JP2019065450A - Sheet material - Google Patents

Abstract

To provide a leather-like sheet material capable of expressing a touch feeling of a natural nubuck leather, and a nap feeling of a suede leather and a melange-tone hue, a deep color and gloss, which a natural leather does not have.SOLUTION: The sheet material includes a fiber structure comprising ultra fine fibers with at least one napped surface, and a resin layer intermittently formed on the napped surface. The resin layer is composed of two or more layers. At least on the fiber structure side, the resin layer is colored or comprises particles and on an outermost surface side, the resin layer is not colored or does not comprise a particle.SELECTED DRAWING: None

Description

  The present invention relates to a leather-like sheet material capable of expressing the feel of natural nubuck leather, napped hair of suede leather, and a melange-like color, deep color and gloss not found in natural leather.

  A suede-like artificial leather composed of ultrafine fibers and a polymer elastic body has excellent properties which natural leather does not have in terms of durability and uniformity. Taking advantage of these features, suede-like artificial leather has been used in a wide range of applications, such as clothing, furniture and automotive interior materials. However, in recent years, a new grade, appearance, touch, and the like different from the suede tone that has been used for many years are required, and development has been performed until now.

  For example, in terms of quality and touch, a leather-like fabric is proposed in which the feel of natural nubuck leather and the feel of suede leather are combined by intermittently arranging raised hair and a resin layer on the sheet surface (see Patent Document 1) ). However, the color of the fabric is colored by the same dyeing method as the conventional suede-like artificial leather, and it has not been possible to express an unprecedented color.

  Moreover, as a thing of the appearance different from conventional suede-like artificial leather, in a non-woven fabric made of ultrafine fibers including polymer elasticity, the elastic polymer is exposed on the surface by suppressing the grinding amount at the time of raising to a small amount. A method of obtaining the quality of the melange tone is proposed (see Patent Document 2). However, it is a method using the dyeing difference of the polymer elastic body and the ultrafine fiber at the time of dyeing, and it can only express the appearance of the melange tone by the shade of a single color.

International Publication No. 2017/022387 JP, 2013-44073, A

  Therefore, an object of the present invention is to provide a leather-like sheet material capable of expressing the feel of natural nubuck leather, napped hair of suede leather, and a melange-like color, deep color and gloss not found in natural leather. It is in.

  The sheet-like material of the present invention has the following constitution as a result of intensive studies to achieve the above-mentioned problems.

  That is, in the sheet-like material of the present invention, at least one surface of the fiber structure containing ultrafine fibers is napped, and a resin layer is intermittently formed on the napped surface, and the resin layer is two or more layers. In the sheet-like material which is configured, at least the resin layer on the side of the fiber structure is colored, and the outermost resin layer is not colored.

  According to a preferred embodiment of the sheet-like material of the present invention, at least one surface of the fiber structure containing microfibers is raised, and a resin layer is intermittently formed on the raised surface, and the resin layer is 2 It is a sheet-like article constituted by layers or more, wherein at least the resin layer on the side of the fiber structure contains particles, and the outermost surface resin layer does not contain the particles and is not colored.

  According to a preferred embodiment of the sheet material of the present invention, the particles are a dye and / or a pigment, at least the fiber structure side resin layer is colored by the particles, and the resin layer on the outermost surface side is It is not colored.

  According to a preferred embodiment of the sheet material of the present invention, the average single fiber diameter of the microfibers is 0.1 μm or more and 8 μm or less.

  According to a preferred embodiment of the sheet-like material of the present invention, the above-mentioned particles consist of minerals.

  According to a preferred embodiment of the sheet material of the present invention, the resin layer is not substantially colored by the particles.

  According to a preferred embodiment of the sheet material of the present invention, the mineral is mica.

  According to a preferred embodiment of the sheet-like material of the present invention, the resin layer has a three-layer structure, and only one layer on the fiber structure side is colored.

  According to a preferred embodiment of the sheet-like material of the present invention, the resin layer has a three-layer structure, and the first and second layers are colored from the fiber structure side.

  According to a preferred embodiment of the sheet material of the present invention, the resin layer has a three-layer structure, and only one layer and two layers of the fiber structure contain the particles.

  According to a preferred embodiment of the sheet material of the present invention, the resin layer has a three-layer structure, and the particles are contained in the first and second layers from the fiber structure side.

  According to a preferred embodiment of the sheet-like product of the present invention, the above-mentioned fiber structure is a non-woven fabric and comprises a polymer elastic body inside.

  According to the present invention, it is possible to obtain a leather-like sheet material capable of expressing the feel of natural nubuck leather, napped hair of suede leather, and a melange-like color, deep color and gloss not found in natural leather. .

  In the sheet-like article of the present invention, at least one surface of a fiber structure containing ultrafine fibers is napped, and a resin layer is intermittently formed on the napped surface, and the resin layer is composed of two or more layers. In the sheet material, at least the resin layer on the fiber structure side is colored, and the resin layer on the outermost surface side is not colored, or at least the resin layer on the fiber structure side contains particles, And the outermost surface side resin layer is a sheet-like thing which does not contain the above-mentioned particles.

  Thus, the sheet-like article of the present invention contains ultrafine fibers.

  The average single fiber diameter of the ultrafine fibers is preferably 0.1 μm to 8 μm, more preferably 0.3 μm to 7 μm, and still more preferably 0.5 μm to 6 μm. By setting the average single fiber diameter of the microfibers to 0.1 μm or more, it is possible to obtain the strength of the sheet material that can withstand practical use. In addition, by setting the average single fiber diameter to 8 μm or less, a sheet-like material excellent in flexibility, dense, and soft surface quality of touch can be obtained.

