JP2019189948A - Substrate for artificial leather, and artificial leather - Google Patents

Abstract

The present invention relates to a substrate for artificial leather comprising a fiber entangled body made of ultrafine fibers and a polymer elastic material, the natural leather-like substrate for artificial leather containing a high content of a biomass resource-derived component contributing to carbon neutrality. is there. The artificial leather substrate is an artificial leather substrate composed of a fiber entangled body made of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less and a polymer elastic body, and is based on ISO16620 (2015). An artificial leather substrate having a specified biomass plasticity of 5% or more and 100% or less. [Selection diagram] None

Description

  The present invention relates to an artificial leather substrate and artificial leather made of a fiber entangled body made of ultrafine fibers and a polymer elastic body, and an artificial artificial material containing a component derived from biomass resources that contributes to carbon neutral in order to reduce the environmental load. The present invention relates to a leather substrate and artificial leather.

  Natural leather-like artificial leather mainly composed of fiber entanglement composed of ultrafine fibers and polymer elastic body has superior characteristics compared to natural leather, such as high durability and uniform quality. As well as being used in various fields such as vehicle interior materials, interiors and shoes and clothing.

  Many of these artificial leathers use ingredients obtained from fossil resources such as oil as raw materials, but there is a concern that oil will be depleted in the future, and a large amount of carbon dioxide is emitted during the manufacturing process and incineration disposal. This has led to a series of problems, such as global warming. Under such circumstances, much attention has been paid to recycled raw materials and materials with low environmental impact.

  In view of such a situation, a method for manufacturing a base for artificial leather using a material having a low environmental load is disclosed (see Patent Document 1).

International Publication No. 2014/034780

  Like the method disclosed in Patent Document 1, it is possible to include a component derived from biomass resources in a part of the components constituting the base for artificial leather, but the proportion of components derived from biomass resources in the base for artificial leather As it was insufficient. In addition, since the artificial leather substrate is a composite material, it is difficult to calculate the ratio of components derived from biomass resources from the artificial leather substrate.

  That is, the present invention is to solve the above-mentioned problems, and the substrate for artificial leather according to the present invention comprises a fiber entangled body composed of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less, and a polymer elasticity. A substrate for artificial leather comprising a body, wherein the biomass plastic degree of the artificial leather substrate defined by ISO 16620 (2015) is 5% or more and 100% or less.

  According to a preferred aspect of the present invention, the biomass plasticity of the artificial leather substrate is 15% or more.

  According to a preferred aspect of the present invention, the biomass plasticity of the artificial leather substrate is 25% or more.

  According to a preferred embodiment of the present invention, the biomass plasticity of the ultrafine fiber and the biomass plasticity of the polymer elastic body are both 5% or more and 100% or less.

  According to a preferred aspect of the present invention, the ultrafine fiber is made of polyester.

  According to a preferred aspect of the present invention, the polymer elastic body is polyurethane.

  According to a preferred aspect of the present invention, the polyurethane is a polyurethane having a polycarbonate diol derived from a biomass raw material as a reaction component.

  According to a preferred embodiment of the present invention, the wet tensile strength of the artificial leather substrate is 10 N / cm or more and 200 N / cm or less.

  According to a preferred aspect of the present invention, there is provided artificial leather comprising the artificial leather substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the base material for artificial leather containing the component derived from the biomass resource which contributes to carbon neutral can be obtained in order to reduce environmental impact.

  The base body for artificial leather of the present invention is a base body for artificial leather composed of a fiber entangled body made of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less, and a polymer elastic body, and is defined by ISO 16620 (2015). It is a base for artificial leather having a biomass plasticity of 5% or more and 100% or less. Details will be described below.

[Fiber entangled body]
As the fibers constituting the fiber entangled body used in the present invention, synthetic fibers are preferably used from the viewpoint of excellent durability, particularly mechanical strength, heat resistance and light resistance, and polyester fibers and polyamide fibers are particularly preferable. Used.

  When a synthetic fiber is used as a fiber constituting the fiber entangled body, the synthetic fiber preferably contains a component derived from biomass resources.

  As a component derived from biomass resources, when a polyester fiber is used as a synthetic fiber, a component derived from biomass resources may be used as a dicarboxylic acid and / or an ester-forming derivative thereof, or as a diol. Although a component derived from a biomass resource may be used, it is preferable to use a component derived from a biomass resource for both dicarboxylic acid and / or an ester-forming derivative thereof and a diol from the viewpoint of reducing environmental burden.

  When using a polyester fiber as a synthetic fiber, examples of the dicarboxylic acid and / or ester-forming derivative thereof include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (for example, 2,6-naphthalenedicarboxylic acid), diphenyldicarboxylic acid ( Fats such as diphenyl-4,4′-dicarboxylic acid), oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid Aliphatic carboxylic acid, cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-sulfoisophthalic acid salt (5-sulfoisophthalic acid lithium salt, 5-sulfoisophthalic acid potassium salt, 5-sulfoisophthalic acid Acid sodium salt, etc.) And aromatic dicarboxylic acids and their ester-forming derivatives can be used.

