine fibers, and the polymer elastic body is 99/1 to 55/45, and further 95/5 to 60/40. It is preferable because it is excellent in balance with softness.
　本実施形態の人工皮革基体は、ニット編み用紐の表面に滑性を付与してニット編みする際に編み針に対する摩擦抵抗を低下させるための滑剤を含むことが好ましい。滑剤の具体例としては、例えば、アミノ変性シリコーン系、アルキルシリコーン系、アミド変性シリコーン系、エポキシ変性シリコーン系などのシリコーン系柔軟剤や、櫨蝋，カルナバワックス，キャンデリラワックスなどの植物性ワックス；蜜蝋，ウールワックスなどの動物性ワックス；モンタンワックス等の鉱物系ワックス；パラフィンワックス，マイクロスタリンワックス等の石油系ワックス；ポリエチレンワックス，フィッシャートロプシュワックス；脂肪酸エステル系ワックス等の合成ワックスなどのワックス類、シルクプロテイン等が挙げられる。これらの中では、シリコーン系柔軟剤が摩擦抵抗低減効果と機械物性や風合いのバランスがとりやすい点から好ましい。 The artificial leather substrate of the present embodiment preferably contains a lubricant for imparting lubricity to the surface of the knitting cord and reducing frictional resistance against a knitting needle when knitting. Specific examples of the lubricant include, for example, silicone-based softeners such as amino-modified silicone-based, alkyl silicone-based, amide-modified silicone-based, and epoxy-modified silicone-based softeners, and vegetable waxes such as persimmon wax, carnauba wax, and candelilla wax; Animal waxes such as beeswax and wool wax; mineral waxes such as montan wax; petroleum waxes such as paraffin wax and microstarine wax; polyethylene wax, Fischer-Tropsch wax; synthetic waxes such as fatty acid ester waxes Silk protein etc. are mentioned. Of these, silicone-based softeners are preferable because they can easily balance the frictional resistance reduction effect with mechanical properties and texture.
　また、ニット編み用紐に含まれる滑剤の含有割合としては、０．０１～３質量％、さらには、０．１～２質量％であることが、ニット編みする際の表面の摩擦抵抗を充分に低下させてニッティングの工程性を向上させる点から好ましい。ニット編み用紐に含まれる滑剤の含有割合が高すぎる場合には、破断強力が低下して工程性が低下する傾向がある。 Further, the content ratio of the lubricant contained in the string for knitting is 0.01 to 3% by mass, and further 0.1 to 2% by mass, so that the friction resistance of the surface during knitting is sufficient. It is preferable from the standpoint that the stepability of knitting is improved by reducing If the content of the lubricant contained in the knitting cord is too high, the breaking strength tends to be low and the processability tends to be low.
　本実施形態の人工皮革基体は、ニット編み用紐としての強度を向上させるため、上述した高分子弾性体の付与後に、仕上げ剤として付与される高分子弾性体の補強材を含んでもよい。このような補強剤の具体例としては、例えば、ポリウレタン、（メタ）アクリル系高分子弾性体、アクリロニトリル系高分子弾性体、オレフィン系高分子弾性体、ポリエステル弾性体、などが挙げられる。これらの中では、アクリル系高分子弾性体が補強性と柔軟性に優れる点からとくに好ましい。このような補強剤は、エマルジョンや溶液の状態で、極細繊維の絡合体である不織布に含浸されたのち、乾燥させたり、貧溶媒を用いて湿式凝固させたりすることにより付与される。補強剤は補強効果をより高めるため、極細繊維の繊維束間に含浸付与されることが好ましい。 The artificial leather substrate of the present embodiment may include a reinforcing material for a polymeric elastic body that is provided as a finishing agent after the application of the polymeric elastic body described above in order to improve the strength as a knitting cord. Specific examples of such a reinforcing agent include polyurethane, (meth)acrylic polymer elastic body, acrylonitrile polymer elastic body, olefin polymer elastic body, polyester elastic body and the like. Among these, the acrylic polymer elastic body is particularly preferable because it has excellent reinforcing properties and flexibility. Such a reinforcing agent is added in the form of an emulsion or a solution by impregnating a non-woven fabric which is an entangled body of ultrafine fibers, and then drying or wet coagulating with a poor solvent. The reinforcing agent is preferably impregnated between the fiber bundles of the ultrafine fibers to enhance the reinforcing effect.
　また、ニット編み用紐に含まれる補強剤の含有割合としては、０．０１～５質量％、さらには、０．５～３質量％であることが、ニット編み用紐の強度を高めてニッティングの工程性を向上させる点から好ましい。ニット編み用紐に含まれる補強剤の含有割合が高すぎる場合には、しなやかさが低下して工程性が低下する傾向がある。 Further, the content ratio of the reinforcing agent contained in the knitting braid is 0.01 to 5% by mass, and further 0.5 to 3% by mass, so that the strength of the knitting braid is increased. It is preferable from the viewpoint of improving the processability of the coating. If the content of the reinforcing agent contained in the knitting cord is too high, the flexibility tends to decrease and the processability tends to decrease.
　次に、人工皮革基体の製造方法について説明する。 Next, a method of manufacturing the artificial leather substrate will be described.
　極細繊維の絡合体である不織布は、例えば、海島型複合繊維（以下、単に海島型繊維とも呼ぶ）等の極細繊維発生型繊維のウェブを三次元的に絡合させた絡合体であるウェブ絡合シートの海成分のみを溶解除去または分解除去することによって得られる。極細繊維発生型繊維としては、海島型繊維の他、剥離分割型複合繊維等を用いてもよい。また、極細繊維を直接紡糸して極細繊維の絡合体である不織布を製造してもよい。本実施形態では、代表例として極細繊維発生型繊維として海島型繊維を製造する場合について詳しく説明する。 A nonwoven fabric that is an entangled body of ultrafine fibers is, for example, a web entangled body that is a three-dimensionally entangled web of ultrafine fiber-generating fibers such as sea-island type composite fibers (hereinafter also simply referred to as sea-island type fibers). It is obtained by dissolving or decomposing and removing only the sea component of the composite sheet. As the ultrafine fiber-generating fiber, a split-separated conjugate fiber or the like may be used in addition to the sea-island fiber. Alternatively, ultrafine fibers may be directly spun to produce a nonwoven fabric which is an entangled body of ultrafine fibers. In the present embodiment, as a typical example, a case where sea-island type fibers are manufactured as ultrafine fiber-generating fibers will be described in detail.
　海島型繊維は、例えば、相溶性を有しない２種のポリマーを混合して溶融し、紡糸口金から吐出する混合紡糸方法や、相溶性を有しない２種のポリマーを別々に溶融し、各溶融物を紡糸口金で合流させ吐出する複合紡糸方法により紡糸される。そして、得られた海島型繊維の海成分を溶解除去または分解除去することにより極細繊維の繊維束が形成される。海島型繊維の断面における島数は１０～１００個、さらには１５～５０個であることが好ましい。また、海成分と島成分との質量比は１０：９０～７０：３０であることが好ましい。 The sea-island type fiber is, for example, a mixed spinning method in which two types of polymers having no compatibility are mixed and melted and then discharged from a spinneret, or two types of polymers having no compatibility are separately melted and then melted. The product is spun by a composite spinning method in which the materials are joined by a spinneret and discharged. Then, the sea component of the obtained sea-island type fibers is dissolved or removed by decomposition to form a fiber bundle of ultrafine fibers. The number of islands in the cross section of the sea-island fiber is preferably 10 to 100, more preferably 15 to 50. The mass ratio of the sea component to the island component is preferably 10:90 to 70:30.
　島成分を形成する樹脂は上述した極細繊維を形成するための樹脂である。また、海成分を形成する樹脂は、海島型繊維の紡糸後に島成分を残して除去される樹脂である。海成分を形成する樹脂は、例えば、水、アルカリ性水溶液、酸性水溶液等により溶解除去または分解除去される熱可塑性樹脂であって、溶融紡糸が可能な樹脂が好ましく用いられる。このような海成分を形成する樹脂の具体例としては、例えば、水溶性ポリビニルアルコール系樹脂（ＰＶＡ系樹脂）やポリエチレン等が挙げられる。 The resin that forms the island component is the resin that forms the ultrafine fibers described above. In addition, the resin forming the sea component is a resin that is removed leaving the island component after spinning the sea-island type fiber. The resin forming the sea component is, for example, a thermoplastic resin that is dissolved or removed by decomposition with water, an alkaline aqueous solution, an acidic aqueous solution, or the like, and a resin capable of melt spinning is preferably used. Specific examples of the resin forming such a sea component include water-soluble polyvinyl alcohol-based resin (PVA-based resin) and polyethylene.