  Ultrafine fibers constituting the sheet material of the present invention include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, and polyamides such as 6-nylon and 66-nylon, Various synthetic fibers made of polymers such as acrylic polyethylene and polypropylene can be used. Among them, polyester fibers made of polymers such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate are preferably used in view of their excellent strength, dimensional stability, light resistance and dyeability. Moreover, the fiber structure can also be mixed with ultrafine fibers of different raw materials as long as the object of the present invention is not impaired.

  Inorganic fibers such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, etc. are added to the ultrafine fibers constituting the fiber structure according to various purposes. can do.

  As the cross-sectional shape of the ultrafine fibers constituting the fiber structure, it is possible to adopt cross-sectional shapes of irregular cross-sections such as oval, flat and triangular polygons, sector-shaped and cross-shaped, in addition to round cross-sections.

  The fiber structure used in the present invention includes a woven fabric, a knitted fabric, a non-woven fabric, and a fiber structure in which a polymer elastic body is filled in these fiber structures, and is required for each use and purpose. It can be properly used according to cost and characteristics. In terms of cost, woven fabrics and knit fabrics are preferably used, and in terms of quality with a feeling of fullness and fine naps, a fiber structure or the like in which a non-woven fabric is filled with a polymeric elastic body is preferably used.

  When a woven fabric or a knitted fabric (hereinafter, these may be collectively referred to as woven or knitted fabric) is used as the fiber structure, as the woven fabric, plain weave, twill weave, satin weave, and various woven fabrics based on those weave structures etc. Can be mentioned. Further, as the knitting, any of warp knitting, weft knitting represented by tricot knitting, lace knitting and various knits based on those knitting structures can be adopted.

  When a non-woven fabric is used as the fiber structure, it is represented in various categories such as general short-fiber non-woven fabric, long-fiber non-woven fabric, needle punched non-woven fabric, paper-fabricated non-woven fabric, spunbonded non-woven fabric, meltblown non-woven fabric, electrospun non-woven fabric, etc. All nonwovens can be applied. Here, non-woven fabrics are preferable in terms of quality due to a feeling of fullness and fine naps.

  The fiber structure in which the polymer elastic body is filled in these fiber structures is more preferably used in terms of excellent durability of the sheet-like material and abrasion resistance of the surface of the sheet-like material.

  Furthermore, in the sheet-like article of the present invention, in the case where the fiber structure is a non-woven fabric, it is a preferred embodiment to include a woven or knitted fabric by laminating inside the structure, from the viewpoint of excellent mechanical strength.

  In the case where the sheet-like material comprises a non-woven fabric and the inside contains a woven or knitted fabric, the yarn constituting the woven or knitted fabric is a synthetic fiber comprising polyester, polyamide, polyethylene, or polypropylene, or copolymers thereof or the like. It is preferably used. Among them, synthetic fibers made of polyester, polyamide and copolymers thereof can be used alone or in combination or in combination. Further, as yarns constituting the woven and knitted fabric, filament yarn, spun yarn, mixed spinning of filaments and short fibers, and the like can be used.

  When the sheet-like material is a non-woven fabric, in the woven or knitted fabric contained therein, a composite fiber in which two or more types of polymers are combined in a side-by-side type or an eccentric core-sheath type (hereinafter referred to as a side-by-side type composite fiber There may also be used a woven or knitted fabric comprising For example, in a side-by-side type composite fiber composed of two or more kinds of polymers having intrinsic viscosity (IV) differences, different internal strains occur between the two components due to stress concentration on the high viscosity side during stretching. Due to this internal strain, the high viscosity side is largely shrunk due to the difference in elastic recovery rate after stretching and the thermal contraction difference in the heat treatment process, and a strain occurs in a single fiber to develop a three-dimensional coil type crimp. The three-dimensional coil type crimp develops stretchability as an artificial leather.

  Examples of the fabric contained inside when the sheet-like material is a non-woven fabric include plain weave, twill weave, satin weave and various woven fabrics based on those woven structures as described above. Further, as the knitting, any of warp knitting, weft knitting represented by tricot knitting, lace knitting and various knits based on those knitting structures can be adopted. Among them, woven fabrics are preferable from the viewpoint of processability, and plain weave fabrics are preferably used particularly in terms of cost. In addition, the weave density of the woven fabric can be set as appropriate depending on the total fineness of the yarn and the equipment and conditions for causing the non-woven fabric to be described later to be entangled with the woven or knitted fabric.

  It is a preferable aspect that the fiber structure which comprises the sheet-like article of this invention contains a polymeric elastic body inside. The inclusion of the polymer elastic body inside improves the form stability of the sheet-like material and the abrasion resistance of the surface.

  When a polymer elastic body is contained in the inside of the fiber structure, polyurethane, styrene butadiene rubber (SBR), nitrile rubber (NBR), acrylic resin, etc. can be used as the polymer elastic body, among which polyurethane It is a preferable aspect to use as a main component. By using polyurethane, it is possible to obtain a composite sheet having a solid feeling, a leather-like appearance and physical properties that endure in actual use.

  When polyurethane is used as the polymer elastic body contained in the inside of the fiber structure, both organic solvent-based polyurethane used in the state of being dissolved in an organic solvent and water-dispersed polyurethane used in the state of being dispersed in water It can be adopted. Further, as the polyurethane, a polyurethane obtained by the reaction of a polymer diol, an organic diisocyanate and a chain extender is preferably used.

  In the case of using a water-dispersed polyurethane as the polymer elastic body in the inside of the fiber structure, it is a preferred embodiment to use an internal emulsifier in order to disperse the polyurethane in water. Examples of the internal emulsifier include cationic internal emulsifiers such as quaternary amine salts, anionic internal emulsifiers such as sulfonates and carboxylates, and nonionic internal emulsifiers such as polyethylene glycol, and further cationic systems. Any of a combination of the above and a nonionic internal emulsifier, and a combination of an anionic and a nonionic internal emulsifier can be employed.