  The “ester-forming derivative” as used in the present invention means lower alkyl esters, acid anhydrides, acyl chlorides and the like of these dicarboxylic acids, and for example, methyl esters, ethyl esters, hydroxyethyl esters and the like are preferably used.

  Examples of the diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, diethylene glycol, 2-methyl-1,3. -Propanediol, polyoxyalkylene glycols having a molecular weight of 500 or more and 20000 or less (such as polyethylene glycol), bisphenol A-ethylene oxide adducts, and the like can be used.

  When polyamide fiber is used as the synthetic fiber, nylon 6, nylon 66, nylon 56, nylon 610, nylon 11, nylon 12, copolymer nylon, etc. can be used, but nylon containing components derived from biomass resources. 56, nylon 610, and nylon 11 are preferably used.

  When synthetic fibers are used as the fibers constituting the fiber entangled body, the polymers forming the fibers include inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet rays depending on various purposes. An absorbent, a conductive agent, a heat storage agent, an antibacterial agent, and the like can be added.

  It is important that the average single fiber diameter of the ultrafine fibers constituting the fiber entangled body is 0.1 μm or more and 10 μm or less. By setting the average single fiber diameter to 10 μm or less, it is possible to obtain a base for artificial leather that is dense and has a soft surface quality that is soft to the touch. On the other hand, when the average single fiber diameter is 0.1 μm or more, an effect excellent in coloring property and fastness after dyeing is exhibited. The average single fiber diameter of the ultrafine fibers is preferably 1 μm or more and 6 μm or less, and more preferably 1.5 μm or more and 4 μm or less.

  The average single fiber diameter was obtained by taking a scanning electron microscope (SEM) photograph of the cross section of the artificial leather substrate, selecting 50 circular or nearly elliptical fibers at random, measuring the single fiber diameter, and measuring 50 single fibers. Calculate by calculating the arithmetic mean. In the case of adopting an irregularly shaped ultrafine fiber, first, the cross-sectional area of the single fiber is measured, and the equivalent fiber diameter is calculated to obtain the single fiber diameter.

The fiber entangled body of the present invention preferably has a bioplastic degree specified by ISO 16620 (2015) of 5% or more and 100% or less. In the present invention, the biomass plasticity is measured as follows.
(1) Based on ISO 16620-2, the bio-based carbon content in the total carbon of the components constituting the sample is measured.
(2) Identify components and component ratios constituting the sample.
In addition, publicly known methods, such as GC-MS, NMR, and elemental analysis, can be used for identification.
(3) From the results of (1) and (2), a component derived from biomass resources is specified.
(4) The ratio (mass ratio) of components derived from biomass resources among the components of the sample is calculated as the biomass plasticity of the sample.

  The degree of biomass plasticity of the fiber entangled body is preferably 15% or more, and more preferably 25% or more, from the viewpoint of reducing the environmental load.

  When measuring the biomass plasticity of a fiber entangled body from a substrate for artificial leather, a method of extracting and isolating the fiber entangled body using a solvent in which the fiber entangled body is soluble, or a polymer from the substrate for artificial leather It can be appropriately employed depending on the constituent components of the artificial leather substrate such as a method of removing the polymer elastic body using a solvent in which the elastic body is soluble.

  As a method of removing components other than the fiber entangled body from the base for artificial leather, for example, a method of extracting a component containing a polymer elastic body using N, N-dimethylformamide heated to 60 ° C. or more and 100 ° C. or less. Can be used.

[Polymer elastic body]
Since the polymer elastic body constituting the artificial leather substrate of the present invention is a binder for gripping the fiber entanglement composed of the ultrafine fibers constituting the artificial leather substrate, the flexible texture of the artificial leather substrate of the present invention can be obtained. In consideration, examples of the elastic polymer used include polyurethane, SBR, NBR, and acrylic resin. Among these, it is preferable to use polyurethane as a main component. By using polyurethane, it is possible to obtain a substrate for artificial leather having a solid tactile sensation, a leather-like appearance, and physical properties that can withstand actual use. Moreover, the main component here means that the mass of polyurethane is more than 50 mass% with respect to the mass of the whole polymer elastic body.

  When polyurethane is used in the present invention, either an organic solvent-based polyurethane used in a state dissolved in an organic solvent or a water-dispersed polyurethane used in a state dispersed in water can be employed. As the polyurethane, a polyurethane obtained by a reaction of a polymer diol, an organic diisocyanate and a chain extender is preferably used.

  The polymer elastic body of the present invention preferably contains a component derived from biomass resources from the viewpoint of reducing environmental load. As a component derived from biomass resources, when polyurethane is used as the polymer elastic body, among components, it is relatively easy to procure raw materials derived from biomass resources. It is preferable to use it.

  When polyurethane is used as the polymer elastic body, the polymer diol used is at least selected from polymer diols such as polyester diol, polyether diol, polycarbonate diol, or polyester polyether diol having an average molecular weight of 500 to 3000. Although one type of polymer diol can be used, it is preferable to include a polycarbonate diol excellent in hydrolysis resistance. When a biomass resource-derived component is used for the polymer diol, the polymer diol may be composed only of a biomass resource-derived component or a copolymer of a biomass resource-derived polymer diol and a petroleum resource-derived polymer diol. Good. From the viewpoint of reducing the environmental burden, it is preferable that the amount of polymer diol derived from biomass resources is larger than that of polymer diol derived from petroleum resources.

