Laminate, and synthetic leather

Abstract

To provide: a laminate capable of realizing presence of a plant-derived material, with an aspect accompanying a high design property; and a vehicle sheet thereof.SOLUTION: A laminate comprises a resin layer containing a colorant, and another resin layer containing a plant-derived fiber. According to the laminate, the plant-derived fiber has a number-average aspect ratio (major diameter / minor diameter) of 1.5 or more and 15 or less; the plant-derived fiber has a number-average major diameter of 0.2 mm or more and 3.0 mm or less; the plant-derived fiber has a number-average minor diameter of 0.03 mm or more and 1.0 mm or less, in an image of the laminates.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminate and an artificial leather. [Background technology]

[0002] Sustainable products are currently attracting attention, and efforts are underway to replace some petroleum-based products with plant-based materials. In the field of synthetic leather, various studies are being conducted, as detailed below.

[0003] US Pat. No. 5,399,433 discloses a method for producing a formulation based on polyurethane and prickly pear mucilage for use in producing synthetic skin-like flexible coatings. Patent Document 2 discloses a composition for producing a laminate made of a cellulose-containing plant material derived from apple waste, a method for producing a laminate from a cellulose-containing plant material derived from apple waste, and a laminate produced by said method.

[0004] Patent Document 3 discloses an artificial leather having a PVC layer containing coconut shell powder modified vermiculite powder. US Pat. No. 5,399,633 discloses the use of coconut fibre in combination with a rubber-like binder for the manufacture of vehicle seat cushions, mattresses, filters or packaging materials.

[0005] Although the products to which the technologies described in Patent Document 1 and Patent Document 2 are applied are touted as being sustainable products, the presence of plant-derived materials cannot be felt by users. Even if the manufacturing methods disclosed in the above patent documents were used to disperse plant-derived materials in a laminate or sheet in a manner that allows the presence of the plant-derived materials to be felt, it would be impossible to achieve both design and performance, and it would not lead to an increase in the value of the product. In other words, there have been no laminates or synthetic leathers that allow the user to feel the presence of plant-derived materials in a highly design-oriented manner. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special table 2022-544741 [Patent Document 2] U.S. Patent Application Publication No. 2021 / 0189642 [Patent Document 3] China Patent Application Publication No. 112721364 [Patent Document 4] International Publication No. 97 / 005313 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to solve the above-mentioned problems in the prior art and to achieve the following object: That is, the present invention aims to provide a laminate and synthetic leather that allow the user to feel the presence of plant-derived materials in a highly designable manner. [Means for solving the problem]

[0008] As a result of intensive research by the inventors to achieve the above-mentioned object, they have discovered that a laminate and synthetic leather can be provided that allow the presence of plant-derived materials to be felt in a highly designable manner, by a laminate having a resin layer containing a colorant and a resin layer containing plant-derived fibers, wherein in an image of the laminate, the number-average aspect ratio (longer diameter / minor diameter) of the plant-derived fibers is 1.5 to 15, the number-average longer diameter of the plant-derived fibers is 0.2 mm to 3.0 mm, and the number-average shorter diameter of the plant-derived fibers is 0.03 mm to 1.0 mm. Here, "an embodiment with a high level of design" refers to an embodiment that evokes an aesthetic feeling, and in which various design variations can be obtained by changing the color, dispersion state, etc. The number average aspect ratio, number average major axis, and number average minor axis of the plant-derived fibers are values ​​measured from images of the laminate or synthetic leather.

[0009] The present invention is based on the above findings by the present inventors, and the means for solving the above problems are as follows. That is, <1> A laminate having a resin layer containing a colorant and a resin layer containing plant-derived fibers, In an image of the laminate, the number average aspect ratio (long axis / short axis) of the plant-derived fibers is 1.5 or more and 15 or less; The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, The laminate is characterized in that the number average short diameter of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less. <2> The above <1> and a base fabric. Effect of the Invention

[0010] According to the present invention, it is possible to solve the above-mentioned problems in the conventional art, achieve the above-mentioned object, and provide a laminate and synthetic leather that allows the user to feel the presence of plant-derived materials in a highly designable manner. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing the layer structure of the laminate. [Diagram 2] FIG. 2 is a photograph of the laminate of Example 1. [Diagram 3] FIG. 3 is a photograph of the laminate of Example 2. [Figure 4] Figure 4 shows an image (part 1) processed using image processing and analysis software. [Diagram 5] Figure 5 is an image (part 2) processed using image processing and analysis software. [Figure 6] Figure 6 is an image (part 3) processed using image processing and analysis software. [Figure 7] FIG. 7 is a schematic diagram of a resin layer containing plant-derived fibers for explaining the degree of envelopment. [Figure 8]FIG. 8 is a photograph of a resin layer containing plant-derived fibers to explain the degree of envelopment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] (Laminate) The laminate has a resin layer containing a colorant and a resin layer containing plant-derived fibers, and may further have other layers. The laminate can be used for various purposes, and can also be used as synthetic leather containing plant-derived fibers.

[0013] <Resin layer containing colorant> The resin layer containing the colorant may include a colorant, a resin, a plasticizer, a filler, and other components.

[0014] The resin layer containing the colorant can be produced by melt-kneading the above-mentioned components and rolling them.

[0015] <<Coloring agent>> The colorant is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include pigments and dyes. These may be used alone or in combination of two or more. Among these, pigments are preferred from the viewpoints of coloring power and hiding power.

[0016] The pigment is not particularly limited and may be appropriately selected depending on the purpose, and may be an inorganic pigment or an organic pigment. These may be used alone or in combination of two or more kinds.

[0017] The inorganic pigment is not particularly limited and can be appropriately selected depending on the purpose. Examples of the inorganic pigment include carbon black, titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow. The organic pigment is not particularly limited and can be appropriately selected depending on the purpose. Examples of the organic pigment include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, and aniline black.

[0018] The content of the colorant in the resin layer containing the colorant is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a laminate and synthetic leather that has a high design quality and allows the presence of plant-derived materials to be felt, the content is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less.