  The polymeric elastic body in the fiber structure includes various additives, for example, pigments such as carbon black, flame retardants such as phosphorus based, halogen based and inorganic based, phenol based, sulfur based and phosphorus based oxidized Inhibitors, UV absorbers such as benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type and oxalylic acid anilide type, light stabilizers such as hindered amine type and benzoate type, hydrolysis resistant stabilizers such as polycarbodiimide, A plasticizer, an antistatic agent, a surfactant, a coagulation regulator, a dye and the like can be contained.

  The content of the polymer elastic body inside the fiber structure can be appropriately adjusted in consideration of the type of polymer elastic body to be used, the method of producing the polymer elastic body, and the feel and physical properties. The content of the polymer elastic body is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 60% by mass, and still more preferably 15% by mass with respect to the mass of the sheet-like material. The content is 45% by mass or less. By setting the content ratio of the polymer elastic body to 5% by mass or more, the sheet strength can be obtained, and by binding the fibers, the entangled state can be maintained, while the content ratio is 80% by mass or less By doing this, the texture can be prevented from becoming hard.

  In the present invention, it is important for the fiber structure to have raised hair on at least one side thereof. By having the napped surface, the adhesiveness to the subsequent resin layer is excellent, and by the napped fibers exposed on the surface of the sheet, it is possible to obtain a surface feel closer to that of the real leather.

  In addition, it is important that an intermittent, that is, non-continuous resin layer is formed on the napped surface. The discontinuous resin layer referred to here means that, as described above, the resin portions are scattered in the form of islands on the surface of the sheet to cover the napped portions, and the napped portions are between the resin portions. The state of the existing surface layer is said.

  By forming the non-continuous resin layer described above, the napped hair of the portion where the resin layer is formed is covered with the resin, the napped hair is not exposed, and the portion where the resin layer is not formed is napped Are left exposed.

  The ratio of the discontinuous resin portion to the surface of the sheet-like material is preferably 10% to 90%, and more preferably 20% to 80%. By setting it as 10% or more, it is excellent in abrasion resistance, and the Nubuck-like surface feeling of a tactile sense can be obtained. Further, by setting the above ratio to 90% or less, it becomes possible to obtain suede-like air permeability and a napping feeling.

  The method of measuring the ratio of the non-continuous resin portion to the surface of the sheet-like material is as follows: using a scanning electron microscope (SEM, VE-7800 manufactured by Keyence Corporation) to measure the surface of the sheet-like material The images were taken and calculated by the ratio of the area of the resin layer to the entire image.

  It is important that the resin layer be composed of two or more layers. By comprising the adhesive layer on the side of the fiber structure and the surface layer that is the outermost surface of the sheet, the adhesive layer containing coloring components such as pigments, dyes, and minerals described later is covered by the surface layer. In the actual use of car seats and sofas, it is possible to prevent coloring components from adhering to clothes etc. and to prevent the falling off of minerals etc., and the wear resistance required for applications requiring durability It becomes possible to satisfy the sex.

  It is a preferable mode in order to further obtain the above-mentioned effect that the resin layer has a three-layer structure including an adhesive layer, an intermediate layer and a surface layer. Moreover, it is preferable that a resin layer is five or less layers in order to set it as the surface feeling of a nubuck tone, and a touch.

  It is important that in the sheet of the present invention, the resin layer on the fiber structure side is colored or contains particles. By coloring the adhesive layer, which is the resin layer on the fiber structure side, to a color different from the color of the fiber structure, it is possible to obtain a surface feeling of melange tone, and for the color of the fiber structure, By coloring to a light similar color, it is possible to express a deeper color tone. The color of the fiber structure and the resin layer is not particularly limited, and can be appropriately selected in order to obtain a desired color tone.

  Further, by adding a mineral having gloss to the resin layer on the fiber structure side, it is possible to impart gloss to the sheet-like material. In the case of adding a mineral, it is preferable that the resin layer is not colored in order to exhibit the effect more.

  The mineral to be added to the resin layer is not particularly limited, but mica particles and the like can be preferably used in that it can impart good gloss.

  The particle size of the mineral is not particularly limited, but is preferably 1 to 200 μm.

  Moreover, in order to suppress the color transfer to clothes etc. in actual use, and drop-off | omission of a mineral, it is important that the surface layer of a resin layer does not contain a coloring component and a particle component.

  Examples of polyurethane include organic solvent-based polyurethane used in a state of being dissolved in an organic solvent, and water-dispersed polyurethane used in a state of being dispersed in water, but either of them can be employed in the present invention.

  As the polyurethane used in the present invention, polyurethane having a structure in which a polyol, a polyisocyanate and a chain extender are appropriately reacted can be used.

  As the polyol, for example, polycarbonate-based diol, polyester-based diol, polyether-based diol, silicone-based diol and fluorine-based diol, or a copolymer obtained by combining these can be used. Among them, polycarbonate-based diols and polyester-based diols are preferably used from the viewpoint of light resistance. Furthermore, polycarbonate-based diols are preferably used from the viewpoints of hydrolysis resistance and heat resistance, but in the adhesive layer in the present invention, polyether-based diols or polyester-based diols are preferable in view of adhesiveness with the fiber structure surface. It is preferably used.

  The polycarbonate-based diol can be produced by the transesterification reaction of an alkylene glycol and a carbonate, or the reaction of phosgene or a chloroformate with an alkylene glycol, or the like.