　極細繊維の絡合体である不織布の製造においては、はじめに海島型繊維からなるウェブを製造する。このようなウェブは、例えば、スパンボンド法により製造することができる。具体的には、例えば、紡糸口金から吐出された海島型繊維を形成するための溶融ポリマーをエアージェットノズルのような吸引装置により２０００～５０００ｍ／分の速度で牽引細化して延伸した後、開繊させながら移動式の捕集面上に堆積させて製造される。延伸された海島型繊維の繊度は１～４ｄｔｅｘ、さらには２～３ｄｔｅｘであることが好ましい。 When manufacturing a nonwoven fabric that is an entangled body of ultrafine fibers, first manufacture a web of sea-island fibers. Such a web can be produced, for example, by the spunbond method. Specifically, for example, the molten polymer for forming the sea-island type fibers discharged from the spinneret is drawn and drawn by a suction device such as an air jet nozzle at a speed of 2000 to 5000 m/min, and then opened. It is manufactured by depositing it on a moving collection surface while making it fine. The drawn sea-island type fiber preferably has a fineness of 1 to 4 dtex, more preferably 2 to 3 dtex.
　そして、得られたウェブを公知のウェブ積層装置（例えばクロスラップ設備）を用いて複数層に積層した積重ウェブを形成した後、積重ウェブを三次元絡合させることにより海島型繊維からなるウェブ絡合シートが得られる。 Then, the web thus obtained is laminated in a plurality of layers using a known web laminating apparatus (for example, a cross lap equipment) to form a stacked web, and the stacked web is three-dimensionally entangled to form sea-island type fibers. A web entangled sheet is obtained.
　積重ウェブの三次元絡合処理は、ニードルパンチ処理や高圧水流などにより行われる。ニードルパンチ処理の場合、例えば、両面から同時または交互に少なくとも１つ以上のバーブが貫通する条件で行うことが好ましい。パンチング密度はとくに限定されないが、３００～５０００パンチ／ｃｍ2の範囲、さらには５００～３５００パンチ／ｃｍ2の範囲であることが好ましい。このようにしてウェブ絡合シートが得られる。 The three-dimensional entanglement treatment of the stacked webs is performed by a needle punching treatment, a high-pressure water stream, or the like. In the case of the needle punching treatment, for example, it is preferable to perform the needle punching treatment under the condition that at least one barb penetrates from both sides simultaneously or alternately. The punching density is not particularly limited, but is preferably in the range of 300 to 5000 punch/cm 2 , and more preferably in the range of 500 to 3500 punch/cm 2 . In this way, the web entangled sheet is obtained.
　ウェブ絡合シートは、湿熱収縮処理により収縮させて海島型繊維を緻密化されることが好ましい。湿熱収縮処理は、スチーム加熱、熱水処理などの湿熱条件下で行うことが好ましい。このような湿熱条件下での処理により、ウェブ絡合シートが収縮する。 The web entangled sheet is preferably densified by shrinking the sea-island type fiber by a wet heat shrinking treatment. The wet heat shrinkage treatment is preferably performed under wet heat conditions such as steam heating and hot water treatment. The web entangled sheet shrinks due to the treatment under such a wet heat condition.
　人工皮革基体の製造においては、海島型繊維を極細繊維化する前後の何れか一方または両方において、極細繊維の素抜け防止や剥離強力の向上、形態安定性や充実感を付与することを目的として、ウェブ絡合シートまたは極細繊維化後の極細繊維の絡合体である不織布の、内部空隙に高分子弾性体を含浸付与する。ウェブ絡合シートまたは極細繊維化後の極細繊維の絡合体である不織布の、内部空隙に高分子弾性体を付与する方法としては、絡合ウェブまたは極細繊維の絡合体である不織布に、高分子弾性体のエマルジョンまたは溶液を、例えば、ディップニップしたり、ナイフコーター、バーコーター、又はロールコーターで含浸し、高分子弾性体を凝固させたりすることにより付与する方法が挙げられる。これらの中では、ウェブ絡合シートまたは極細繊維化後の極細繊維の絡合体である不織布に、高分子弾性体のエマルジョンまたは溶液をディップニップにより付与した後、乾燥又は湿式凝固法により凝固させる方法が好ましい。 In the production of the artificial leather substrate, either before or after the sea-island type fibers are made into ultrafine fibers, or both, for the purpose of preventing the fine fibers from slipping off, improving peeling strength, and imparting morphological stability and solidity. A polymeric elastic body is impregnated into the internal voids of a web entangled sheet or a nonwoven fabric which is an entangled body of ultrafine fibers after being made into ultrafine fibers. A web entangled sheet or a nonwoven fabric which is an entangled body of ultrafine fibers after ultrafine fiber formation, as a method for imparting a polymeric elastic body to the internal voids, a nonwoven fabric which is an entangled web or entangled body of ultrafine fibers, a polymer Examples thereof include a method in which an emulsion or solution of an elastic body is applied by dip nip or by impregnating with a knife coater, bar coater, or roll coater to solidify the polymeric elastic body. Among these, a method of applying an emulsion or solution of a polymer elastic body to a nonwoven fabric, which is a entangled body of web entangled sheets or ultrafine fibers after ultrafine fiber formation, by a dip nip, and then coagulating by a dry or wet coagulation method. Is preferred.
　次に、ウェブ絡合シートの海島型繊維中の海成分の樹脂を抽出除去する極細繊維化処理について説明する。 Next, the ultrafine fiberizing process for extracting and removing the sea component resin in the sea-island type fibers of the web entangled sheet will be explained.
　極細繊維化処理は、ウェブ絡合シートを、水、アルカリ性水溶液、酸性水溶液等で熱水加熱処理することにより、海成分を形成する樹脂を溶解除去または分解除去して極細繊維の絡合体である不織布を形成させる工程である。 The ultrafine fiber treatment is an entangled body of ultrafine fibers obtained by dissolving or decomposing and removing the resin forming the sea component by subjecting the web entangled sheet to hot water heating with water, an alkaline aqueous solution, an acidic aqueous solution, or the like. This is a step of forming a non-woven fabric.
　熱水加熱処理の条件の具体例としては、例えば、湿熱収縮処理されたウェブ絡合シートを、８５～１００℃の熱水中で１００～６００秒間処理することが好ましい。また、海成分の溶解効率を高めるために、必要に応じて、ディップニップ処理、高圧水流処理、超音波処理、シャワー処理、攪拌処理、揉み処理等を行ってもよい。これらの操作は必要に応じて繰り返し行うことが好ましい。 As a specific example of the condition of the hot water heat treatment, for example, it is preferable that the wet heat shrinkable web entangled sheet is treated in hot water of 85 to 100° C. for 100 to 600 seconds. Further, in order to enhance the dissolution efficiency of the sea component, dip nip treatment, high-pressure water stream treatment, ultrasonic treatment, shower treatment, stirring treatment, kneading treatment, etc. may be performed as necessary. These operations are preferably repeated if necessary.
　熱水加熱処理により、海島型繊維から海成分を除去する際に、形成される極細繊維が大きく捲縮する。この捲縮により繊維密度が緻密になるために、より高密度の極細繊維の絡合体である不織布が形成される。 　The hot water heat treatment significantly crimps the ultrafine fibers that are formed when removing sea components from the sea-island type fibers. This crimping causes the fiber density to become dense, so that a non-woven fabric which is an entangled body of higher density ultrafine fibers is formed.