[0019] The color of the colorant is not particularly limited and can be appropriately selected depending on the purpose, but is preferably black, white, brown, yellow, red, blue, green, or purple. An example of the black colorant is carbon black. An example of the white colorant is Pigment White 6. An example of the brown colorant is Pigment Red 101. Examples of the yellow colorant include Pigment Brown 24 and Pigment Yellow 181. Examples of the red colorant include Pigment Red 221 and Pigment Red 254. An example of the blue colorant is Pigment Blue 15. An example of the green colorant is Pigment Green 7. An example of the purple colorant is Pigment Violet 23. The above colors can also be mixed to create grays and beiges.

[0020] <<Resin>> The resin is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include polyvinyl chloride (PVC) (vinyl chloride resin), urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, acrylic-styrene resin, acrylic-silicone resin, etc. These may be used alone or in combination of two or more. Among these, polyvinyl chloride (PVC) (vinyl chloride resin) is preferred because it is durable and can be easily decorated in various ways.

[0021] The polyvinyl chloride (PVC) can be produced by a polymerization reaction of vinyl chloride (chloroethylene). Commercially available polyvinyl chloride (PVC) can also be used. The polymerization reaction is not particularly limited and may be appropriately selected depending on the purpose. Examples of the polymerization reaction include a suspension polymerization method and an emulsion polymerization method (paste polymerization method).

[0022] The properties of the polyvinyl chloride (PVC) are not particularly limited and can be appropriately selected depending on the purpose, but polyvinyl chloride (PVC) having an average degree of polymerization of 800 or more and 2500 or less is preferred. The polyvinyl chloride (PVC) may be a modified polyvinyl chloride (PVC).

[0023] Examples of commercially available polyvinyl chloride (PVC) products include the TE series and TH series manufactured by Taiyo Vinyl Chloride Co., Ltd., the TK series manufactured by Shin-Etsu Chemical Co., Ltd., and the PSH series and PSM series manufactured by Kaneka Corporation.

[0024] <<Plasticizer>> The plasticizer is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phthalates such as dialkyl phthalates, adipic esters, trimellitic esters, etc. These may be used alone or in combination of two or more.

[0025] The content of the plasticizer relative to the resin in the resin layer containing the colorant is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of producing a synthetic leather having strength and durability, however, the content is preferably 50% by mass or more and 150% by mass or less, and more preferably 80% by mass or more and 120% by mass or less.

[0026] <<Filling agent>> The filler is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include alumina, titanium dioxide, zinc oxide, cerium dioxide, calcium carbonate, silica, talc, magnesium hydroxide, mica, barium sulfate, silicic acid, ammonium polyphosphate, aluminum dialkylphosphinate, polymelamine phosphate, carbon black, carbon nanotubes, carbon fibers, etc. These may be used alone or in combination of two or more.

[0027] The content of the filler relative to the resin in the resin layer containing the colorant is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of producing synthetic leather having strength and durability, however, the content is preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 10% by mass or less.

[0028] <<Other ingredients>> The other components are not particularly limited and can be appropriately selected depending on the purpose. Examples of the other components include a stabilizer.

[0029] The thickness of the resin layer containing the colorant is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of strength and durability, however, the thickness is preferably 20 μm or more and 1000 μm or less, more preferably 100 μm or more and 500 μm or less, even more preferably 150 μm or more and 350 μm or less, and particularly preferably 200 μm or more and 300 μm or less.

[0030] <Resin layer containing plant-derived fibers> The resin layer containing plant-derived fibers can contain plant-derived fibers, resin, plasticizer, filler, and other components. The resin layer containing the plant-derived fibers may contain a colorant. The content of the colorant is from 0% by mass to 5% by mass, and preferably from 0% by mass to 3% by mass. By coloring the resin layer containing the plant-derived fibers, the plant-derived fibers may not be unnecessarily conspicuous, leading to a more natural impression, and at the same time, there is also an effect of increasing the coloring power and hiding power of the laminate as a whole. The colorant is as described above in <Resin layer containing colorant>.

[0031] The resin layer containing the plant-derived fibers can be produced by melt-kneading the above-mentioned components and rolling them. Among these, in order to prevent re-adsorption of moisture and deterioration during transportation, it is preferable to dry the plant-derived fibers and, immediately after drying, melt-knead the plant-derived fibers and powdered materials such as the resin to form pellets. The pelletization is carried out using a twin-screw extruder after mixing the material powders. The content of the plant-derived fibers in the pellets is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 30% by mass or more and 60% by mass or less. When preparing the pellets, plasticizers, stabilizers, lubricants, and gelation accelerators may be added as necessary. The gelation accelerators create a pseudo-crosslinked state with the resin molecules, imparting melt elasticity. Acrylic polymers are used as gelation accelerators for polyvinyl chloride (PVC).

[0032] The resin, plasticizer, filler, and other components are as described above in <Resin layer containing colorant>.

[0033] <<Plant-derived fiber>> The plant-derived fibers are not particularly limited and can be appropriately selected from fibers made of plant materials depending on the purpose. These fibers may be used alone or in combination of two or more kinds.

[0034] Although not necessarily an essential or academic classification, plants can be broadly divided into woody and herbaceous plants as follows. woody plant group of plants that grow by annual accumulation of xylem cells herbaceous group of plants that have no woody tissue and die within one or several years Any fibrous material that satisfies the aspect ratio, major axis, and minor axis ranges of the present invention can be used, regardless of whether it is woody or herbaceous. However, for reasons such as ease of procurement and processing, the fact that it is not an edible part, and the difficulty of using it for other purposes such as fuel, fibrous materials such as the leaves, stems, and petals of herbaceous plants and non-woody leaves, fruits, and petals of woody plants are preferred.

[0035] Specific examples of herbaceous plants include the leaves of grasses, rice, wheat, barley, rye, etc., rice husks after threshing, corn leaves, husks, and hairs (pistils), petals of ornamental plants, and evergreen perennial plants such as Erianthus and Miscanthus. Examples of fibrous materials such as leaves, fruits, petals, etc. other than wood of woody plants include pine leaves, cherry blossoms and leaves, fruit skins (coffee bean shells, apple, mandarin orange, banana peels, peanut shells and skins, walnut shells), bamboo leaves, bamboo leaves, coconuts, etc. Among these, preferred are fibers derived from coconut trees, which are discarded in large quantities because they are difficult to use for other purposes and are said to generate greenhouse gases such as methane gas when decomposed, and coconut fiber is more preferred.