  In the case of using polyurethane as the polymer elastic body, the isocyanate to be used includes aromatic type such as 4,4′-diphenylmethane diisocyanate, alicyclic type such as isophorone diisocyanate, and aliphatic type diisocyanate such as hexamethylene diisocyanate, etc. And at least one diisocyanate selected from

  When polyurethane is used as the polymer elastic body, the chain extender used is at least one kind having two or more active hydrogen atoms such as water, ethylene glycol, butanediol, ethylenediamine, and 4,4′-diaminodiphenylmethane. These are low molecular compounds. From the viewpoint of reducing the environmental burden, it is preferable to use a chain extender containing a component derived from biomass resources.

  In addition, various additives depending on the purpose, for example, pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based and inorganic-based materials, and phenol-based, sulfur-based, and phosphorus-based oxidation materials are used for the polymer elastic body. UV absorbers such as inhibitors, benzotriazoles, benzophenones, salicylates, cyanoacrylates and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimides, A plasticizer, an antistatic agent, a surfactant, a coagulation modifier, a dye, and the like can be contained.

  The content of the polymer elastic body in the artificial leather substrate can be appropriately adjusted in consideration of the type of the polymer elastic body to be used, the method for producing the polymer elastic body, the texture and physical properties. The content of the polymer elastic body is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and still more preferably 20% by mass with respect to the mass of the fiber entangled body. It is 40 mass% or less. When the content of the polymer elastic body is less than 10% by mass, the bond between the fibers due to the polymer elastic body becomes weak, and the wear resistance of the artificial leather substrate tends to be inferior. On the other hand, when the content of the elastic polymer exceeds 60% by mass, the texture of the artificial leather substrate tends to be hard.

  The polymer elastic body of the present invention preferably has a biomass plasticity specified by ISO 16620 (2015) of 5% or more and 100% or less. The biomass plasticity is measured by the above-described method, and is preferably 15% or more, and more preferably 25% or more, from the viewpoint of reducing the environmental load.

  When measuring the biomass plasticity of a polymer elastic body from a substrate for artificial leather, a method for extracting and isolating the polymer elastic body using a solvent in which the polymer elastic body is soluble, or a substrate for artificial leather The method can be appropriately employed depending on the constituent components of the substrate for artificial leather, such as a method of removing the ultrafine fibers using a solvent in which the ultrafine fibers are soluble.

  When an organic solvent-based polymer elastic body is used as the polymer elastic body, the polymer elastic body can be extracted and isolated with an organic solvent such as N, N-dimethylformamide. When a water-dispersed polymer elastic body is used as the polymer elastic body, a solvent that dissolves fibers (in the case of polyester, 1,1,1,3,3,3-hexafluoro-2-propanol or ortho A method of removing fibers using chlorophenol or the like, or a method of decomposing and extracting a water-dispersed polymer elastic body with N, N-dimethylformamide heated to 60 ° C. or more and 100 ° C. or less can be used.

[Substrate for artificial leather]
It is important that the base for artificial leather of the present invention has a biomass plasticity specified by ISO 16620 (2015) of 5% or more and 100% or less. From the viewpoint of reducing the environmental burden, the biomass plasticity is preferably 15% or more, and more preferably 25% or more.

  Since the artificial leather substrate of the present invention is composed of a fiber entangled body and a polymer elastic body, the biomass plasticity of the artificial leather substrate in the present invention is determined by the above-described method. The degree of biomass plastics of the elastic body is obtained and calculated by the following [Equation 1].

  In the artificial leather substrate of the present invention, the fiber entangled body is preferably in the form of a nonwoven fabric. By using a non-woven fabric, a uniform and elegant appearance and texture can be obtained when the surface is raised.

  As the form of the nonwoven fabric, both a long-fiber nonwoven fabric and a short-fiber nonwoven fabric are used, but a short-fiber nonwoven fabric is a preferred embodiment because the number of raised fibers on the product surface is large and an elegant appearance can be easily obtained.

  The fiber length of the ultrafine fibers when using the short fiber nonwoven fabric is preferably 25 mm or more and 90 mm or less. By setting the fiber length to 90 mm or less, good quality and texture can be obtained, and by setting the fiber length to 25 mm or more, a base for artificial leather having excellent wear resistance can be obtained. The fiber length is more preferably 35 mm or more and 80 mm or less, and further preferably 40 mm or more and 70 mm or less.

The basis weight of the fiber entangled body constituting the substrate for artificial leather is measured in accordance with JIS L1913 (2010) 6.2, and is preferably in the range of 50 g / m ^{2 to} 400 g / m ² , more preferably 80 g / m. in the range of ² or more 300 g / ^{m 2} or less. When the basis weight of the fiber entangled body is less than 50 g / m ² , the artificial leather substrate becomes paper-like and has a poor texture. On the other hand, if the basis weight of the fiber entangled body exceeds 400 g / m ² , the texture of the artificial leather substrate tends to be hard.

  In the artificial leather substrate of the present invention, for the purpose of improving the strength and the shape stability, it is also a preferable aspect that a woven fabric is laminated inside or on one side of the fiber entangled body and entangled and integrated.