　このようにして得られた極細繊維の絡合体である不織布は、極細繊維が配向している方向に沿って加熱延伸処理されることが好ましい。このような加熱延伸処理により、極細繊維をより配向させるとともに、極細繊維をさらに延伸することにより、破断強力を向上させることができる。加熱延伸処理は、例えば、スチーム乾燥機や赤外線乾燥機等の加熱炉を用いて、荷重を掛けながら、雰囲気温度８０～１３０℃の条件で延伸処理するような条件が選ばれる。 The non-woven fabric which is an entangled body of ultrafine fibers thus obtained is preferably heat-stretched along the direction in which the ultrafine fibers are oriented. By such a heat-stretching treatment, the ultrafine fibers can be more oriented, and the ultrafine fibers can be further stretched to improve the breaking strength. For the heating and stretching treatment, for example, a heating furnace such as a steam dryer or an infrared dryer is used, and a condition is selected such that the stretching treatment is carried out under an atmospheric temperature of 80 to 130° C. while applying a load.
　このようにして平均繊度０．５ｄｔｅｘ以下の極細繊維の絡合体である不織布と、不織布に含浸付与された高分子弾性体とを含む人工皮革基体が得られる。人工皮革基体は、必要に応じて、さらに公知の揉み処理等が施されてもよい。揉み処理により、柔軟性をさらに向上させることができる。 In this way, an artificial leather substrate including a nonwoven fabric, which is an entangled body of ultrafine fibers having an average fineness of 0.5 dtex or less, and a polymeric elastic body impregnated into the nonwoven fabric is obtained. The artificial leather substrate may be further subjected to known kneading treatment or the like, if necessary. The rubbing treatment can further improve the flexibility.
　人工皮革基体は、必要に応じて厚さ方向に垂直な方向に複数枚にスライスしたり、研削したりすることにより厚さ調節される。さらに、表面をバフィングすることにより、立毛面であるスエード調の表面を形成してもよい。バフィングは、例えば、１２０～６００番手程度のサンドペーパーやエメリーペーパーを用いて行うことが好ましい。スエード調表面を有する場合には、ニッティング工程において編み針に対する摩擦抵抗がとくに低くなる点から好ましい。 The thickness of the artificial leather substrate is adjusted by slicing into multiple pieces in a direction perpendicular to the thickness direction or grinding as necessary. Further, by buffing the surface, a suede-like surface which is a napped surface may be formed. The buffing is preferably performed using, for example, sandpaper or emery paper having a count of 120 to 600. It is preferable to have a suede-like surface because the frictional resistance to the knitting needle is particularly low in the knitting process.
　一方、人工皮革基体は、必要に応じて、表面にポリウレタン等の高分子弾性体からなる銀面調の樹脂表皮層が形成されてもよい。樹脂表皮層は、例えば、離型紙上に乾式造面された高分子弾性体シートを不織布の表面に接着剤で接着した後、離型紙を剥離する乾式造面法や、不織布の表面に高分子弾性体の溶液を塗布した後、凝固浴に浸漬して不織布の表面で高分子弾性体を凝固させる湿式造面法等により形成される。 On the other hand, the artificial leather substrate may have a silver-like resin skin layer made of a polymeric elastic material such as polyurethane formed on the surface, if necessary. The resin skin layer is, for example, a dry surface-forming method of peeling the release paper after adhering a polymer elastic sheet dry-formed on the release paper to the surface of the nonwoven fabric with an adhesive, or a polymer on the surface of the nonwoven fabric. It is formed by a wet surface-forming method or the like in which the elastic body solution is applied and then immersed in a coagulation bath to coagulate the polymeric elastic body on the surface of the nonwoven fabric.
　このようにして得られる人工皮革基体の厚さは、例えば、０．４～３．０ｍｍ、とくには、０．５～２．０ｍｍであることが好ましい。また、人工皮革基体の見かけ密度としては、０．２～０．７ｇ／ｃｍ3、さらには、０．３～０．６ｇ／ｃｍ3であることが充実感としなやかな風合いとのバランスに優れる点から好ましい。 The thickness of the artificial leather substrate thus obtained is, for example, 0.4 to 3.0 mm, and particularly preferably 0.5 to 2.0 mm. In addition, the apparent density of the artificial leather substrate is 0.2 to 0.7 g/cm 3 , and further 0.3 to 0.6 g/cm 3, which is excellent in balance between fullness and supple texture. It is preferable from the point of view.
　さらに、人工皮革基体は、滑剤を含むことが好ましい。人工皮革基体に滑剤を含浸付与する方法は特に限定されないが、例えば、人工皮革基体の全体に、滑剤の溶液または分散液を含浸した後、乾燥することにより、人工皮革基体の内部の繊維又は高分子弾性体に滑剤を被着させることができる。また、別の方法としては、ウェブ絡合シートまたは極細繊維の絡合体である不織布に、高分子弾性体を付与する際に、高分子弾性体のエマルジョンや溶液に配合して、高分子弾性体と同時に付与してもよい。 Furthermore, the artificial leather substrate preferably contains a lubricant. The method of impregnating the artificial leather substrate with the lubricant is not particularly limited, and, for example, by impregnating the entire artificial leather substrate with the solution or dispersion of the lubricant and then drying the fibers, the fibers or the inside of the artificial leather substrate are increased. A lubricant can be applied to the molecular elastic body. Further, as another method, when a polymer elastic body is applied to a nonwoven fabric, which is a web entangled sheet or an entangled body of ultrafine fibers, the polymer elastic body is mixed with an emulsion or solution of the polymer elastic body. You may give at the same time.
　滑剤は分散液の状態で人工皮革基体に含浸した後、乾燥して付与することがとくに好ましい。このような方法によれば、人工皮革基体の全体に滑剤を付与することができる。滑剤の分散液は、滑剤の分散液を、所定の濃度、例えば、分散液の固形分として、０．１～２０質量％程度になるように調製することが好ましい。 It is particularly preferable to apply the lubricant after impregnating the artificial leather substrate in a dispersion state and then drying. According to such a method, the lubricant can be applied to the entire artificial leather substrate. The lubricant dispersion is preferably prepared so that the lubricant dispersion has a predetermined concentration, for example, about 0.1 to 20% by mass as the solid content of the dispersion.
　また、人工皮革基体は、紐の強度を補強する目的として上述したような補強剤を付与して仕上げてもよい。人工皮革基体に補強剤を含浸付与する方法は特に限定されない。例えば、人工皮革基体の全体に、補強剤の溶液または分散液を含浸した後、乾燥することにより、人工皮革基体の内部の繊維又は高分子弾性体に補強剤を被着させることができる。 Also, the artificial leather substrate may be finished by adding the above-mentioned reinforcing agent for the purpose of reinforcing the strength of the string. The method of impregnating the artificial leather substrate with the reinforcing agent is not particularly limited. For example, by impregnating the entire artificial leather substrate with the solution or dispersion of the reinforcing agent, and then drying it, the reinforcing agent can be applied to the fibers or the polymer elastic body inside the artificial leather substrate.
　補強剤は分散液の状態で人工皮革基体に含浸した後、乾燥して付与することがとくに好ましい。このような方法によれば、人工皮革基体の全体に補強剤を付与することができる。補強剤の分散液は、補強剤の分散液を、所定の濃度、例えば、分散液の固形分として、０．１～２０質量％程度になるように調製することが好ましい。 It is particularly preferable to apply the reinforcing agent by impregnating the artificial leather substrate in a dispersion state and then drying it. According to such a method, the reinforcing agent can be applied to the entire artificial leather substrate. The dispersion liquid of the reinforcing agent is preferably prepared so that the dispersion liquid of the reinforcing agent has a predetermined concentration, for example, about 0.1 to 20% by mass as the solid content of the dispersion liquid.
　このようにして得られた人工皮革基体は、例えば、０．５～３ｍｍ、好ましくは、０．８～２ｍｍのスリット幅で裁断機等により裁断されることにより紐に加工される。このようにして、人工皮革基体を含む紐であるニット編み用紐が製造される。 The artificial leather substrate thus obtained is cut into a string with a slitting machine having a slit width of, for example, 0.5 to 3 mm, preferably 0.8 to 2 mm. In this way, a string for knitting, which is a string including the artificial leather substrate, is manufactured.