[0036] The coconut-derived fiber is a fiber derived from a plant belonging to the palm family. The plant belonging to the palm family is not particularly limited and can be appropriately selected depending on the purpose. For example, plants belonging to the subfamily Areca, Ceroxylon, Araceae, Acanthaceae, and Nipahae can be mentioned. Among these, plants belonging to the Areca subfamily are preferred in order to produce a laminate that allows the user to feel the presence of plant-derived materials.

[0037] Plants belonging to the Areca subfamily are not particularly limited and can be appropriately selected depending on the purpose. Examples include plants belonging to the tribes Areca, Cocos, Euterpe, Geonoma, Iriartea, Leoportinia, Orania, Pelagodoxa, Podococcus, Reinhardtia, Roystonea, and Sclerosperma. Among these, plants belonging to the family Cocosidae are preferred in order to produce a laminate in which the presence of a plant-derived material can be clearly felt.

[0038] The plant belonging to the family Cocosidae is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include coconut palm (Cocos nucifera), oil palm (Elaeis oleracea), and Bactris chontaduro. Among these, coconut palm of the genus Cocos is preferred from the viewpoint of producing a laminate in which the presence of a plant-derived material can be clearly felt.

[0039] There are no particular restrictions on the part of the plant belonging to the palm family, and it can be selected appropriately depending on the purpose, but from the viewpoint of producing a laminate that allows the presence of plant-derived materials to be felt, the fruit is preferred, and the fruit skin (coconut fiber) is more preferred.

[0040] The method for producing the plant-derived fibers is not particularly limited and can be appropriately selected depending on the purpose. For example, there is a method in which a fiber raw material (long fiber) having a length of several tens of centimeters is crushed using a cutter mill (φ2 mm screen) from the outer skin of the fruit of a plant belonging to the palm family (coconut fiber), and then the fiber is passed through a mesh with a desired mesh size and then dried.

[0041] The temperature for drying after the grinding is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of preventing deterioration of the plant-derived fibers, however, a temperature of 50°C or higher and 100°C or lower is preferable, a temperature of 50°C or higher and 80°C or lower is more preferable, and a temperature of 50°C or higher and 70°C or lower is particularly preferable.

[0042] The drying time after the grinding is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of producing a laminate in which no moisture remains, the drying time is preferably from 2 hours to 100 hours, and more preferably from 10 hours to 80 hours.

[0043] The moisture content of the plant-derived fiber is preferably 2.0% by mass or less, and particularly preferably 1.5% by mass or less. The moisture content of the plant-derived fiber is measured using an infrared moisture meter, FD-600 (manufactured by Kett Electric Laboratory Co., Ltd.).

[0044] The moisture content of the plant-derived fibers can be reduced by appropriately adjusting the drying conditions and drying time. However, since plant-derived fibers re-adsorb moisture at a very rapid rate even in a room temperature environment, it is necessary to control the re-adsorption of moisture after drying until the fibers are introduced into the melt-kneading process.

[0045] The number-average aspect ratio (long axis / short axis) of the plant-derived fibers in the image of the laminate is not particularly limited as long as it is 1.5 or more and 15 or less, and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a laminate and synthetic leather in which the presence of the plant-derived material stands out and which evokes an aesthetic impression, the aspect ratio is preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, even more preferably 3 or more and 8 or less, and particularly preferably 3 or more and 5 or less. If the plant-derived fibers have a number-average aspect ratio (major axis / minor axis) of more than 15, the fibers will overlap and become entangled, causing a foreign body sensation. If the number-average aspect ratio (major axis / minor axis) of the plant-derived fibers is less than 1.5, the fiber material will not feel like a natural fiber material and will feel like a foreign object.

[0046] The number-average major axis of the plant-derived fibers in the image of the laminate is not particularly limited as long as it is 0.2 mm or more and 3.0 mm or less, and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a laminate and synthetic leather in which the presence of the plant-derived material stands out and which evokes an aesthetic impression, the number-average major axis is preferably 0.2 mm or more and 2.0 mm or less, more preferably 0.3 mm or more and 1.0 mm or less, and particularly preferably 0.4 mm or more and 0.8 mm or less.

[0047] In the image of the laminate, it is preferable that the plant-derived fibers do not contain fibers having a major diameter that is 2.5 times or more the number average major diameter. If the fibers contain such fibers, the impression of aesthetics is impaired even if the average value falls within the range of the major diameter.

[0048] The number average minor axis (thickness) of the plant-derived fibers in the image of the laminate is not particularly limited as long as it is 0.03 mm or more and 1.0 mm or less, and can be appropriately selected according to the purpose. Due to the nature of plant-derived fibers, they are prone to cracking along the fiber direction when crushed, so in order to obtain plant-derived fibers in the above range of major axis, it is preferable to prepare them so that the average minor axis (thickness) is in the range of 1.0 mm or less. From the viewpoint of producing a laminate and synthetic leather that allows the presence of plant-derived materials to be felt in a highly designable form, it is preferably 0.05 mm or more and 0.7 mm or less, more preferably 0.1 mm or more and 0.3 mm or less, and particularly preferably 0.1 mm or more and 0.2 mm or less.

[0049] As for the combination of the number average aspect ratio, number average major axis and number average minor axis of the plant-derived fibers in the image of the laminate, from the viewpoint of producing a laminate and synthetic leather in which the presence of the plant-derived material stands out and which evokes an aesthetic impression, a combination in which the number average major axis is in the range of 0.2 mm or more and 2.0 mm or less, the number average minor axis is in the range of 0.05 mm or more and 0.7 mm or less, and the number average aspect ratio is in the range of 1.5 or more and 15 or less is preferred, a combination in which the number average major axis is in the range of 0.3 mm or more and 1.0 mm or less, the number average minor axis is in the range of 0.1 mm or more and 0.3 mm or less, and the number average aspect ratio is in the range of 2 or more and 10 or less is more preferred, and a combination in which the number average major axis is in the range of 0.4 mm or more and 0.8 mm or less, the number average minor axis is in the range of 0.1 mm or more and 0.3 mm or less, and the number average aspect ratio is in the range of 2 or more and 8 or less is most preferred.