  Filaments, spun yarns, innovative spun yarns, mixed composite yarns of filaments and spun yarns, etc. can be used as the types of fibers constituting the woven fabric used when the fabrics are entangled and integrated. When the structure has many fluffs on the surface and the nonwoven fabric is entangled with the woven fabric, it is disadvantageous if the fluffs come off and are exposed on the surface. Therefore, it is more preferable to use a filament, and it is preferable to use a multifilament as the filament. .

  The fiber diameter of the single fiber constituting the woven fabric is preferably 1 μm or more and 50 μm or less. By setting the fiber diameter of the single fiber to 50 μm or less, an artificial leather base excellent in flexibility can be obtained, and by setting the fiber diameter of the single fiber to 1 μm or more, the form stability of the product as the base for artificial leather Will improve.

  The total fineness of the yarns constituting the woven fabric is measured by JIS L1013 (2010) 8.3b (simple method), and is preferably 30 dtex or more and 170 dtex or less. By setting the fineness to 170 dtex or less, a substrate for artificial leather excellent in flexibility can be obtained. By setting the total fineness to 30 dtex or more, the shape stability of the product as the artificial leather substrate is improved. At this time, the total fineness of the multifilaments of the warp and the weft is preferably the same.

  The component of the fiber constituting the woven fabric is preferably the same component as the component of the fiber entangled body, and from the viewpoint of reducing environmental burden, it is preferable to contain a component derived from biomass resources.

  The substrate for artificial leather of the present invention preferably has a thickness measured by JIS L1913 (2010) 6.1A method in the range of 0.2 mm or more and 1.2 mm or less. When the thickness of the artificial leather substrate is less than 0.2 mm, the processability during production deteriorates, and when the thickness is greater than 1.2 mm, the flexibility of the artificial leather substrate tends to be impaired. The thickness of the artificial leather substrate is more preferably from 0.3 mm to 1.1 mm, still more preferably from 0.4 mm to 1 mm.

  The substrate for artificial leather of the present invention preferably has a tensile strength when wet measured by JIS L1913 (2010) 6.3.2 in the range of 10 N / cm to 200 N / cm. If the tensile strength when the artificial leather substrate is wet is 10 N / cm or less, durability during actual use is poor, and workability such as breakage occurs during dyeing, which is not preferable. Further, if it is 200 N / cm or more, the molding processability is poor. The tensile strength when the artificial leather substrate is wet is more preferably 15 N / cm or more and 180 N / cm, and further preferably 25 N / cm or more and 150 N / cm or less. In general, biomass resource-derived raw materials are produced from raw materials obtained by fermenting biomass resources, so the content of isomers of raw material chemicals tends to be higher than that of petroleum resource-derived raw materials. When the biomass plasticity is increased, the crystallinity and orientation of the polymer tend to decrease due to the influence of isomers. For this reason, the physical properties of the resultant artificial leather substrate tend to be lowered, and the tensile strength when wet is particularly affected. The base material for artificial leather of the present invention is manufactured using a biomass resource-derived raw material in which the content of isomers and impurities is reduced so that the tensile strength when wet can be maintained even when the biomass plasticity is increased.

  The content of isomers and impurities of the biomass resource-derived raw material is preferably 1000 ppm or less, more preferably 500 ppm or less, with respect to the biomass plastic.

  The content of isomers and impurities of the biomass resource-derived raw material can be measured using a known method such as GC-MS or NMR. For example, when the fiber entangled body is made of polyester, the content of isomers and impurities can be measured by GC-MS measurement after the polyester is thermally decomposed in an aqueous ammonia solution.

[Artificial leather]
The substrate for artificial leather of the present invention is also preferably used as a suede-like artificial leather having napped surfaces. In the case of a suede-like artificial leather, napping may be provided only on one side of the artificial leather, and it is allowed to be provided on both sides. The napped form in the case of having napped on the surface has napped length and directional flexibility to the extent that a so-called finger mark is generated, leaving a mark when the napped direction changes when traced with a finger from the viewpoint of design effect It is preferable. More specifically, the napped length of the surface is preferably 100 μm or more and 400 μm or less, and more preferably 150 μm or more and 350 μm or less. The surface length of the surface of the artificial leather is measured by taking an SEM image of the cross section of the artificial leather upside down at a magnification of 50 times, measuring the height of the raised portion (layer consisting of ultrafine fibers) at 10 points, and calculating the average value. Calculate by calculating.

[Method of manufacturing substrate for artificial leather]
Next, the manufacturing method of the base body for artificial leather of this invention is demonstrated.

  In the present invention, as a means for obtaining ultrafine fibers constituting the fiber entangled body, it is preferable to use ultrafine fiber expression type fibers. After the ultrafine fiber expression type fiber is entangled in advance to obtain a nonwoven fabric, the nonwoven fabric formed by entanglement of the ultrafine fiber bundle can be obtained by ultrafinening the fibers.

  As the ultrafine fiber-expressing type fiber, two components having different solvent solubility (two or three components when the island fiber is a core-sheath composite fiber) are used as a sea component and an island component, and the sea component is a solvent. It is possible to use sea-island type composite fibers that use island components as ultrafine fibers by dissolving and removing them, etc., and when removing sea components, an appropriate gap is provided between island components, that is, between ultrafine fibers inside the fiber bundle. Therefore, it is preferable from the viewpoint of the texture and surface quality of the artificial leather substrate.