  As an alkylene glycol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, etc. Linear alkylene glycol or branched alkylene glycol such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5 pentanediol, 2-methyl-1,8-octanediol, 1 And alicyclic diols such as 4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

  In the present invention, any polycarbonate diol obtained from a single alkylene glycol or any copolymerized polycarbonate diol obtained from two or more alkylene glycols can be used.

  Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate, and aromatic polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. Can be used in combination. Among them, aromatic polyisocyanates such as diphenylmethane diisocyanate are preferred when importance is placed on durability and heat resistance, and aliphatic hydrocarbons such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferred when light resistance is emphasized. Polyisocyanates are preferably used.

  Examples of chain extenders that can be used include amine chain extenders such as ethylene diamine and methylene bis aniline, diol chain extenders such as ethylene glycol, and polyamines obtained by reacting polyisocyanate with water.

  The resin used in the resin layer in the present invention can contain polyester-based, polyamide-based and polyolefin-based elastomer resins, acrylic resin, ethylene-vinyl acetate resin and the like within the range that does not impair the abrasion resistance and texture. . In addition, these resins include various additives, for example, flame retardants of phosphorus, halogen and inorganic type, antioxidants of phenol, sulfur and phosphorus and light such as hindered amine and benzoate. Stabilizers, hydrolysis resistant stabilizers such as polycarbodiimides, plasticizers, antistatic agents, surfactants, coagulation regulators and the like can be contained.

  Moreover, it is preferable that the total thickness of the resin layer of this invention is 1 micrometer or more and 200 micrometers or less. By setting the total thickness to 1 μm or more, a touch of natural nubuck leather is obtained, and by setting the total thickness to 200 μm or less, the sheet becomes a flexible texture. More preferably, it is 5 micrometers or more and 100 micrometers or less, More preferably, it is a range of 10 micrometers or more and 50 micrometers or less.

  For the total thickness of the resin layer, use a scanning electron microscope (SEM, VE-7800 manufactured by Keyence Corporation) to cut the cross section of the sheet-like product, and use 10 cross sections of the cross section of the leather-like fabric From these photographed images, the direction parallel to the cross section is horizontal, the napped layer side of the cross section is the top, and the other surface is the top, the lowest position z1 of the resin layer and the minimum of the resin layer The distance between two points at position z2 was obtained, and the total thickness of the resin layer was calculated. Furthermore, the average value of ten values obtained by calculation was taken as the total thickness of the resin layer.

  The thickness of each layer is preferably 1 μm or more and 100 μm or less.

  Next, the method for producing the sheet-like material of the present invention will be described.

  The ultrafine fibers constituting the sheet-like material of the present invention can be obtained, for example, using an ultrafine fiber-represented fiber consisting of two or more types of polymer substances having different solubility in a solvent.

  An ultra-fine fiber expression type fiber is a sea-island type in which two thermoplastic resins having different solubility in solvent are used as a sea component and an island component, and the sea component is dissolved and removed using a solvent to make an island component as an ultrafine fiber It is possible to employ a peelable composite fiber or the like in which composite fibers or two-component thermoplastic resin are alternately arranged in radial or multilayer form on the fiber surface, and separated into fine fibers by peeling and dividing by solvent treatment. . Above all, since the sea-island composite fiber can provide an appropriate gap between island components, that is, between ultrafine fibers inside the fiber bundle by removing the sea component, it is possible also from the viewpoint of flexibility and texture of the base material. It is preferably used.

  For production of sea-island composite fiber, using a sea-island composite spinneret, a polymer mutual alignment system in which two components of sea component and island component are mutually arranged and spun, and two components of sea component and island component are mixed. Although it is possible to use a mixed spinning method in which spinning is performed, a method of producing a sea-island composite fiber by a polymer array method is more preferably used in that ultrafine fibers having a uniform fineness can be obtained.

  It is a preferred embodiment that the microfibers are in the form of non-woven fabric (microfiber web) in the fiber structure. By using a non-woven fabric, uniform and elegant appearance and texture can be obtained. As a form of a nonwoven fabric (ultrafine fiber web), any of a staple fiber nonwoven fabric and a long fiber nonwoven fabric may be sufficient.

  The fiber length of the microfibers in the case of the short fiber non-woven fabric can be appropriately selected according to the form of the non-woven fabric. It is preferable that the fiber length in the case of a normal short fiber nonwoven fabric is 25 mm or more and 90 mm or less. By setting the fiber length of the ultrafine fibers to 90 mm or less, good quality and texture can be obtained, and by setting the fiber length to 25 mm or more, a sheet-like material having good abrasion resistance can be obtained. Moreover, it is preferable that the fiber length in the case of the nonwoven fabric by the paper-making method is 0.1 mm or more and 10 mm or less. By setting the fiber length to 10 mm or less, a stable suspension can be obtained, and unevenness in the basis weight and thickness of the non-woven fabric can be suppressed. Further, by setting the fiber length to 0.1 mm or more, it is possible to suppress fuzz from the non-woven fabric.

  Moreover, in order to promote the entanglement of fibers, it is preferable to give a crimp process to the microfiber generation type fiber of this invention. A well-known method can be used for crimp processing and cut processing.

  Next, the obtained raw cotton is made into a fiber web with a cross wrapper or the like, and entangled to obtain a non-woven fabric. A needle punch, a water jet punch, etc. can be used as a method of intertwining a fiber web and obtaining a nonwoven fabric. Also, the basis weight of the fiber web can be appropriately set in consideration of the design of the final product, the dimensional change in the post process, the characteristics of the processing machine, and the like.