[0050] The number average major axis and number average minor axis of the plant-derived fibers in the raw material are determined by crushing the plant-derived fibers, passing a sample through a mesh having openings of a desired range, drying the sample, and then examining the sample with an optical microscope. The number average major axis and the number average minor axis of the plant-derived fibers in the image of the laminate are measured by observing the produced laminate with an optical microscope. In both cases, the long and short diameters of 300 particles are measured by comparing them with the scale lines from a photograph of the particle image taken at 30x magnification, and the arithmetic mean values ​​of the long and short diameters and aspect ratios of the 300 particles are calculated. At this time, flake-like dust particles with a diameter of less than 0.10 mm and an aspect ratio of less than 1.5 are excluded from the measurement. The major axis is the length of a perpendicular line connecting two parallel lines that are tangent to the contour of the plant-derived fiber particle image and have the greatest distance between the two parallel lines. The minor axis is the length connecting two intersections between a straight line that is parallel to the two parallel lines and passes through the half point of the perpendicular line and the contour of the plant-derived fiber particle image.

[0051] As a method for adjusting the number average major axis and number average minor axis of the plant-derived fibers, when the particle size is reduced using a fine grinder with a classification mechanism (generally a grinder such as a jet mill aiming for 10 μm or less), the number of times of processing in the grinder increases, so the aspect ratio tends to approach 1. However, the plant-derived fibers of the present invention having a number average aspect ratio of 1.5 to 15, a number average major axis of 0.2 mm to 3.0 mm, and a number average minor axis of 0.03 mm to 1.0 mm can be produced by using a cutter mill and adjusting the screen size and the gap between the screen and the rotor, without using a fine grinder such as a jet mill.

[0052] Since fibrous materials easily pass through a screen in the direction of their long diameter, it is possible to obtain coarsely pulverized materials with a large long diameter by adjusting the clearance between the screen and the rotor to a wide size. In addition, it is also possible to obtain coarsely pulverized materials with a large long diameter by using a screen with large openings. Due to the nature of plant-derived fibers, they tend to break along the fiber direction when crushed, so increasing the number of times they are processed with a cutter mill tends to reduce their short diameter (thickness). Therefore, to obtain fibrous particles with the desired long diameter, a single coarse grinding process can produce particles with a smaller short diameter (thickness) than a two-stage process in which the clearance between the screen and the rotor is gradually narrowed, even if the long diameter is the same. By using such a multi-stage process in which the clearance between the screen and the rotor is changed stepwise, it is possible to obtain fibrous particles with various combinations of long and short diameters (thickness). A classification step may be provided in which the coarsely pulverized material is classified using a classifier such as an air classifier or an elbow jet to remove fine dust and separate the material by size. The classification step may be provided between multiple pulverization steps. Since plant-derived fibers have a tendency to split along the fiber direction, it is preferable to prepare them so that the average short diameter (thickness) is within a range of 1.0 mm or less; if the short diameter (thickness) exceeds this range, it may be difficult to obtain fibrous particles with the desired long diameter.

[0053] Furthermore, coarse particles can be removed by passing the fibrous particles after crushing or classification through a mesh. Since fibrous materials tend to pass through a screen in the long diameter direction, they may contain coarse particles with a large long diameter. However, such coarse particles can be removed by adjusting the vibration frequency and amplitude when passing through the mesh. In this case, multiple meshes with different mesh openings can be used. In this manner, fibrous particles having the desired aspect ratio, major axis, and minor axis can be obtained. Similarly, fibers having a major axis that is 2.5 times or more the number-average major axis can be removed.

[0054] The content of the plant-derived fibers in the resin layer containing the plant-derived fibers is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoints of allowing the presence of the plant-derived fibers to be felt, evoking a sense of beauty, and giving a natural impression without a busy (messy) impression, the content is preferably 0.2% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 8.0% by mass or less, and even more preferably 1.0% by mass or more and 4.0% by mass or less.

[0055] The average value of the area ratio of the plant-derived fibers in an image of a resin layer containing the plant-derived fibers (100 x area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of creating a beautiful and natural impression, it is preferably 3.0% or more and 8.0% or less, and more preferably 4.0% or more and 6.0% or less.

[0056] In an image of a resin layer containing the plant-derived fibers, there is no particular restriction on the lower limit of the average value of the envelopment degree of the plant-derived fibers (an index representing the aggregation state of the plant-derived fibers: (envelopment perimeter (C PERI) (Convex perimeter: perimeter when connecting the convex parts of a figure) / (perimeter (PERI) (Perimeter: perimeter of the figure)) and this can be appropriately selected depending on the purpose. However, from the viewpoint of creating an aesthetic feeling and giving a natural impression, a lower limit of 98.0% or more is preferable, and 99.0% or more is more preferable. In an image of a resin layer containing the plant-derived fibers, there is no particular restriction on the upper limit of the average value of the envelopment degree of the plant-derived fibers (an index representing the aggregation state of the plant-derived fibers: (envelopment perimeter (C PERI) (Convex Perimeter: the perimeter when connecting the convex parts of a figure) / perimeter (PERI) (Perimeter: the perimeter of the figure)) and this can be appropriately selected depending on the purpose. However, from the viewpoint of creating a sense of beauty and giving a natural impression, a value of 99.9 or less is preferable. Among these, a content of 98.0% or more and 99.9% or less is preferred because it can create a sense of beauty and give a natural impression. In an image of the resin layer containing the plant-derived fibers, the ratio of the number of particles having an average envelopment degree of the plant-derived fibers of 90% or less is preferably 5.0% or less, more preferably less than 5.0%, and even more preferably none.

[0057] An image of the resin layer is obtained under the following (image capturing conditions), and the occupied area ratio and envelopment degree of the plant-derived fiber are measured under the following (image processing conditions).

[0058] (Image capture conditions) Digital image acquisition optical microscope: Keyence digital microscope Magnification: When measuring the exclusive area ratio, the magnification is 30 times. When measuring the envelopment, the magnification is 50 times.

[0059] (Image processing conditions) Processing image size: When measuring the occupied area ratio (magnification 30 times), it is 7.35 mm x 9.80 mm When measuring the envelopment (magnification 50x), it is 4.41mm x 5.88mm.

[0060] The calculation is performed using the image processing and analysis software WinROOF CLOUD manufactured by Mitani Shoji Co., Ltd., by carrying out the following process.