  As a sea-island type composite fiber, a polymer inter-array is used in which a sea-island type composite base is used, and two components of the sea component and the island component (3 components if the island fiber is a core-sheath composite fiber) are mutually aligned and spun. The method used is preferable from the viewpoint that ultrafine fibers having a uniform single fiber fineness can be obtained.

  As sea components of sea-island type composite fibers, polyethylene, polypropylene, polystyrene, copolymerized polyester copolymerized with sodium sulfoisophthalic acid or polyethylene glycol, and polylactic acid can be used. From this viewpoint, polystyrene and copolyester are preferably used.

  Further, the fiber entangled body preferably takes the form of a nonwoven fabric, and as described above, either a short fiber nonwoven fabric or a long fiber nonwoven fabric can be used, but the short fiber nonwoven fabric faces the thickness direction of the artificial leather substrate. This is preferable because the number of fibers is larger than that of the long-fiber non-woven fabric, and a high density feeling can be obtained on the surface of the artificial leather substrate when raised.

  When a short fiber nonwoven fabric is used as the fiber entangled body, the obtained ultrafine fiber-expressing fiber is preferably crimped and cut into a predetermined length to obtain raw cotton. A known method can be used for crimping or cutting.

  Next, the obtained raw cotton is made into a fiber web with a cross wrapper or the like and entangled to obtain a short fiber nonwoven fabric. As a method for entanglement of the fiber web to obtain a short fiber nonwoven fabric, needle punching, water jet punching, or the like can be used.

  Further, when the artificial leather substrate includes a woven fabric, the obtained short fiber nonwoven fabric and the woven fabric are laminated and entangled together. To entangle and integrate the short fiber nonwoven fabric and the fabric, the fabric is laminated on one or both sides of the short fiber nonwoven fabric, or the fabric is sandwiched between a plurality of short fiber nonwoven webs, and then needle punching or water jet Short fiber nonwoven fabric and textile fibers can be entangled by punching or the like.

Apparent density of the short-fiber nonwoven fabric composed of the composite fiber after needle punching or water jet punching (microfine fiber phenotype fibers) is preferably 0.15 g / cm ³ or more 0.45 g / cm ³ or less. By making the apparent density preferably 0.15 g / cm ³ or more, the artificial leather base material can have sufficient form stability and dimensional stability. On the other hand, when the apparent density is preferably 0.45 g / cm ³ or less, a sufficient space for applying the polymer elastic body can be maintained.

  Next, the fiber entangled body can be impregnated with an aqueous solution of a water-soluble resin and dried to give the water-soluble resin. By adding a water-soluble resin to the fiber entangled body, the fiber is fixed and the dimensional stability is improved.

  When using an ultrafine fiber expression type fiber, the obtained fiber entangled product is treated with a solvent to express an ultrafine fiber having an average single fiber diameter of 0.1 μm or more and 10 μm or less.

  When the ultrafine fiber-expressing fiber is a sea-island type composite fiber, as the solvent for dissolving and removing the sea component, when the sea component is polyethylene, polypropylene, and polystyrene, an organic solvent such as toluene or trichlorethylene can be used. Further, when the sea component is a copolyester or polylactic acid, an aqueous alkali solution such as sodium hydroxide can be used. When the sea component is a water-soluble thermoplastic polyvinyl alcohol resin, hot water can be used.

  Next, the fiber entangled body is impregnated with a solvent solution of a polymer elastic body and solidified to give a polymer elastic body to obtain a substrate for artificial leather. As a method of fixing the polymer elastic body to the fiber entangled body, there is a method of impregnating the fiber entangled body with the solution of the polymer elastic body and then wet coagulation or dry coagulation, depending on the type of the polymer elastic body to be used. These methods can be selected as appropriate.

  From the viewpoint of production efficiency, the artificial leather substrate is preferably cut in the thickness direction.

[Manufacturing method of artificial leather]
The surface of the artificial leather base or the half-finished artificial leather base can be subjected to raising treatment to obtain a suede-like artificial leather. The raising treatment can be performed by a grinding method using sandpaper or a roll sander. The artificial leather is preferably subjected to a dyeing treatment. Examples of the dyeing process include immersion dyeing such as liquid dyeing using a jigger dyeing machine or liquid dyeing machine, thermosol dyeing using a continuous dyeing machine, roller printing, screen printing, ink jet printing, sublimation, and the like. For example, printing on a napped surface by printing, vacuum sublimation printing, or the like can be used. Among them, it is preferable to use a liquid dyeing machine because a soft texture can be obtained. Moreover, if necessary, various resin finishing processes can be performed after dyeing.

  When calculating the degree of biomass plastics of dyed artificial leather, it can be calculated by extracting and measuring fiber entangled bodies and / or polymer elastic bodies from dyed artificial leather using the procedure described above. it can.

  Moreover, the above-mentioned artificial leather can be provided with a design property on the surface as necessary. For example, post-processing such as drilling such as perforation, embossing, laser processing, pin sonic processing, and print processing can be performed.