　ニット編み用紐の断面のアスペクト比（幅/厚さ）としては、０．７～２．５、さらには１～２であることが好ましい。なお、厚さは、人工皮革基体の厚さであり、幅は人工皮革を細断するときのスリット幅である。アスペクト比（厚さ/幅）が低すぎる場合には、人工皮革基体の裁断時に、極細繊維が裁断されて短くなりすぎて、強度にムラがでてニッティング工程において切断しやすくなり、高すぎる場合には、得られたニット製品にねじれ部分が生じて編目欠点のように見える外観低下を生じさせやすくなる。 The aspect ratio (width/thickness) of the cross section of the knitting cord is preferably 0.7 to 2.5, and more preferably 1 to 2. The thickness is the thickness of the artificial leather substrate, and the width is the slit width when the artificial leather is shredded. If the aspect ratio (thickness/width) is too low, when the artificial leather substrate is cut, the ultrafine fibers will be cut and become too short, resulting in uneven strength and easy cutting in the knitting process, and too high. In this case, a twisted portion is formed in the obtained knit product, which tends to cause a deterioration in appearance that looks like a stitch defect.
　このようにして得られる本実施形態の紐は、その破断強力（ｋｇ/ｃｍ）をＴ，紐同士の摩擦抵抗（ｋｇ）をＳとした場合、１０≧Ｔ≧４．６Ｓ+０．５，Ｓ＜０．１８を満たすように調整されている。ニット編成時に編み紐は、互いにこすれあって摩擦抵抗を生じる。人工皮革からなる編み紐は、人工皮革を細断した際の断面に多くの極細繊維断面が存在するため、通常の紡績糸などと比べて摩擦抵抗が大きくなりやすい。また、人工皮革を細断した紐は、不織布を構成する極細繊維が紐の幅に合わせて切断されてしまうため、通常の紡績糸などと比べて強度が弱くなりやすい。上述したような破断強力と紐同士の摩擦抵抗の関係式を満たす紐によれば、優れたニッティング性を確保できる。また、さらに、Ｔ≧１２Ｓ+０．５をさらに満たす場合には、インレイ編み要素としてもメリヤス編み要素としてもニッティング工程においてとくに切断を生じさせにくい点から好ましい。なお、切片の０．５は、摩擦抵抗および破断強力はどちらも理論上０にはならないため、摩擦抵抗および破断強力が低い領域において、実測データから導き出された補正値である。 When the breaking strength (kg/cm) is T and the frictional resistance (kg) between the strings is S, the thus obtained cord of the present embodiment is 10≧T≧4.6S+0.5, It is adjusted to satisfy S<0.18. When knitting, the braids rub against each other to generate frictional resistance. Since the knitted cord made of artificial leather has many ultrafine fiber cross-sections when the artificial leather is shredded, friction resistance tends to be larger than that of ordinary spun yarn. In addition, the string obtained by chopping artificial leather tends to be weaker in strength than ordinary spun yarn, because the ultrafine fibers constituting the nonwoven fabric are cut according to the width of the string. A string satisfying the relational expression between the breaking strength and the frictional resistance between the strings as described above can ensure excellent knitting property. Further, when T≧12S+0.5 is further satisfied, it is preferable that both the inlay knitting element and the knitting knitting element are less likely to cause cutting in the knitting process. It should be noted that 0.5 of the intercept is a correction value derived from the actual measurement data in the region where the frictional resistance and the breaking strength are low, since neither the frictional resistance nor the breaking strength theoretically becomes 0.
　ニット編み用紐の破断強力Ｔ（ｋｇ/ｃｍ）としては、０．５～１０ｋｇ/ｃｍ、さらには、０．６～８ｋｇ/ｃｍであることが、ニッティング工程において切断しにくい紐になるとともに、充分なしなやかさを保持する点から好ましい。１０ｋｇ/ｃｍを超える場合には、しなやかさが低下し、また、ニット編み機の針に過度な負荷がかかることにより設備を破損させやすくなる。 The breaking strength T (kg/cm) of the knitting cord is 0.5 to 10 kg/cm, and further 0.6 to 8 kg/cm, which makes the cord difficult to cut in the knitting process. It is preferable from the viewpoint of maintaining sufficient flexibility. When it exceeds 10 kg/cm, the suppleness is lowered, and the needle of the knitting machine is excessively loaded, so that the equipment is easily damaged.
　また、ニット編み用紐の破断伸び（％）としては、５０～３００％、さらには、６０～２５０％であることが、ニッティング工程において切断しにくい紐になる点から好ましい。 Further, the breaking elongation (%) of the knitting cord is preferably 50 to 300%, and more preferably 60 to 250% from the viewpoint that it becomes difficult to cut in the knitting process.
　また、ニット編み用紐の摩擦抵抗Ｓ（ｋｇ）は、Ｓ＜０．１８であり、０．０２≦Ｓ＜０．１８、さらには、０．０２５≦Ｓ≦０．１６であることが、ニッティング工程において切断しにくい紐になる点から好ましい。なお、本実施形態における摩擦抵抗Ｓの測定方法は後に詳述する。 Also, the friction resistance S (kg) of the knitting cord is S<0.18, 0.02≦S<0.18, and further 0.025≦S≦0.16. It is preferable because it becomes a string that is difficult to cut in the knitting step. The method of measuring the frictional resistance S in this embodiment will be described in detail later.
　本実施形態のニット編み用紐は、充実感としなやかを保持し、ニッティング工程性に優れた紐である。このようなニット編み用紐を用いて編み物を製造することにより、充実感としなやかを保持し、新規な意匠を有するニット製品を得ることができる。 The knitting cord of the present embodiment is a cord that retains a sense of fulfillment and suppleness and is excellent in knitting processability. By manufacturing a knitted product using such a knitting cord, it is possible to obtain a knit product having a new design while maintaining a sense of fulfillment and suppleness.
　図１は、実施形態のニット編み用紐１を含むニット製品１０の模式図である。また、図２は、ニット編み用紐１をインレイ編み要素として用いたニット製品２０の模式図である。 FIG. 1 is a schematic view of a knit product 10 including the knitting cord 1 of the embodiment. 2 is a schematic diagram of a knit product 20 using the knitting cord 1 as an inlay knitting element.
　図１のニット製品１０は、ニット編み用紐１をメリヤス編みであるゴム編みしたときの模式図を示す。メリヤス編みとしては、ゴム編みの他、平編み、パール編み、経編み等特に限定なく採用できる。また、図２のニット製品２０は、従来から知られた、毛糸やナイロン糸等のニット編み用糸２をメリヤス編みし、ニット編み用紐１をインレイ編み要素として用いたときの模式図を示す。 The knit product 10 shown in FIG. 1 is a schematic diagram when the knitting cord 1 is knitted with rubber which is knitting. As the knitting, not only rubber knitting but also plain knitting, pearl knitting, warp knitting and the like can be adopted without particular limitation. The knit product 20 shown in FIG. 2 is a schematic diagram when a knitting yarn 2 such as a knitting yarn or a nylon yarn, which is conventionally known, is knitted and the knitting string 1 is used as an inlay knitting element. ..
　上述したようなニット製品は、従来から知られた丸編機やよこ編み機を用いて製造される。本実施形態のニット編み用紐は、破断強力と摩擦特性とを規制されたことにより、ニッティング工程において切断させにくい。 The knit product as described above is manufactured using a conventionally known circular knitting machine or weft knitting machine. The knitting cord of the present embodiment is difficult to cut in the knitting step because the breaking strength and the frictional properties are regulated.
　次に本発明を実施例により詳細に説明するが、本発明の範囲は実施例に限定されるものではない。 Next, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
［実施例１～６、９～１３、及び比較例１～６］
　水溶性ＰＶＡを海成分とし、イソフタル酸変性度６モル％のＰＥＴを島成分とし、繊維１本あたりの島数が２５島で、海成分／島成分が２５／７５（質量比）となるような溶融複合紡糸用口金を用い、２６０℃で海島型のフィラメントを口金より吐出した。そして、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、平均繊度２．５ｄｔｅｘの連続繊維の海島型繊維をネット上に捕集し、目付３０～４０ｇ／ｍ２の連続繊維のウェブを得た。 [Examples 1 to 6, 9 to 13 and Comparative Examples 1 to 6]
Water-soluble PVA as the sea component, PET with an isophthalic acid modification degree of 6 mol% as the island component, and the number of islands per fiber is 25 islands, so that the sea component/island component is 25/75 (mass ratio) Using a melt-composite spinning die, a sea-island type filament was discharged from the die at 260°C. Then, the ejector pressure was adjusted so that the spinning speed was 4000 m/min, the sea-island type continuous fibers having an average fineness of 2.5 dtex were collected on the net, and the continuous fiber web having a basis weight of 30 to 40 g/m 2 was collected. Got