[0061] <Sampling> 1. Monochrome imaging If the image is a color image, it is converted to a monochrome image. Monochrome imaging can be performed by selecting monochrome imaging processing or RGB (red, green, blue) separation processing from the menu of the image analysis software WinROOF CLOUD manufactured by Mitani Shoji. 2. Noise Reduction Next, in order to remove fine noise that cannot be seen with the naked eye, the image is processed in noise removal mode, with the conditions for removing noise of 50 μm or less. 3. Density conversion (binarization) Next, the image density is adjusted by density conversion so that the outline of the part where the plant-derived fiber is present becomes clear. (1) It is confirmed by visual inspection that the part where the plant-derived fiber is present in the original image and (2) the outline of the image after density conversion (the part where the measurement target sample (plant-derived fiber) is present is displayed in white on the screen) completely overlap. If there is no complete overlap in the density conversion (for example, if the outline of (2) is larger than (1) or if the outline of (1) is larger than (2)), the input image density range for the density conversion is adjusted so that the part where the plant-derived fiber is present in the original image and the outline of the image after density conversion completely overlap. 4.Binarization Next, a binarization process is performed. The parts where plant-derived fibers exist are binarized into parts that are not. Visually check to see that (1) the parts of the original image where plant-derived fibers exist and (2) the contours of the binarized image (parts where the measurement target sample (plant-derived fibers) exists are displayed in green on the screen) completely overlap. In automatic binarization mode, if there is no complete overlap (for example, if the contour of (2) is larger than (1) or if the contour of (1) is larger than (2)), the sampling brightness range is adjusted so that the parts of the original image where plant-derived fibers exist and the contours of the binarized image completely overlap. FIG. 4 shows the original image at 50x magnification after processing using image processing and analysis software. FIG. 5 shows the images after 1. monochrome imaging, 2. noise removal, and 3. density conversion (binarization) in processing using image processing and analysis software. FIG. 6 shows the image after binarization process (4) in the processing using image processing analysis software.

[0062] <Exclusive area ratio> Particles are measured from the measurement menu of the image analysis software WinROOF CLOUD manufactured by Mitani Shoji, the data of the sampled particles is transferred to a spreadsheet software, and the total area value of particles having an equivalent circle diameter of 50 μm or more among the sampled particles is calculated by dividing the total area by the area of ​​the entire image. The average value of the exclusive area ratio calculated from 10 images is used.

[0063] <Envelope degree> Particle measurements are performed from the measurement menu of the image analysis software WinROOF CLOUD manufactured by Mitani Shoji, and the data of the sampled particles are transferred to a spreadsheet software. The envelopment ratio is calculated from the perimeter and the envelopment perimeter for each particle among the sampled particles that has a circle equivalent diameter of 100 μm or more. The average value of the envelope ratio calculated from 10 images is used. At this time, the sampling number is drawn on the image. This operation makes it possible to compare the data of each particle on the image with the data of each sampled particle by sampling number.

[0064] The envelope is defined by the following formula 1.

number

[0065] <Perimeter length (PERI)> The perimeter (PERI) is the perimeter of the figure.

[0066] <Envelope perimeter (C PERI)> The convex perimeter (C PERI) is the perimeter when connecting the convex portions of the figure.

[0067] The degree of envelopment is 100% (the maximum value) when all particles are separated, and decreases as more particles overlap.

[0068] For example, in the particle group shown in Figure 7, when the particles are separated (the two particles on the left), the perimeter and the envelope perimeter are the same, so the envelopment degree of each particle is 100%, but when the particles overlap (the two overlapping particles on the right), the envelope perimeter is the length of the dotted line portion, which is a smaller value than the perimeter, so the envelopment degree is a value lower than 100%.

[0069] In the particle shown in FIG. 8 with a circle equivalent diameter of 401 μm, two fibers are in contact with each other, but the degree of envelopment is 69.5%. In this way, when two particles are in contact or overlapping with each other, the perimeter becomes larger than the envelope perimeter, and the value of the degree of envelopment becomes lower. Such particles with a low degree of envelopment impair the aesthetic appearance and give a foreign body feeling that is not a natural fiber material.

[0070] In order to bring the degree of envelopment closer to 100, i.e., closer to a non-overlapping state, it is preferable that the pellets containing plant-derived fibers are diluted uniformly when they are diluted with the resin melt, and it is preferable to use plasticized pellets containing a plasticizer in the range of 50 parts by weight to 200 parts by weight per 100 parts by weight of resin as such pellets. Generally, when preparing a pellet-shaped master batch for the purpose of dispersing a colorant in a hard resin, a plasticizer is not used in order to apply a strong shear force. However, in order to obtain a laminate containing the plant-derived fibers of the present invention, in which the average envelopment degree (%) of the plant-derived fibers in an image of the resin layer containing the plant-derived fibers is 98.0% or more and 99.9 or less, and the number ratio of particles of the plant-derived fibers having an envelopment degree of 90% or less is 5.0% or less, it is preferable to add a plasticizer during pelletization to prepare plasticized, relatively soft pellets, and then uniformly dilute the pellets in the resin melt.

[0071] The thickness of the resin layer containing the plant-derived fibers is not particularly limited and can be appropriately selected depending on the purpose. From the standpoint of strength and durability, however, it is preferably from 20 μm to 1000 μm, more preferably from 100 μm to 500 μm, even more preferably from 150 μm to 400 μm, and particularly preferably from 200 μm to 300 μm.

[0072] <Other layers> The other layers are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other layers include a base fabric, an adhesive layer, a surface treatment layer, and a skin layer (also referred to as a "surface layer").

[0073] <<Base fabric>> The base fabric is not particularly limited and can be appropriately selected depending on the purpose. Examples of the base fabric include nonwoven fabric, woven fabric, and knitted fabric.

[0074] The material of the base fabric is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include polyester, polyethylene, nylon, acrylic, polyurethane, acetate, rayon, polylactic acid, cotton, hemp, silk, wool, glass fiber, etc. These may be used alone or in combination of two or more kinds. Of these, polyester is preferred. The base fabric may be made of fabric (fiber aggregate) made of fibers in the form of nonwoven fabric, woven fabric, knitted fabric, etc., and among these, it is preferable to use woven fabric or knitted fabric because they are inexpensive. In addition to the above materials, a sheet material having a porous structure obtained by impregnating a fabric with a synthetic resin such as a polyurethane resin may also be used as the base fabric. The base fabric has a function of supporting and reinforcing the layer formed on its front side. The provision of the base fabric can increase the strength and shape stability of the laminate sheet. The base fabric may be bonded to the layer formed on its front side by an adhesive.