  Next, the artificial leather substrate of the present invention and the production method thereof will be described with reference to examples. In addition, about the matter which has no special description, it measured according to the said method.

<Evaluation method>
A. Biomass plastic degree of substrate for artificial leather:
The calculation was performed according to the following procedures (1) to (5).
(1) The weight of the artificial leather substrate is measured.
(2) The mass ratio of the fiber entangled body in the artificial leather substrate is calculated by isolating the fiber entangled body from the artificial leather substrate and measuring the weight.
(3) The mass ratio of the polymer elastic body in the artificial leather base is calculated from the result of (2).
(4) The biomass plasticity of the fiber entangled body and the polymer elastic body is calculated by the above method.
(5) The biomass plasticity of the substrate for artificial leather is calculated by the calculation of [Formula 1].

B. Tensile strength when wet of artificial leather substrate:
A test piece having a width of 20 mm and a length of 200 mm was cut out from the base body for artificial leather. In JIS L 1913 (2010) 6.3.2, the gripping interval was set to 100 mm with an Instron type tensile tester, and the tensile speed was set to 100 mm. It pulled as 200 mm / min and made the strength at the time of fracture | rupture the tensile strength at the time of wetness.

<Notation of chemical substances>
DMF: N, N-dimethylformamide PVA: polyvinyl alcohol [Production of raw cotton A]
Polyethylene terephthalate (PET A. PET A. isomers and impurities) consisting of ethylene glycol (content of isomers and impurities: 50 ppm) as biomass and terephthalic acid derived from biomass resources as an island component. Content: 250 ppm), a polystyrene having a melt flow rate (MFR) of 2.2 as a sea component, a sea-island type composite die having a number of islands of 16 islands / hole, and a spinning temperature of 285 ° C. Then, after melt spinning with an island component / sea component mass ratio of 80/20, the fiber was stretched 2.7 times, subjected to crimping using an indentation type crimper, and then cut to a length of 51 mm. As a result, raw cotton A of sea-island type composite fiber having a single fiber fineness of 4.2 dtex was obtained. The bio-based carbon content based on ISO 16620-2 of the ultrafine fiber obtained by removing polystyrene from the raw cotton A is 100%, and the components measured by elemental analysis and GC-MS are components derived from ethylene glycol. And the component derived from terephthalic acid in a mass ratio of 31:69. From the above results, the calculated biomass plasticity was 100%.

[Production of raw cotton B]
Except for the use of polyethylene terephthalate (PET B) with an intrinsic viscosity (IV) of 0.73 as an island component, consisting of ethylene glycol derived from biomass resources (content of isomers and impurities: 50 ppm) and terephthalic acid derived from petroleum resources Raw cotton B was obtained in the same manner as in the production of raw cotton A. The bio-based carbon content based on ISO 16620-2 of the ultrafine fiber obtained by removing polystyrene from the raw cotton B is 20%, and the components measured by elemental analysis and GC-MS are components derived from ethylene glycol. And the component derived from terephthalic acid in a mass ratio of 31:69. From the above results, the calculated biomass plasticity was 31%.

[Manufacture of raw cotton C]
The raw cotton C is produced in the same manner as the raw cotton A except that polyethylene island terephthalate (PET C) having an intrinsic viscosity (IV) of 0.73 made of ethylene glycol derived from petroleum resources and terephthalic acid derived from petroleum resources is used as the island component. Got. The bio-based carbon content based on ISO 16620-2 of the ultrafine fiber obtained by removing polystyrene from the raw cotton C is 0%, and the components measured by elemental analysis and GC-MS are components derived from ethylene glycol. And the component derived from terephthalic acid in a mass ratio of 31:69. From the above results, the calculated biomass plasticity was 0%.

[Manufacture of raw cotton D]
Other than using polybutylene terephthalate (PBT A) having an intrinsic viscosity (IV) of 0.73 consisting of butylene glycol derived from biomass resources (content of isomers and impurities: 100 ppm) and terephthalic acid derived from petroleum resources as island components Produced raw cotton D in the same manner as in the production of raw cotton A. The bio-based carbon content based on ISO 16620-2 of the ultrafine fiber obtained by removing polystyrene from the raw cotton D is 33%, and the components measured by elemental analysis and GC-MS are components derived from butylene glycol. And the component derived from terephthalic acid in a mass ratio of 40:60. From the above results, the calculated biomass plasticity was 40%.

[Manufacture of raw cotton E]
Polyethylene terephthalate (PET A: isomer and impurity) consisting of ethylene glycol derived from biomass resources (content of isomers and impurities: 50 ppm) and terephthalic acid derived from biomass resources as an island component and having an intrinsic viscosity (IV) of 0.73 Content: 250 ppm), polystyrene having a melt flow rate (MFR) of 18 as a sea component, a sea-island type composite die having a number of islands of 36 islands / hole, and a spinning temperature of 285 ° C. After melt spinning with a component / sea component mass ratio of 55/45, it is stretched 3.5 times, subjected to crimping using an indentation type crimper, and then cut into a length of 51 mm. A raw cotton E of sea-island type composite fiber having a fiber fineness of 3.2 dtex was obtained. The bio-based carbon content based on ISO 16620-2 of the ultrafine fiber obtained by removing polystyrene from the raw cotton E is 100%, and the components measured by elemental analysis and GC-MS are components derived from ethylene glycol. And the component derived from terephthalic acid in a mass ratio of 31:69. From the above results, the calculated biomass plasticity was 100%.