　得られたウェブをクロスラッピングすることにより６～２０枚重ね、これに、針折れ防止油剤をスプレーした。そして、６バーブのニードル針で２０００パンチ／ｃｍ２のパンチ密度でニードルパンチングすることにより、目付３００～８５０ｇ／ｍ2の海島型繊維の絡合体を得た。そして、海島型繊維の絡合体を水蒸気により熱収縮させた。熱収縮された海島型繊維の絡合体に、ポリウレタンエマルジョンを含浸させた後、１２０℃で１０分間乾燥した。 The resulting web was cross-lapped to stack 6 to 20 sheets, and a needle-breakage preventive oil agent was sprayed onto this. Then, needle-punching was performed with a 6 barb needle needle at a punch density of 2000 punches/cm 2 to obtain an entangled body of sea-island type fibers having a basis weight of 300 to 850 g/m 2 . Then, the entangled body of the sea-island type fibers was thermally shrunk by steam. The entangled body of heat-shrinked sea-island fibers was impregnated with the polyurethane emulsion, and then dried at 120° C. for 10 minutes.
　そして、ポリウレタンを含浸させた海島型繊維の絡合体を９５℃の熱水中に１０分間浸漬することにより海成分を除去して極細繊維を形成させた後、１２０℃で１０分間乾燥させた。次いで両面を＃２４０および＃３２０のサンドペーパーでバフィング処理した。このようにして平均繊度０．０７ｄｔｅｘの変性ＰＥＴ繊維の不織布及び１０質量％のポリウレタンを含むスエード調の人工皮革基体が得られた。 Then, the entangled body of sea-island type fibers impregnated with polyurethane was immersed in hot water at 95°C for 10 minutes to remove sea components to form ultrafine fibers, and then dried at 120°C for 10 minutes. Both sides were then buffed with #240 and #320 sandpaper. Thus, a suede-like artificial leather substrate containing a non-woven fabric of modified PET fiber having an average fineness of 0.07 dtex and 10% by mass of polyurethane was obtained.
　スエード調の人工皮革基体を、８０℃の熱水中に２０分間湯通しして熱水になじませると共に生地をリラックスさせた後、高圧液流染色機（（株）日阪製作所サーキュラー染色機））を用いて分散染料で染色した。 A suede-like artificial leather substrate is boiled in hot water at 80°C for 20 minutes to allow it to adapt to the hot water and to relax the fabric, after which a high-pressure jet dyeing machine (circular dyeing machine, Hisaka Manufacturing Co., Ltd.) is used. Was dyed with a disperse dye.
　得られた染色後のスエード調の人工皮革基体に、滑剤として、アミノ変性シリコーン（吉村油化学製ソフトロンＤＸ－１），脂肪酸エステル化合物（大京化学製ラステックスＬＢ），またはシルクプロテイン（洛東化成製ラクセットＫ－５００）を、補強剤としてアクリル樹脂（日華化学製カセゾールＡＲＳ－２）を、または、それらを添加せずに、表１に示した固形分付着量となるように濃度調整した水分散液を含浸付与して１３０℃で乾燥させた。 On the obtained suede-like artificial leather substrate after dyeing, as a lubricant, amino-modified silicone (Yoshimura Yushi Kagaku Softlon DX-1), fatty acid ester compound (Daikyo Kagaku Lastex LB), or silk protein (Rakusu) Tokasei Co., Ltd. Lacset K-500), acrylic resin (Casesol ARS-2 manufactured by Nichika Kagaku Co., Ltd.) as a reinforcing agent, or without adding them, the solid content shown in Table 1 was obtained. A concentration-adjusted aqueous dispersion was impregnated and dried at 130°C.
　このようにして得られた厚さ０．８～３ｍｍ、見掛け密度０．５３～０．５６ｇ／ｃｍ3のスエード調の人工皮革基体を繊維配向方向に平行な方向で幅０．７～３ｍｍに細断して紐を作成した。そして、以下の方法により評価した。 The suede-like artificial leather substrate having a thickness of 0.8 to 3 mm and an apparent density of 0.53 to 0.56 g/cm 3 thus obtained was made to have a width of 0.7 to 3 mm in a direction parallel to the fiber orientation direction. I made a string by chopping it. And it evaluated by the following methods.
（１）人工皮革基体の紐の厚さ及び幅
　定圧厚み測定器ＦＦＧ－２（尾崎製作所製、測定子径５ｍｍ、測定力０．８Ｎ以下）を用いて、任意の５点における紐の厚さおよび幅を測定し、その平均値を求めた。 (1) Thickness and width of string of artificial leather base Using a constant pressure thickness gauge FFG-2 (manufactured by Ozaki Seisakusho, measuring element diameter 5 mm, measuring force 0.8 N or less), the thickness of the string at any 5 points And the width were measured, and the average value was calculated.
（２）紐の破断強力（Ｔ）
　得られた紐の破断強力（Ｔ）を次のようにして測定した。１本の紐を長さ方向１０ｃｍに切断して試験片とし、引張試験機にて応力－歪み曲線から紐が破断したときの応力を読み取り、破断強力（Ｔ）を求めた。なお、引っ張り試験機のチャック間距離は５０ｍｍ、ヘッドスピードは５０ｍｍ／分であった。 (2) String breaking strength (T)
The breaking strength (T) of the obtained string was measured as follows. A test piece was obtained by cutting one string in the length direction of 10 cm, and the stress at the time when the string was broken was read from the stress-strain curve by a tensile tester to determine the breaking strength (T). The distance between chucks of the tensile tester was 50 mm, and the head speed was 50 mm/min.
（３）紐の摩擦抵抗（Ｓ）
　得られた紐の摩擦抵抗（Ｓ）を次のようにして測定した。測定する紐を長さ方向１０ｃｍ及び３０ｃｍにそれぞれ切断した試験片を作成した。そして１０ｃｍの紐を中央部分で折り曲げて紐の両端をそろえた状態で、長さ３ｃｍ程度の紐の輪ができるよう、チャック間距離が２００ｍｍにセットされた引張試験機の上部チャックにセットした。次いで、３０ｃｍの紐の一端を下部チャックにセットし、もう一端を上部チャックにセットされた紐の輪を通したのちに１０ｇのおもりをぶら下げた。ヘッドスピード１００ｍｍ／分で、ヘッドの移動距離が１００ｍｍの範囲での応力測定を行い、得られたチャートから最大荷重を読み取り、紐の両端にかかる荷重の２０ｇを引いた値を摩擦抵抗（Ｓ）とした。 (3) Friction resistance of string (S)
The friction resistance (S) of the obtained string was measured as follows. A test piece was prepared by cutting the string to be measured into 10 cm and 30 cm in the longitudinal direction. Then, a 10 cm string was bent at the central portion and both ends of the string were aligned, and the string was set on the upper chuck of a tensile tester in which the chuck distance was set to 200 mm so that a string loop having a length of about 3 cm was formed. Next, one end of a 30 cm string was set on the lower chuck, the other end was passed through the string loop set on the upper chuck, and then a 10 g weight was hung. Stress was measured at a head speed of 100 mm/min and a head moving distance of 100 mm, the maximum load was read from the obtained chart, and the value obtained by subtracting 20 g of the load applied to both ends of the cord was measured as the frictional resistance (S). And
（４）極細繊維の繊度
　スエード調人工皮革の厚さ方向の垂直断面を、走査型電子顕微鏡（ＳＥＭ）で１００～５００倍で観察して画像を得た。そして、画像から満遍なく選んだ１０個の繊維束を構成する極細繊維の断面積を求め、平均化した。そして、得られた平均断面積とポリエステルの比重（１．３８ｇ／ｃｍ3）から極細繊維の平均繊度を求めた。 (4) Fineness of Ultrafine Fiber A vertical cross section in the thickness direction of the suede-like artificial leather was observed with a scanning electron microscope (SEM) at 100 to 500 times to obtain an image. Then, the cross-sectional areas of the ultrafine fibers constituting 10 fiber bundles uniformly selected from the image were obtained and averaged. Then, the average fineness of the ultrafine fibers was determined from the obtained average cross-sectional area and the specific gravity of polyester (1.38 g/cm 3 ).
（５）メリヤス編みニッティング性
　得られた紐を、紐の太さや硬さ等の状態に応じて３～１０ゲージの間の適切な設定の横編機にかけてメリヤス編み物を製造した。編み地は、幅４００ｍｍで、５ｍ生産したときの紐の切断回数に応じて、以下の通り判定した。
　Ａ：切断が生じなかった。
　Ｂ：１～３回の切断が生じた。
　Ｃ：４回以上の切断が生じた。 (5) Knitting knitting property The knitting knitted fabric was manufactured by applying the obtained cord to a flat knitting machine with an appropriate setting between 3 and 10 gauge depending on the thickness and hardness of the cord. The knitted fabric had a width of 400 mm and was judged as follows according to the number of times the string was cut when 5 m was produced.
A: No cutting occurred.
B: 1-3 breaks occurred.
C: Cutting occurred 4 times or more.
（６）インレイ編みニッティング性