[0075] The thickness of the base fabric is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 300 μm or more and 1,300 μm or less, and most preferably 400 μm or more and 700 μm or more.

[0076] In the laminate, a resin layer containing the colorant may be provided on the base fabric, and a resin layer containing the plant-derived fiber may be provided on the opposite side of the resin layer containing the colorant to the base fabric. The base fabric and the resin layer containing the colorant may be in direct contact with each other, or an adhesive layer may be provided between the base fabric and the resin layer containing the colorant.

[0077] <<Adhesive layer>> The adhesive layer may be provided between the base fabric and the resin layer containing the colorant.

[0078] The adhesive layer may include an adhesive. The adhesive layer can bond the base fabric and the resin layer containing the colorant.

[0079] The thickness of the adhesive layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 80 μm or less.

[0080] <<Surface treatment layer>> In the laminate, the surface treatment layer may be provided on the side of the resin layer containing plant-derived fibers opposite to the base fabric side. The surface treatment layer and the resin layer containing the plant-derived fibers may be in direct contact with each other, or the skin layer may be provided between the base fabric and the resin layer containing the plant-derived fibers.

[0081] The surface treatment layer may include polyurethane.

[0082] The content of the polyurethane in the surface treatment layer is not particularly limited and can be appropriately selected depending on the purpose.

[0083] The thickness of the surface treatment layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 5 μm to 20 μm, and more preferably from 10 μm to 20 μm.

[0084] <<Skin layer>> The skin layer may be provided between the resin layer containing the plant-derived fibers and the surface treatment layer.

[0085] The skin layer may comprise polyvinyl chloride or polyurethane.

[0086] The content of the polyvinyl chloride or polyurethane in the skin layer is not particularly limited and can be appropriately selected depending on the purpose.

[0087] The thickness of the skin layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15 μm or more and 30 μm or less.

[0088] 1 is a diagram showing a schematic layer structure of a laminate 1 according to one embodiment. The laminate 1 can have a base fabric 2, an adhesive layer 6, a resin layer 3 containing a colorant, a resin layer 4 containing plant-derived fibers, a skin layer 7, and a surface treatment layer 5, in this order.

[0089] (Method of manufacturing laminate) The method for producing the laminate is not particularly limited and may be appropriately selected depending on the purpose. Examples of the method include a calendar method and a casting method.

[0090] The calendaring method is not particularly limited and may be appropriately selected depending on the purpose. For example, a resin compound obtained by adding plant-derived fibers, plasticizers, fillers, etc. to a resin obtained by a suspension polymerization method is rolled using a calendar roll to obtain a resin layer, and the obtained resin layer is laminated on a base fabric.

[0091] Specifically, an adhesive is applied to one surface of the resin layer containing the plant-derived fibers, and the adhesive is laminated with a base fabric to obtain a laminate having a resin layer containing the plant-derived fibers, an adhesive layer, and a base fabric in that order, and a surface layer is applied to the surface of the resin layer containing the plant-derived fibers opposite the adhesive layer of the obtained laminate and dried, and further a surface treatment layer is applied to the surface of the surface layer opposite the resin layer containing the plant-derived fibers and dried.

[0092] In the case of the laminate of the present invention, the following production method is preferred. (1) A resin layer containing the colorant and a resin layer containing the plant-derived fiber are separately prepared in advance. In addition, when the resin layer containing the plant-derived fibers is prepared using pellets containing material powder, the pellets can be melt-kneaded with the resin in a previous step of this process to dilute the composition consisting of the resin and plant-derived fibers at the desired concentration. (2) Apply adhesive to the base fabric. (3) The base fabric coated with the adhesive and the resin layer containing the colorant are bonded together, and then the resin layer containing the plant-derived fiber is further laminated thereon. The resulting laminate is heated and bonded through a calendar roll.

[0093] The casting method is not particularly limited and may be appropriately selected depending on the purpose. For example, a method may be used in which a resin paste sol obtained by adding plant-derived fibers, a plasticizer, a filler, and the like to a resin obtained by emulsion polymerization (paste polymerization) is coated on a release paper or the like, and the resin layer obtained by heating and gelling is then laminated with a colorant-containing layer and a base fabric. Although it is possible to produce the laminate of the present invention by casting, by sequentially laminating onto release paper or the like, the specific calendaring method described above is preferably used for efficient mass production.

[0094] (synthetic leather) The synthetic leather of the present invention comprises the laminate of the present invention and a base fabric.

[0095] The laminate (the laminate of the present invention) is as described above in (Laminate). The base fabric is as described in <<Base Fabric>> of <<Other Layers>> of the above (Laminate).

[0096] (Vehicle seats) The vehicle seat of the present invention comprises the laminate of the present invention. The laminate of the present invention can be suitably used as a vehicle seat when it exhibits a level equivalent to that of a reference vehicle seat in which no plant fiber is added to PVC (a reference vehicle seat having a polyvinyl chloride (PVC) layer containing no plant-derived fiber) in a bending resistance test.

[0097] The laminate (the laminate of the present invention) is as described above in (Laminate). EXAMPLES

[0098] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0099] <Production Example 1: Production of plant-derived fibers> Coconut fiber raw material (long fibers) several tens of centimeters in length was processed with a φ2 mm screen pass using a cutter mill, and further passed twice through a mesh with 455 μm openings. The number average major axis of the obtained particles (number average major axis of the plant-derived fibers in the raw material) was 2.67 mm, and the number average minor axis (number average minor axis of the plant-derived fibers in the raw material) was 0.39 mm.