[Production of Polymer Elastic Body A]
A four-necked flask equipped with a stirrer and a thermometer is copolymerized with 1,10-decanediol (content of isomers and impurities: 400 ppm) derived from biomass and 1,4-butanediol derived from petroleum 100 parts by mass of diol (number average molecular weight 2,000, molar ratio: 91/9), copolymer polycarbonate diol (number of 3-methyl-pentanediol derived from petroleum raw material and 1,6-hexanediol derived from petroleum raw material (Average molecular weight 2,000, mol% ratio: 50/50) 100 parts by mass, 7.6 parts by mass of ethylene glycol derived from biomass raw material, 61.6 parts by mass of 4,4′-diphenylmethane diisocyanate derived from petroleum raw material, and 628 parts by mass of DMF And reacted for 15 hours in a dry nitrogen atmosphere at 70 ° C. A solution of polymer elastic body A in an amount of% was obtained. The polymer elastic body A obtained by distilling off DMF from the polymer elastic body A solution has a bio-based carbon content based on ISO 16620-2 of 37% and is measured by elemental analysis and GC-MS. The components derived from 1,10-decanediol, 1,4-butanediol, 3-methyl-pentanediol, 1,6-hexanediol, ethylene glycol The component derived from the component derived from 4,4′-diphenylmethane diisocyanate was in a mass ratio of 35: 2: 37: 3: 23. From the above results, the calculated biomass plasticity was 38%.

[Production of polymer elastic body B]
A solution of the polymer elastic body B having a resin concentration of 30% by mass was obtained in the same manner as in the production of the polymer elastic body A, except that 1,10-decanediol was derived from a petroleum raw material. The polymer elastic body B obtained by distilling off DMF from the solution of the polymer elastic body B has a bio-based carbon content based on ISO 16620-2 of 0%, and is measured by elemental analysis and GC-MS. The components derived from 1,10-decanediol, 1,4-butanediol, 3-methyl-pentanediol, 1,6-hexanediol, ethylene glycol The component derived from the component derived from 4,4′-diphenylmethane diisocyanate was in a mass ratio of 35: 2: 37: 3: 23. From the above results, the calculated biomass plasticity was 0%.

[Example 1]
Using raw cotton A as raw cotton, through a card and cross wrapping process, a laminated fiber web is formed, needle punched with a punch number of 2400 pieces / cm ² , a thickness of 2.3 mm, and a density of 0.24 g An intertwined sheet (felt) of / cm ³ was obtained.

  The entangled sheet obtained as described above was shrunk with hot water at a temperature of 96 ° C., and then impregnated with a 12% by mass PVA aqueous solution having a saponification degree of 88%, based on the solid fiber content. The sheet was squeezed with a target amount of 30% by mass and dried while migrating PVA with hot air at a temperature of 140 ° C. for 10 minutes to obtain a sheet with PVA. Next, the sheet with PVA thus obtained is immersed in trichlorethylene, and squeezing and compressing with a mangle is performed 10 times to dissolve and remove sea components and compress the sheet with PVA. A sheet with seawater-free PVA formed by entanglement of the provided ultrafine fiber bundle was obtained.

  The compressed sheet with deseased PVA obtained as described above is impregnated with a DMF solution of polymer elastic body A having a solid content adjusted to 13% by mass, and a target weight of 34% by mass with respect to the fiber content of the solids is obtained. The polymer elastic body was coagulated in an aqueous solution having a DMF concentration of 30% by mass. Then, PVA and DMF are removed with hot water, dried with hot air at a temperature of 120 ° C. for 10 minutes, and the average short fiber diameter of the ultrafine fibers is 4.4 μm, the thickness is 1.7 mm, the fiber entangled body and the polymer A base for artificial leather having an elastic body mass ratio of 75:25 was obtained. A polymer elastic body was extracted from the obtained artificial leather substrate using DMF, and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured. As a result, the fiber entangled body was 100% and the polymer elastic body was 38. %Met. The biomass plasticity of the base for artificial leather calculated from the above results was 85%, and the environmental load was low. Moreover, the tensile strength when wet was 26 N / cm, and it had strength.

[Example 2]
An artificial leather substrate was obtained in the same manner as in Example 1 except that the raw cotton B was used as the raw cotton. When the polymer elastic body was extracted from the obtained artificial leather substrate using DMF and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured, the fiber entangled body was 31% and the polymer elastic body was 38%. %Met. The biomass plasticity of the artificial leather substrate calculated from the above results was 33%, which was inferior to the artificial leather substrate of Example 1 but had a low environmental load. Moreover, the tensile strength when wet was 33 N / cm, and it had strength.