  It is also a preferred embodiment to obtain a laminated sheet of non-woven fabric and woven and knitted fabric made of ultrafine fiber-generating fibers by entanglement and integration of a fiber structure consisting of woven and knitted fabric and ultrafine fiber-generating fibers. As a method of entwining and integrating the two, a method such as a needle punch or a water jet punch can be used. Among them, the entanglement process by needle punching is a preferred embodiment from the viewpoint of bonding property and product quality. Thus, from the viewpoint of densification, the laminated sheet of the fiber structure and the woven and knitted fabric comprising the ultrafine fiber-generating fibers is obtained from the viewpoint of densification in the dry heat and / or the wet heat or both It is a preferred embodiment to shrink and further densify it. This contraction treatment can be carried out before or after the development of the microfibers, but it can be carried out before the generation of the microfibers in that the characteristics of the sea component polymer of the microfiber generation type fiber can be utilized for the contraction. It is a preferred embodiment to carry out the contraction treatment.

  Moreover, it is preferable that the range of the area contraction rate of the lamination sheet in this shrinkage | contraction process is 15% or more and 35% or less. By setting the area contraction rate to 15% or more, it is possible to preferably obtain the improvement effect of the grade by the contraction. Further, by setting the area shrinkage ratio to 35% or less, it is possible to leave room for shrinkage in the woven or knitted fabric integrated with the non-woven fabric, and it is possible to efficiently shrink after applying the polymer elastic body later. Become. The range of the area shrinkage ratio is more preferably 13% or more and 30% or less, and still more preferably 15% or more and 25% or less.

  The method of measuring the area shrinkage ratio calculates the shrinkage ratio in the longitudinal direction and the shrinkage ratio in the direction from the length before and after processing in the shrinkage process and the width, and is calculated by the following formula.

Length shrinkage ratio = Length after shrinkage processing / Length before shrinkage processing Width shrinkage ratio = Width after shrinkage processing / Length before shrinkage processing Area shrinkage ratio (%) = (1- (1-length shrinkage) Rate) x (1-width shrinkage rate)) x 100
As a method of shrinkage, known methods such as hot water shrinkage, steam shrinkage, dry heat shrinkage can be adopted. The time and temperature of the shrinking process may be adjusted to achieve the above-described area shrinkage rate depending on the method of shrinkage employed, the type of fibers of the fiber structure, and the like.

  The method for producing a sheet-like article according to the present invention processes the laminated sheet of the fiber structure consisting of the ultrafine fiber generating type fibers and the woven and knitted fabric to express ultrafine fibers having an average single fiber diameter of 0.1 μm to 8 μm. Including the step of As a method of generating and processing ultrafine fibers, a method of dissolving one of the resins constituting the ultrafine fiber generating fibers with a solvent may be mentioned. In particular, a method of dissolving the sea component is preferable for the ultrafine fiber-forming sea-island composite fiber in which the sea component is a readily soluble polymer and the island component is a poorly soluble polymer.

  As a solvent for dissolving the sea component, when the sea component is a polyolefin such as polyethylene or polystyrene, an organic solvent such as toluene or trichloroethylene is used. When the sea component is polylactic acid or copolyester, an aqueous alkaline solution such as sodium hydroxide can be used. Moreover, this ultrafine fiber generation | occurrence | production process (seawater removal process) can be performed by immersing the fiber entangled body which consists of an ultrafine fiber generation | occurence | production type | mold fiber in a solvent, and carrying out drainage.

  Next, the resulting fiber structure containing ultrafine fibers is subjected to a treatment of applying a polymer elastic body. It is also possible to adopt a method in which any of the treatment for developing the ultrafine fiber from the ultrafine fiber-represented fiber and the treatment for applying the polymer elastic body is performed first. When the expression processing of the microfibers is performed first, the polymer elastic body grips the microfibers, so that there is no detachment of the microfibers and the like, and it can withstand long-term use. In addition, when the polymer elastic body is applied first, since the polymer elastic body has a structure in which the microfibers are not gripped, artificial leather with a good texture can be obtained. It can be selected suitably according to the kind etc. of polyurethane to be used which is performed first.

  In addition, in the case of applying the polymer elastic body after the expression treatment of the microfibers, it is preferable to provide a step of applying a water-soluble resin between the two steps. By providing the step of applying the water-soluble resin, the surface of the fiber bundle of the ultrafine fibers and the fibers constituting the woven and knitted fabric is protected by the water-soluble resin, and the fiber bundle of the ultrafine fibers and the surface of the fibers constituting the woven and knitted fabric The location where the polymer elastic body is directly bonded is not continuous but is intermittently present, and the bonding area can be appropriately suppressed. As a result, it is possible to obtain an artificial leather having high stretchability when using a woven or knitted fabric made of composite fibers such as side-by-side type and soft texture while having a good hand-feel by a polymer elastic body. .

  As such a water-soluble resin, polyvinyl alcohol, polyethylene glycol, saccharides, starch and the like can be used. Among them, polyvinyl alcohol having a degree of saponification of 80% or more is preferably used.

  As a method for applying the water-soluble resin to the fiber entangled body, a method of impregnating a fiber structure with an aqueous solution of the water-soluble resin and drying may be mentioned. From the viewpoint of suppressing the shrinkage of the woven or knitted fabric, the drying conditions such as the drying temperature and the drying time are preferable to suppress the temperature of the fiber entangled body itself to which the water-soluble resin is applied to 110 ° C. or less.

  The application amount of the water-soluble resin is preferably 1 to 30% by mass with respect to the mass of the fiber entangled body immediately before the application. By setting the application amount to 1% by mass or more, good stretchability can be obtained in the case of a sheet-like product using a woven or knitted fabric made of composite fibers such as side-by-side type and good texture. In addition, by setting the application amount to 30% by mass or less, a sheet having good processability and good physical properties such as abrasion resistance can be obtained. In addition, since the amount of polymer elastic body that can be applied to the fiber entangled body is increased in the later step, the densification of the sheet-like material and the densification of the tactile sensation become possible.