　インレイ編み可能な横編機を用い、１８番手の双糸を一本取りで１０ゲージの横編み機で編成する際、横目３目ごとに得られた紐を通過させるインレイ編みを行った。編み地は、幅４００ｍｍで、５ｍ生産したときの紐の切断回数に応じて、以下の通り判定した。
　Ａ：切断が生じなかった。
　Ｂ：１～３回の切断が生じた。
　Ｃ：４回以上の切断が生じた。 (6) Inlay knitting knitting property When using a flat knitting machine capable of inlay knitting, when knitting a single yarn of 18th count twine on a 10 gauge flat knitting machine, the cord obtained every 3rd weft is passed. I knit an inlay. The knitted fabric had a width of 400 mm and was judged as follows according to the number of times the string was cut when 5 m was produced.
A: No cutting occurred.
B: 1-3 breaks occurred.
C: Cutting occurred 4 times or more.
（７）メリヤス編み外観
　（５）および（６）のニッティング性確認用に作成した編み地を用いて、任意の３００ｍｍ×３００ｍｍの範囲にて糸の捻じれが生じ、不均一な編目になっている箇所をカウントし、５箇所の平均を取って以下の通り判定した。
　Ａ：不均一な編目は１か所以下であった。
　Ｂ：２～３か所で不均一な編目が生じていた。
　Ｃ：４か所以上で不均一な編目が生じていた。 (7) Appearance of knitting Using the knitted fabric created for checking the knitting properties of (5) and (6), twisting of the yarn occurs in an arbitrary area of 300 mm × 300 mm, resulting in an uneven stitch. The number of spots was counted, the average of 5 spots was taken, and the judgment was made as follows.
A: The number of uneven stitches was one or less.
B: Uneven stitches were formed at 2 to 3 places.
C: Uneven stitches were generated at four or more places.
　結果を下記表１に示す。 The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［実施例７］
　実施例１において、平均繊度０．０７ｄｔｅｘの変性ＰＥＴ繊維の不織布に代えて、平均繊度０．３ｄｔｅｘの変性ＰＥＴ繊維の不織布を形成させた以外は、実施例１～６と同様に処理し、厚さ１．４ｍｍの染色後のスエード調の人工皮革基体を得た。そして、幅１．０ｍｍに細断して紐を作成し、評価した。結果を表１に示す。 [Example 7]
The same treatment as in Examples 1 to 6 was performed except that a modified PET fiber nonwoven fabric having an average fineness of 0.3 dtex was formed instead of the modified PET fiber nonwoven fabric having an average fineness of 0.07 dtex in Example 1 A 1.4 mm thick suede-like artificial leather substrate after dyeing was obtained. Then, it was chopped into pieces having a width of 1.0 mm to create a string and evaluated. The results are shown in Table 1.
［実施例８］
　島数が２５島となるように、海成分としてポリエチレン５０質量部、島成分としてナイロン６ ５０質量部を、海成分／島成分の質量比５０／５０となるように溶融したストランドを２８５℃の口金を有する溶融複合用口金から吐出させた。そして、単位時間あたりの吐出量と得られる長繊維の繊度の比率から間接的に求められる紡糸速度が、３６００ｍ／ｍｉｎとなるように口金直下に設置したエアジェット吸引装置のエアー圧力を調整して、口金から吐出させた溶融したストランドを牽引細化させながら冷却することにより、繊度２．９ｄｔｅｘの長繊維の海島型繊維を紡糸した。そして、得られた海島型繊維を吸引装置直下に設置した移動式ネット上に連続的に捕集したのち、表面温度６０℃の金属ローラを用いてプレスすることにより目付２２ｇ／ｍ2の長繊維の海島型繊維の繊維ウェブを得た。 [Example 8]
To obtain 25 islands, 50 parts by mass of polyethylene as a sea component and 50 parts by mass of nylon 6 as an island component were melted so that the mass ratio of sea component/island component was 50/50. It was discharged from a melt-composite die having a die. Then, the air pressure of the air jet suction device installed directly under the spinneret is adjusted so that the spinning speed indirectly obtained from the ratio of the discharge amount per unit time and the fineness of the obtained long fibers becomes 3600 m/min. By cooling the molten strand discharged from the die while pulling and thinning the filament, a sea-island type fiber having a fineness of 2.9 dtex was spun. Then, the obtained sea-island type fibers are continuously collected on a movable net installed directly under a suction device, and then pressed using a metal roller having a surface temperature of 60° C. to obtain long fibers having a basis weight of 22 g/m 2 . A fiber web of sea-island type fiber was obtained.
　得られたウェブをクロスラッピングすることにより１６枚重ね、これに、針折れ防止油剤をスプレーした。そして、６バーブのニードル針で２０００パンチ／ｃｍ２のパンチ密度でニードルパンチングを実施した後、１５０℃の乾燥機で３分間加熱して冷却ロールプレス処理で表面平滑化処理をすることにより、目付６００ｇ／ｍ2の海島型繊維の絡合体を得た。 16 webs were piled up by cross wrapping the obtained web, and the needle-breakage preventing oil agent was sprayed on this. Then, after performing needle punching with a 6 barb needle needle at a punch density of 2000 punches/cm 2 , heating was performed for 3 minutes in a dryer at 150° C. and surface smoothing treatment was performed with a cooling roll press treatment to give a basis weight. An entangled body of sea-island type fibers of 600 g/m 2 was obtained.
　そして、海島型繊維の絡合体に、ポリウレタンを主体とするポリウレタン組成物１８質量部とＤＭＦ ８２質量部よりなる溶液を含浸し、ポリウレタンを凝固させ、水洗した。そして、海島型繊維中のポリエチレンを抽出除去することにより、長繊維の繊維束状のポリアミド６の極細繊維の不織布とポリウレタンとを含む人工皮革基体を得た。次いで両面を＃２４０および＃３２０のサンドペーパーでバフィング処理した。このようにして平均繊度０．０３ｄｔｅｘのポリアミド６の不織布及び３０質量％のポリウレタンを含むスエード調の人工皮革基体が得られた。 Then, the sea-island type entangled body was impregnated with a solution consisting of 18 parts by mass of a polyurethane composition mainly composed of polyurethane and 82 parts by mass of DMF, and the polyurethane was solidified and washed with water. Then, the polyethylene in the sea-island type fiber was extracted and removed to obtain an artificial leather substrate containing a nonwoven fabric of ultrafine fibers of polyamide 6 in the form of a long fiber bundle and polyurethane. Both sides were then buffed with #240 and #320 sandpaper. Thus, a suede-like artificial leather substrate containing a nonwoven fabric of polyamide 6 having an average fineness of 0.03 dtex and 30% by mass of polyurethane was obtained.
　スエード調の人工皮革基体を、８０℃の熱水中に２０分間湯通しして熱水になじませると共に生地をリラックスさせた後、ウインス染色機を用いて含金染料で染色した。 　The suede-like artificial leather substrate was boiled in hot water at 80°C for 20 minutes to allow it to adapt to the hot water, and after relaxing the fabric, it was dyed with a gold-containing dye using a Wins dyeing machine.
　次いで、表１に示したように、アミノ変性シリコーン０．７１質量％を含浸付与することにより、厚さ１．０ｍｍ、見掛け密度０．４０ｇ／ｃｍ3のスエード調の人工皮革基体を得た。 Then, as shown in Table 1, 0.71% by mass of amino-modified silicone was impregnated to give a suede-like artificial leather substrate having a thickness of 1.0 mm and an apparent density of 0.40 g/cm 3 .
　このようにして得られたスエード調の人工皮革基体を繊維配向方向に平行な方向で幅１．０ｍｍに細断して紐を作成した。そして、実施例１と同様にして評価した。結果を表１に示す。 The suede-like artificial leather substrate thus obtained was chopped to a width of 1.0 mm in a direction parallel to the fiber orientation direction to form a string. And it evaluated similarly to Example 1. The results are shown in Table 1.
　図３は、実施例及び比較例の結果をプロットしたグラフである。図３に示すように、１０≧Ｔ≧４．６Ｓ+０．５，Ｓ＜０．１８を満たす実施例で得られた紐は、何れもメリヤス編み性及びインレイ編み性がＢ以上であった。また、Ｔ≧１２Ｓ+０．５をさらに満たす実施例1～８の紐は、さらに、メリヤス編み性及びインレイ編み性のいずれもがＡであった。 FIG. 3 is a graph in which the results of Examples and Comparative Examples are plotted. As shown in FIG. 3, the cords obtained in Examples satisfying 10≧T≧4.6S+0.5 and S<0.18 all had a knitting property and an inlaying property of B or more. .. Further, in the cords of Examples 1 to 8 which further satisfy T≧12S+0.5, both knitting property and inlay knitting property were A.
１　ニット編み用紐
２　糸
１０　ニット編み用紐でメリヤス編みしたニット編み製品
２０　インレイ要素を含むニット編み製品 1 Knit Knitting String 2 Yarn 10 Knit Knitting Product Knitted with Knit Knitting String 20 Knit Knitting Product Inlay Elements