[Example 3]
An artificial leather substrate was obtained in the same manner as in Example 1 except that the raw cotton C was used as the raw cotton. The polymer elastic body was extracted from the obtained artificial leather substrate using DMF, and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured. The fiber entangled body was 0%, and the polymer elastic body was 38%. %Met. The biomass plasticity of the artificial leather substrate calculated from the above results was 10%, which was inferior to the artificial leather substrate of Example 1 but had a low environmental load. Moreover, the tensile strength when wet was 38 N / cm, and it had strength.

[Example 4]
An artificial leather substrate was obtained in the same manner as in Example 1 except that the raw cotton D was used as the raw cotton. The polymer elastic body was extracted from the obtained artificial leather substrate using DMF, and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured. The fiber entangled body was 40%, and the polymer elastic body was 38%. %Met. The biomass plasticity of the artificial leather substrate calculated from the above results was 40%, which was inferior to the artificial leather substrate of Example 1 but had a low environmental load. Moreover, the tensile strength when wet was 32 N / cm, and it had strength.

[Example 5]
An artificial leather base having an average short fiber diameter of 2.0 μm of ultrafine fibers was obtained in the same manner as in Example 1 except that the raw cotton E was used as the raw cotton. The polymer elastic body was extracted from the obtained artificial leather substrate using DMF, and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured. The fiber entangled body was 100% and the polymer elastic body was 38. %Met. The biomass plasticity of the artificial leather substrate calculated from the above results was 85%, and the environmental load was low. Moreover, the tensile strength when wet was 25 N / cm and had strength.

[Comparative Example 1]
An artificial leather substrate was obtained in the same manner as in Example 1 except that the raw cotton C was used as the raw cotton, and the polymer elastic body B was used as the polymer elastic body. When the polymer elastic body was extracted from the obtained artificial leather substrate using DMF and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured, the fiber entangled body was 0% and the polymer elastic body was 0. %Met. The biomass plasticity of the substrate for artificial leather calculated from the above results was 0%, and the environmental load was high. Moreover, the tensile strength when wet was 40 N / cm, and it had strength.

  The artificial leather base of the present invention is a natural leather-like artificial leather base containing components derived from biomass resources that contribute to carbon neutral in order to reduce environmental burdens. Although it can be used in various fields such as building materials, it is preferably used in interior materials for vehicles that are particularly environmentally friendly.

That is, the present invention is intended to solve the above-mentioned problems, and the substrate for artificial leather according to the present invention is derived from a fiber entangled body made of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less and a biomass raw material. A base material for artificial leather comprising a polyurethane having a polycarbonate diol as a reaction component , wherein the biomass plasticity of the base material for artificial leather defined by ISO 16620 (2015) is any of the fiber entangled body and the polyurethane. also Ri der 100% to 15% or less, a tensile strength of wet of not more than 10 N / cm or more 200 N / cm, and the content of isomers and impurities of the biomass-resource-derived raw material to 100% by weight biomass plastic Ru der 1000ppm or less for a suede-like artificial leather made of artificial leather for the base.

The substrate for artificial leather of the present invention is a substrate for artificial leather made of polyurethane having a fiber entangled body made of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less and a polycarbonate diol derived from a biomass raw material as reaction components. biomass plastics degree defined by ISO16620 (2015) is, in the above fiber-entangled body and said polyurethane, both Ri der 100% to 15% or less, a tensile strength at wetting 10 N / cm or more 200 N / cm less and and der Ru 1000ppm or less with respect to 100 mass% content of isomers and impurities biomass plastics biomass-resource-derived raw material, a suede artificial leather made of artificial leather for substrates. Details will be described below.

[ Reference Example 1 ]
An artificial leather substrate was obtained in the same manner as in Example 1 except that the raw cotton C was used as the raw cotton. The polymer elastic body was extracted from the obtained artificial leather substrate using DMF, and the biomass plasticity of the fiber entangled body and the polymer elastic body was measured. The fiber entangled body was 0%, and the polymer elastic body was 38%. %Met. The biomass plasticity of the artificial leather substrate calculated from the above results was 10%, which was inferior to the artificial leather substrate of Example 1 but had a low environmental load. Moreover, the tensile strength when wet was 38 N / cm, and it had strength.

Claims (9)

  A substrate for artificial leather comprising a fiber entangled body composed of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less and a polymer elastic body, and has a biomass plastic degree of 5% or more as defined by ISO 16620 (2015) A substrate for artificial leather which is 100% or less.   The base material for artificial leather according to claim 1, wherein the biomass plasticity of the base material for artificial leather is 15% or more.   The base material for artificial leather according to claim 1, wherein the biomass plasticity of the base material for artificial leather is 25% or more. 2. The artificial leather substrate according to claim 1, wherein a biomass plasticity of the fiber entangled body and a biomass plasticity of the polymer elastic body are both 5% or more and 100% or less.   The artificial leather base according to any one of claims 1 to 4, wherein the ultrafine fibers are polyester.   The artificial leather substrate according to any one of claims 1 to 5, wherein the polymer elastic body is polyurethane.   The base material for artificial leather according to claim 6, wherein the polyurethane is a polyurethane having a polycarbonate diol derived from a biomass raw material as a reaction component.   The substrate for artificial leather according to any one of claims 1 to 7, wherein the tensile strength when wet is 10 N / cm or more and 200 N / cm or less.   Artificial leather comprising the base for artificial leather according to any one of claims 1 to 8.