  In the method for producing a sheet-like material of the present invention, it is possible to go through the step of semi-cutting the fiber structure (precursor sheet of artificial leather) to which the polymer elastic body is applied in the planar direction. By including the half-pressing process, the productivity of the artificial leather can be improved. For example, in the case of adopting a method of sandwiching a non-woven fabric layer made of ultrafine fiber-generating fibers with a woven and knitted fabric layer as a method of laminating woven and knitted fabric, semi-cut the precursor sheet and make the inner surface a napped surface. Is a preferred embodiment as a method for achieving precise quality.

  It is important for the sheet material of the present invention to have raised hair on at least one side. The napping treatment can be performed by buffing the surface of the fiber structure using a sandpaper, a roll sander or the like. In particular, by using sand paper, uniform and precise napped hair can be formed. Furthermore, in order to form uniform naps on the surface of the fiber structure, it is preferable to reduce the grinding load.

  The fiber structure of the present invention is preferably dyed. After dyeing the fiber structure, a colored resin layer is formed to obtain a melange appearance. Dyeing is preferably carried out using a disperse dye, cationic dye or other reactive dye, and also by a high-temperature high-pressure dyer in order to soften the texture of the sheet to be dyed.

  Furthermore, if necessary, finishing treatments such as softeners such as silicone, antistatic agents, water repellents, flame retardants and light resistance agents can be performed, and finishing treatments may be performed after dyeing or in the same bath as dyeing it can. For flame retardant treatment, known halogen-based flame retardants such as bromine and chlorine and non-halogen-based flame retardants such as phosphorus can be used, and even if applied after immersion, the back such as knife coating or rotary screen method It can also be applied by coating.

  It is important for the sheet material of the present invention that a discontinuous resin layer is formed on the napped surface. The method for forming the resin layer in the present invention is not particularly limited as long as it can be applied discontinuously on the surface of the fiber structure to be a sheet, but a screen method such as flat screen or rotary screen or gravure coating After forming a resin layer by drying after application by a method or the like, or after forming a discontinuous resin film on a supporting base fiber such as release paper, an adhesive is applied to the surface of the resin film, The method of forming a resin layer, etc. is mentioned by bonding together and adhering to the surface used as a fiber structure, and peeling a release paper.

  It is important that the resin layer of the sheet-like material of the present invention has a layer structure of two or more layers. Furthermore, it is a more preferable aspect that the said resin layer consists of a three-layer structure which consists of an adhesive layer, an intermediate | middle layer, and a surface layer. Here, the adhesive layer has an adhesive function of the sheet-like material, the resin layer of the intermediate layer and the surface layer, and a function of expressing color and gloss of the resin layer. The intermediate layer serves as the base of the resin layer, and the surface layer has the role of forming the grade and touch, and the function of suppressing the color development of the resin layer or the color transfer to the clothes or the like and the dropping of minerals. In order to make a resin layer into two layers or three layers, it can form by repeating said application method 2 times or 3 times. Moreover, about the said method, the same method may be repeated and it can also be used combining two or more types.

  The sheet-like material of the present invention obtained from the above is a leather-like sheet capable of expressing the feel of natural nubuck leather, napped hair of suede leather, and a melange-like color or deep color and gloss not found in natural leather. It can be used in a wide range of applications from furniture, chairs and vehicle interior materials, which are objects to which suede-like artificial leather is conventionally used, to clothing applications.

  Next, the sheet-like material of the present invention will be described in more detail by way of examples.

[Measurement method and processing method for evaluation]
(1) Average single fiber diameter of ultrafine fibers:
Take a scanning electron microscope (SEM) photograph of the cross section of the sheet-like skin sheet, randomly select 100 round or nearly circular oval fibers, measure the diameter of single fiber, and calculate the average value of 100 Calculated by When the ultrafine fiber of atypical cross section was adopted, the diameter of the circumscribed circle of the ultrafine fiber was regarded as a single fiber diameter, and the same calculation was made.

(2) Surface feel evaluation of sheet-like material:
The surface texture of the sheet was evaluated by a sensory test of 10 subjects. Single nucleated circles are those judged by 5 to 7 people that are judged by eight or more people to have fine and wet tactile sensations (double circles: ◎) as compared with the dense and wet tactile sensations of natural nubuck ○) What was judged by 3 to 4 people (triangle: Δ), and those judged by 2 people or less were classified as (×). Passed by double circle and single circle. In this determination, the one having a natural nubuck tone is high.

(3) Evaluation of surface napping feeling of sheet material:
The surface napping feeling of the sheet-like material was evaluated by a sensory test of 10 subjects. Those judged by 8 or more people to have suede-like napped hair compared with those of natural suede (double circle: ◎), those judged by 5 to 7 people (single circle:)), Those judged by 3 to 4 persons were classified as (triangles: Δ) and those judged by 2 or less persons as (x). Passed by double circle and single circle. In this determination, those having a natural suede-like touch are high.

(4) Fastness to rubbing evaluation was performed by the wet test of JIS L1096 8.54.7. In addition, I passed the third grade or higher.

Example 1
<Raw cotton>
After melt spinning with an island / sea mass ratio of 80/20 using polyethylene terephthalate as the island component, polystyrene as the sea component, and a sea-island composite spinner with 16 islands, it is drawn and crimped. Then, it was cut to a length of 51 mm to obtain a raw cotton of sea-island type composite fiber.