[0100] <Example 1-1: Production of resin layer 1 containing plant-derived fibers> The temperature was set to 150°C and the two rolls were heated sufficiently until the temperature stabilized. The following materials were all added simultaneously to the two rolls and melt-kneading was started. The plant-derived fibers used were those produced in Production Example 1, having a number average major axis (number average major axis of the plant-derived fibers in the raw material) of 2.67 μm and a number average minor axis (number average minor axis of the plant-derived fibers in the raw material) of 0.39 mm. After the addition, the mixture was melt-kneaded for 5 minutes at a set temperature of 150° C., and then rolled using a rolling machine to produce a resin layer 1 (thickness: 250 μm) containing plant-derived fibers. PVC TK-1300 (Shin-Etsu Chemical Co., Ltd.) 100 parts by weight Plasticizer Dialkyl phthalate 90 parts by weight Filler: Calcium carbonate 10 parts by weight Plant-derived fiber produced in Production Example 1: 4 parts by mass (equivalent to 1.96% by mass)

[0101] <Example 1-2: Production of resin layer A containing colorant> Similarly to Example 1-1, a resin layer A (thickness: 250 μm) containing a colorant was produced using the following materials. PVC TK-1300 (Shin-Etsu Chemical Co., Ltd.) 100 parts by weight Plasticizer Dialkyl phthalate 90 parts by weight Filler: Calcium carbonate 10 parts by weight Flame retardant: Antimony trioxide 10 parts by mass Pigment Red 101 8 parts by mass

[0102] <Example 1-3: Production of laminate> A resin layer 1 containing plant-derived fibers and a resin layer A containing a colorant were prepared, and the base fabric (polyester fabric), the resin layer containing plant-derived fibers, and the resin layer A containing a colorant were bundled together in a roll (raw material). The following steps were carried out continuously by supplying the raw material.

[0103] An adhesive was applied to the surface of the base fabric, and a resin layer A containing a colorant was attached to it. Next, a resin layer 1 containing plant-derived fibers was further superimposed on the surface of the resin layer A containing the colorant, and two rolls were added to apply heat and pressure (the resin layer A containing the colorant and the resin layer 1 containing plant-derived fibers were bonded together by the action of heat and pressure without using an adhesive).

[0104] By the above operation, a laminate having, in this order, a resin layer 1 containing plant-derived fibers, a resin layer A containing a colorant, an adhesive layer, and a base fabric was obtained. A surface layer (polyurethane) was applied to the surface of the plant-derived fiber-containing resin layer 1 of the obtained laminate opposite the adhesive layer and dried at 80°C to 100°C. Furthermore, a surface treatment layer (polyurethane) was applied to the surface of the surface layer opposite the plant-derived fiber-containing resin layer 1 and dried to produce a laminate 1.

[0105] The thickness of the base fabric was 490 μm, the thickness of the resin layer 1 containing plant-derived fibers was 250 μm, the thickness of the resin layer A containing a colorant was 250 μm, the thickness of the surface layer was 20 μm, and the thickness of the surface treatment layer was 10 μm. A photograph of the laminate of Example 1 is shown in FIG.

[0106] <Example 2> A laminate was produced in the same manner as in Example 1, except that the resin layer A containing a colorant used in Example 1 was replaced with a resin layer B containing a colorant described below. A photograph of the laminate of Example 2 is shown in FIG. Similarly to Example 1-1, a resin layer B (thickness: 250 μm) containing a colorant was produced using the following materials. PVC TK-1300 (Shin-Etsu Chemical Co., Ltd.) 100 parts by weight Plasticizer Dialkyl phthalate 90 parts by weight Filler: Calcium carbonate 10 parts by weight Flame retardant: Antimony trioxide 10 parts by mass Carbon black 18 parts by weight

[0107] <Production Example 2-1: Production of plant-derived fibers> The plant-derived fibers produced in Production Example 1 were further treated with a φ0.5 mm screen pass using a cutter mill, and then passed twice through a mesh with 318 μm openings. The number average major axis of the obtained particles (number average major axis of the plant-derived fibers in the raw material) was 0.65 mm, and the number average minor axis (number average minor axis of the plant-derived fibers in the raw material) was 0.21 mm.

[0108] <Production Example 2-2: Production of pellets> Pellet 1 was produced using the following materials. PVC TK-1300 (Shin-Etsu Chemical Co., Ltd.) 100 parts by weight Plasticizer Dialkyl phthalate 100 parts by mass 200 parts by mass of plant-derived fiber produced in Production Example 2 (equivalent to 50% by mass) The plant-derived fibers were soaked in a plasticizer, stirred while adding polyvinyl chloride (PVC) powder, and melt-kneaded at 150°C using a twin-screw extruder (Bausano MD-30 / 19). Immediately after being discharged from the extruder, the mixture was cut and cooled to obtain polyvinyl chloride (PVC) pellets 1 containing plant-derived fibers.

[0109] <Production Examples 3 to 20: Production of plant-derived fibers and production of pellets> By changing the conditions, such as changing the screen opening of the cutter mill and gradually narrowing the clearance between the screen and the rotor, plant-derived fibers with different number-average major axis and number-average minor axis were obtained in the same manner as in Production Example 2. In the same manner as in Production Example 2, plant-derived fibers having different number average major diameters (number average major diameters of plant-derived fibers in the raw material) and number average minor diameters (number average major diameters of plant-derived fibers in the raw material) were pelletized. A list of pellets 2 to 19 is shown in Table 1.

[0110] [Table 1]

[0111] <Example 3> A laminate was produced in the same manner as in Example 1, except that the resin layer 1 containing plant-derived fibers used in Example 1 was replaced with a resin layer 2 containing plant-derived fibers described below. <Production of Resin Layer 2 Containing Plant-Derived Fibers> The temperature was set to 150°C and the two rolls were heated sufficiently until the temperature stabilized. The following materials were all added simultaneously to the two rolls and melt-kneading was started. After the addition, the mixture was melt-kneaded for 5 minutes at a set temperature of 150° C., and then rolled using a rolling machine to produce a resin layer (thickness 250 μm) containing plant-derived fibers. PVC TK-1300 (Shin-Etsu Chemical Co., Ltd.) 100 parts by weight Plasticizer Dialkyl phthalate 90 parts by weight Filler: Calcium carbonate 10 parts by weight Pellet 1 8.2 parts by weight (Plant-derived fiber content: equivalent to 1.96% by mass)

[0112] <Examples 4 to 19> Laminates were produced in the same manner as in Example 3, except that pellet 1 in Example 3 was replaced with pellets 2 to 17, respectively.

[0113] <Example 20> A laminate was produced in the same manner as in Example 3, except that 3.82 parts by mass of pellet 1 was used to adjust the plant-derived fiber content to equivalent to 0.94% by mass.

[0114] <Example 21> A laminate was produced in the same manner as in Example 3, except that 16.7 parts by mass of pellet 1 was used to adjust the plant-derived fiber content to equivalent to 3.85% by mass.