Claims (6)

  1. 　人工皮革基体を含む紐であって、
    　前記人工皮革基体は、平均繊度０．５ｄｔｅｘ以下の極細繊維の絡合体である不織布と、前記不織布に含浸付与された高分子弾性体とを含み、
    　該紐の破断強力（ｋｇ/ｃｍ）をＴ，該紐同士の摩擦抵抗（ｋｇ）をＳとした場合、
    　１０≧Ｔ≧４．６Ｓ+０．５，Ｓ＜０．１８を満たす、ニット編み用紐。     A string including an artificial leather base,
    The artificial leather substrate includes a nonwoven fabric which is an entangled body of ultrafine fibers having an average fineness of 0.5 dtex or less, and a polymeric elastic body impregnated into the nonwoven fabric,
    When the breaking strength (kg/cm) of the string is T and the frictional resistance (kg) between the strings is S,
    A knitting cord satisfying 10≧T≧4.6S+0.5 and S<0.18.
  2. 　Ｔ≧１２Ｓ+０．５をさらに満たす請求項１に記載のニット編み用紐。 The knitting cord according to claim 1, further satisfying T≧12S+0.5.
  3. 　滑剤を０．１～２質量％含む請求項１または２に記載のニット編み用紐。 The knitting cord according to claim 1 or 2, which contains 0.1 to 2 mass% of a lubricant.
  4. 　前記滑剤がシリコーン系柔軟剤である請求項１～３の何れか１項に記載のニット編み用紐。 The knitting cord according to any one of claims 1 to 3, wherein the lubricant is a silicone softener.
  5. 　スエード調表面を有する請求項１～４の何れか１項に記載のニット編み用紐。 The knitting cord according to any one of claims 1 to 4, which has a suede-like surface.
  6. 　請求項１～５の何れか１項に記載のニット編み用紐を含む、ニット製品。 A knit product including the knitting cord according to any one of claims 1 to 5.
PCT/JP2019/050496 2018-12-28 2019-12-24 Knitting string and knitted product WO2020138029A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020563282A JP7356457B2 (en) 2018-12-28 2019-12-24 Knitting cord and knitted products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018247504 2018-12-28
JP2018-247504 2018-12-28