<Laminated sheet with laminated web (nonwoven fabric) and woven and knitted fabric>
Using the raw cotton of the islands-in-sea type composite fiber described above, a laminated web (nonwoven fabric) is formed through a card and cross wrapper process, and 100 fibers / cm ² to suppress fabric wrinkles due to rapid width change after fabric bonding. Needle punching was performed with the number of punches. Separately, a single yarn consisting of a single component with an intrinsic viscosity (IV) of 0.65 and a multifilament (84 dtex, 72 filaments) consisting of 2500 T / m of twist number is used for the weft, and the intrinsic viscosity (IV) is 0.65 Single yarn consisting of a single component, using a multifilament (84 dtex, 72 filaments) with a twist number of 2500 T / m as a warp, a weave density of 97 yarns / 2.54 cm, and 76 yarns / 2.54 cm A plain weave was woven. The obtained plain woven fabric was laminated on the upper and lower sides of the above-mentioned laminated web (nonwoven fabric).

After that, needle punching is performed with a punch number (density) of 2500 / cm ² , and a laminate of a non-woven fabric made of ultrafine fiber generating fibers having a basis weight of 740 g / m ² and a thickness of 3.4 mm and a heat-shrinkable fabric I got a sheet.

<Fiber structure>
The laminated sheet obtained in the above step is treated with hot water at a temperature of 96 ° C. to shrink, then impregnated with a PVA (polyvinyl alcohol) aqueous solution and dried with hot air at a temperature of 110 ° C. for 10 minutes, A sheet substrate having a PVA mass of 7.6% by mass relative to the mass of the laminated sheet was obtained. The area shrinkage of the laminated sheet was 22%. A dewatered sheet obtained by immersing the sheet substrate thus obtained in trichloroethylene to dissolve and remove polystyrene of the sea component, and intertwining an ultrafine fiber having an average single fiber fineness of 4.4 μm and a plain woven fabric I got The dewatered sheet consisting of the non-woven fabric and plain fabric made of ultrafine fibers thus obtained is immersed in a solution of polyurethane adjusted to a solid concentration of 12% in DMF (dimethylformamide) solution, and then the DMF concentration is 30%. The polyurethane was coagulated in an aqueous solution of Thereafter, the PVA and DMF are removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a fiber structure having a polyurethane mass of 27% by mass with respect to the total mass of the ultrafine fibers consisting of island components and the plain woven fabric. Precursor sheet was obtained.

  The precursor sheet of the fiber structure thus obtained is half cut in the thickness direction and the non-woven fabric layer inside the precursor sheet perpendicular to the thickness direction, and the half cut sheet surface is the number 320 of the sandpaper. Grinding with endless sand paper to form a napped surface on the surface layer portion, a fiber structure with a thickness of 0.90 mm was obtained. The fiber structure thus obtained is simultaneously shrunk and dyed under a temperature of 120 ° C. using a jet flow dyeing machine, then dried in a drier and colored brown. Fiber structure is obtained.

<Resin layer formation>
A DMF (dimethylformamide) solution of polyurethane colored in yellow, which is adjusted to a solid concentration of 25%, is applied to the napped surface of the fiber structure obtained in the above step by a rotary coating method, and then dried and sheeted I got a thing. Then, a DMF solution of polyurethane similar to that of the first time except that it did not turn yellow was applied and dried in the same manner to obtain a sheet.
In the surface of the obtained sheet, resin layer portions are scattered like islands, and resin portions and napped portions are arranged irregularly and discontinuously, and the ratio of resin portions to the surface of the fiber structure Was 60%. In addition, the surface had a brown and yellow mélange-like appearance and was excellent in rub fastness. The results are shown in Table 1.

Example 2
<Raw cotton ~ fiber structure>
The same as Example 1 was used except that the fiber structure was dyed in red.

<Resin layer formation>
A solid solution concentration was adjusted to 25%, and a DMF solution of a black colored polyurethane was applied to the napped surface of the fiber structure obtained in the above step by a rotary coating method, and a sheet was obtained after drying. . Subsequently, the same polyurethane solution as that of the first time except that it did not color black was applied and dried twice in the same manner to obtain a sheet.

  In the surface of the obtained sheet, resin layer portions are scattered like islands, and resin portions and napped portions are arranged irregularly and discontinuously, and the ratio of resin portions to the surface of the fiber structure Was 60%. In addition, the surface had a red and black mélange-like appearance, and was excellent in rub fastness. The results are shown in Table 1.

[Example 3]
<Raw cotton>
After melt spinning with an island / sea mass ratio of 80/20 using polyethylene terephthalate as the island component, polystyrene as the sea component, and a sea-island composite spinneret with 100 islands, it is drawn and crimped. Then, it was cut to a length of 51 mm to obtain a raw cotton of sea-island type composite fiber.

<Laminated web (non-woven fabric) and laminated sheet with woven and knitted fabric ~ fiber structure>
A fiber structure having an average single fiber diameter of 0.3 μm was obtained in the same manner as in Example 1 except that the raw cotton of the sea-island type composite fiber was used and it was dyed in red. In addition, the area shrinkage ratio of the laminated sheet was 27%.

<Resin layer formation>
Apply a solution of polyurethane colored in black adjusted to a solid concentration of 25% on the napped surface of the fiber structure obtained in the previous step by a gravure coating method, and perform the drying operation twice to form a sheet I got a thing. Next, a similar polyurethane DMF solution was applied and dried in the same manner as in the first and second times, except that it did not color black, and a sheet was obtained.
In the surface of the obtained sheet, resin layer portions are scattered like islands, and resin portions and napped portions are arranged irregularly and discontinuously, and the ratio of resin portions to the surface of the fiber structure Was 70%. In addition, the surface had a red and black mélange-like appearance, and was excellent in rub fastness. The results are shown in Table 1.

Example 4
<Raw cotton>
After melt spinning with an island / sea mass ratio of 80/20 using polyethylene terephthalate as the island component, polystyrene as the sea component, and a sea-island composite spinneret with eight islands, this is drawn and crimped. Then, it was cut to a length of 51 mm to obtain a raw cotton of sea-island type composite fiber.

<Laminated web (non-woven fabric) and laminated sheet with woven and knitted fabric ~ fiber structure>
A fiber structure having an average single fiber diameter of 7.0 μm was obtained in the same manner as in Example 1 except that the raw cotton of the sea-island type composite fiber was used. Moreover, the area contraction rate of the laminated sheet was 18%.

<Resin layer formation>
A sheet was obtained in the same manner as in Example 1.
In the surface of the obtained sheet, resin layer portions are scattered like islands, and resin portions and napped portions are arranged irregularly and discontinuously, and the ratio of resin portions to the surface of the fiber structure Was 60%. In addition, the surface had a brown and yellow mélange-like appearance and was excellent in rub fastness. The results are shown in Table 1.

[Example 5]
<Raw cotton ~ fiber structure>
The same fiber structure as in Example 1 was used.

<Resin layer formation>
A DMF solution of polyurethane prepared by adjusting the solid concentration to 25% and adding mica particles with a particle diameter of 10 μm to 3% with respect to the polyurethane solid content is used for rotary coating on the napped surface of the fiber structure obtained in the above step. After coating and drying, a sheet was obtained. Subsequently, the same polyurethane solution as polyurethane was applied and dried twice in the same manner as in the first process except that mica particles were not added, and a sheet was obtained.

  In the surface of the obtained sheet, resin layer portions are scattered like islands, and resin portions and napped portions are arranged irregularly and discontinuously, and the ratio of resin portions to the surface of the fiber structure Was 60%. Moreover, the surface was the appearance which has gloss, and was excellent in abrasion fastness. The results are shown in Table 1.

Comparative Example 1
<Raw cotton ~ fiber structure>
The same one as in Example 1 was used.

<Resin layer formation>
A solution of polyurethane (yellowish colored polyurethane) adjusted to a solid content concentration of 25% is applied to the napped surface of the fiber structure obtained in the above step by a rotary coating method and dried twice. , Obtained a sheet-like material.
In the surface of the obtained sheet, resin layer portions are scattered like islands, and resin portions and napped portions are arranged irregularly and discontinuously, and the ratio of resin portions to the surface of the fiber structure Was 60%. Also, the surface had a brown and yellow melange appearance, but the fastness to rubbing was poor. The results are shown in Table 1.

Comparative Example 2
<Raw cotton ~ fiber structure>
The same one as in Example 1 was used.

<Resin layer formation>
A solution of polyurethane colored in yellow was prepared by adjusting the solid concentration to 25% and applying the solution to the whole of the napped surface of the fiber structure obtained in the above step by a rotary coating method, and after drying, a sheet was obtained. . Then, a DMF solution of polyurethane similar to that of the first time except that it did not turn yellow was applied and dried in the same manner to obtain a sheet. The surface of the obtained sheet was only the resin layer, and the proportion of the resin portion on the surface of the fiber structure was 100%. In addition, the surface had an appearance of only yellow, but the fastness to rubbing was excellent.

  The sheet-like material of the present invention can be suitably used as a covering material or wall material for furniture and chairs, and as a covering material for seats, ceilings, pillars, doors and the like in vehicle compartments such as automobiles, trains and aircrafts. Furthermore, clothing materials used for shirts, jackets, trousers, bags, belts, wallets, etc., and parts of them, casual shoes, sports shoes, uppers, trims, accessory cases such as men's shoes, women's shoes, etc. And for display applications.

Claims (13)

In a sheet-like article in which at least one surface of a fiber structure comprising ultrafine fibers is napped, a resin layer is intermittently formed on the napped surface, and the resin layer is composed of two or more layers, at least the fibers The sheet-like article in which the resin layer on the structure side is colored and the outermost surface resin layer is not colored. A sheet-like article in which at least one surface of a fiber structure comprising ultrafine fibers is napped, and a resin layer is intermittently formed on the napped surface, and the resin layer is composed of two or more layers, An uncolored, sheet-like article comprising particles in at least the resin layer on the side of the fiber structure and the outermost surface resin layer not comprising the particles. The sheet-like material according to claim 2, wherein the particles are a dye and / or a pigment, at least the resin layer on the fiber structure side is colored by the particles, and the outermost surface resin layer is not colored. . The sheet-like material according to any one of claims 1 to 3, wherein an average single fiber diameter of the ultrafine fibers is 0.1 μm or more and 8 μm or less. The sheet-like material according to any one of claims 2 to 4, wherein the particles consist of a mineral. The sheet-like material according to claim 5, wherein the resin layer is not substantially colored by the particles. The sheet-like material according to claim 6, wherein the mineral is mica. The sheet-like material according to any one of claims 1 to 7, wherein the resin layer has a three-layer structure, and only one layer on the fiber structure side is colored. The sheet-like material according to any one of claims 1 to 8, wherein the resin layer has a three-layer structure, and the first and second layers are colored from the side of the fiber structure. The sheet-like article according to claim 8 or 9, wherein the coloring is by particles. The sheet-like material according to any one of claims 5 to 7, wherein the resin layer has a three-layer structure, and only one layer and two layers of a fiber structure comprise the particles. The sheet-like material according to any one of claims 5 to 7, wherein the resin layer has a three-layer structure, and the particles are contained in the first layer and the second layer from the fiber structure side. The sheet-like material according to any one of claims 1 to 12, wherein the fiber structure is a non-woven fabric and contains a polymer elastic body inside.