Publications (1)

Publication Number Publication Date
WO2020138029A1 true WO2020138029A1 (en) 2020-07-02

Family

ID=71125769

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/050496 WO2020138029A1 (en) 2018-12-28 2019-12-24 Knitting string and knitted product

Country Status (3)

Country Link
JP (1) JP7356457B2 (en)
TW (1) TW202039949A (en)
WO (1) WO2020138029A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57143279U (en) * 1981-03-03 1982-09-08
WO2008120702A1 (en) * 2007-03-30 2008-10-09 Kuraray Co., Ltd. Leather-like sheet bearing grain finish and process for producing the same
JP2012046849A (en) * 2010-08-27 2012-03-08 Kuraray Co Ltd Method for producing suede tone leather like sheet
JP2012207353A (en) * 2011-03-30 2012-10-25 Kuraray Co Ltd Leather-like substrate, manufacturing method thereof and rope using leather-like substrate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57143279U (en) * 1981-03-03 1982-09-08
WO2008120702A1 (en) * 2007-03-30 2008-10-09 Kuraray Co., Ltd. Leather-like sheet bearing grain finish and process for producing the same
JP2012046849A (en) * 2010-08-27 2012-03-08 Kuraray Co Ltd Method for producing suede tone leather like sheet
JP2012207353A (en) * 2011-03-30 2012-10-25 Kuraray Co Ltd Leather-like substrate, manufacturing method thereof and rope using leather-like substrate

Also Published As

Publication number Publication date
JPWO2020138029A1 (en) 2021-11-18
TW202039949A (en) 2020-11-01
JP7356457B2 (en) 2023-10-04

Similar Documents

Publication Publication Date Title
KR101317055B1 (en) Base for synthetic leather and synthetic leathers made by using the same
CN101331265B (en) Suede like artificial leather with excellent strength and elongation properties
TWI447281B (en) Substrate for artificial leather and process for manufacturing it
JP4911140B2 (en) Method for producing leather-like sheet
JP2017106127A (en) Dyed napped artificial leather and method for producing the same
JP2008297673A (en) Filament nonwoven fabric and method for producing base material for artificial leather
JP6613764B2 (en) Artificial leather and method for producing the same
CN106661826B (en) Sheet-like article and method for producing same
JP7008018B2 (en) Rising hair-like artificial leather and its manufacturing method
WO2021049413A1 (en) Napped artificial leather
JP4770228B2 (en) Leather-like sheet and manufacturing method thereof
JP6623646B2 (en) Sheet
WO2020044911A1 (en) Artificial leather base material, method for production thereof, and napped artificial leather
WO2020138029A1 (en) Knitting string and knitted product
JP7211956B2 (en) Raised artificial leather
JP4869462B2 (en) Artificial leather base
JP3008414B2 (en) Napped fiber sheet and manufacturing method thereof
JP5586516B2 (en) Leather-like substrate, method for producing the same, and string using the leather-like substrate
JP6688593B2 (en) Artificial leather base material, artificial leather and method for manufacturing artificial leather base material
JP6065440B2 (en) Artificial leather
JP4910709B2 (en) Leather-like sheet
JP4390907B2 (en) Nonwoven manufacturing method
JP2009001945A (en) Leather-like sheet and method for producing the same
JP4973257B2 (en) Leather-like sheet
JPS5924236B2 (en) Leather-like sheet material and manufacturing method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19904066

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020563282

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19904066

Country of ref document: EP

Kind code of ref document: A1