[0115] <Example 22> A laminate was produced in the same manner as in Example 2, except that 16.7 parts by mass of the plant-derived fiber produced in Production Example 2 was used to adjust the plant-derived fiber content to equivalent to 3.85% by mass.

[0116] <Example 23> A laminate was produced in the same manner as in Example 2, except that 49 parts by mass of the plant-derived fiber produced in Production Example 2 was used to adjust the plant-derived fiber content to equivalent to 9.98% by mass.

[0117] <Comparative Example 1> A laminate was manufactured in the same manner as in Example 1, except that wood chips (number average aspect ratio 1.1, number average major axis 0.22 mm, number average minor axis 0.20 mm) crushed using a jet mill were used instead of the plant-derived fibers used in Example 1.

[0118] <Comparative Example 2> A laminate was produced in the same manner as in Example 1, except that the resin layer A containing a colorant used in Example 1 was replaced with a transparent layer containing no colorant.

[0119] <Comparative Example 3> A laminate was manufactured in the same manner as in Example 1, except that instead of the plant-derived fibers used in Example 1, white plastic pieces (white PET film with a thickness of 0.09 mm cut to have a number-average aspect ratio of 7.0, a number-average major axis of 2.8 mm, and a number-average minor axis of 0.4 mm) were used.

[0120] <Comparative Example 4> Pellets 18 were produced in the same manner as in Example 3, except that instead of the plant-derived fibers used in Example 3, plant-derived fibers having a number-average major axis of 0.26 mm and a number-average minor axis of 0.03 mm were used, and a laminate was produced in the same manner as in Example 3.

[0121] <Comparative Example 5> Pellets 19 were produced in the same manner as in Example 3, except that instead of the plant-derived fibers used in Example 3, plant-derived fibers having a number-average major axis of 0.41 mm and a number-average minor axis of 0.03 mm were used, and a laminate was produced in the same manner as in Example 3.

[0122] In the images of the laminates of Examples 1 to 23 and Comparative Examples 1 to 5, the number average major axis and number average minor axis of the plant-derived fibers were measured by observing the produced laminates with an optical microscope. From a photograph of particle images taken at a magnification of 30x, the number average major axis (number average major axis of the plant-derived fibers in the image of the laminate) and the number average minor axis (number average minor axis of the plant-derived fibers in the image of the laminate) were measured for 300 particles by comparing with the scale lines, and the arithmetic mean values ​​of the number average major axis (number average major axis of the plant-derived fibers in the image of the laminate), the number average minor axis (number average minor axis of the plant-derived fibers in the image of the laminate), and the aspect ratio (aspect ratio of the plant-derived fibers in the image of the laminate) for the 300 particles were calculated. In this case, flake-like dust particles with a diameter of less than 0.10 mm and an aspect ratio of less than 1.5 were excluded from the measurement. The major axis is the length of a perpendicular line connecting two parallel lines that are tangent to the contour of the plant-derived fiber particle image and have the greatest distance between the two parallel lines. The minor axis is the length connecting two intersections between a straight line that is parallel to the two parallel lines and passes through the half point of the perpendicular line and the contour of the plant-derived fiber particle image. The results are shown in Table 2.

[0123] [Table 2]

[0124] For the laminates of Examples 1 to 23 and Comparative Examples 1 to 5, images of the resin layers containing the plant-derived fibers were obtained, and the occupied area ratio and envelopment degree of the plant-derived fibers were measured. The results are shown in Table 3. In addition, 40 office workers were selected as panelists and a preference-based sensory test was conducted on the following questions: (1) Could they recognize the presence of the added powder in the laminate? (2) Did they find the laminate beautiful? The results are shown in Table 4.

[0125] An image of the resin layer was obtained under the following (image capturing conditions), and the occupied area ratio and envelopment degree of the plant-derived fiber were measured under the following (image processing conditions).

[0126] (Image capture conditions) Digital image acquisition optical microscope: Keyence digital microscope Magnification: When measuring the exclusive area ratio, the magnification is 30 times. When measuring the envelopment, the magnification is 50 times.

[0127] (Image processing conditions) Processing image size: When measuring the occupied area ratio (magnification 30 times), it is 7.35 mm x 9.80 mm When measuring the envelopment (magnification 50x), it is 4.41mm x 5.88mm.

[0128] The calculations were performed using the image processing and analysis software WinROOF CLOUD manufactured by Mitani Shoji Co., Ltd., by carrying out the following processing.

[0129] <Sampling> 1. Monochrome imaging If the image was a color image, it was converted to a monochrome image. The monochrome imaging was performed by selecting monochrome imaging processing or RGB (red, green, blue) separation processing from the menu of the image analysis software WinROOF CLOUD manufactured by Mitani Shoji. 2. Noise Reduction Next, to remove fine noise that cannot be seen with the naked eye, the sample was processed in noise removal mode, with the conditions set to remove noise of 50 μm or less. 3. Density conversion (binarization) Next, the image density was adjusted by density conversion so that the outline of the part where the plant-derived fiber was present would be clear. (1) The part where the plant-derived fiber was present in the original image and (2) the outline of the image after density conversion (the part where the measurement target sample (plant-derived fiber) was present was displayed in white on the screen) were visually confirmed to be completely overlapped. If there was no complete overlap in the density conversion (for example, when the outline of (2) was larger than (1) or when the outline of (1) was larger than (2)), the input image density range for the density conversion was adjusted so that the part where the plant-derived fiber was present in the original image and the outline of the image after density conversion were completely overlapped. 4.Binarization Next, a binarization process was performed. The parts where the plant-derived fibers existed were binarized from the other parts, and it was confirmed by visual inspection that (1) the parts where the plant-derived fibers existed in the original image and (2) the contours of the binarized image (the parts where the measurement target sample (plant-derived fibers) existed were displayed in green on the screen) completely overlapped. In the automatic binarization mode, if there was no complete overlap (for example, if the contour of (2) was larger than (1) or if the contour of (1) was larger than (2)), the sampling brightness range was adjusted so that the parts where the plant-derived fibers existed in the original image and the contours of the binarized image completely overlapped.

[0130] <Exclusive area ratio> Particle measurements were performed from the measurement menu, and the data of the sampled particles was transferred to a spreadsheet software. The total area value of the sampled particles with a circular equivalent diameter of 50 μm or more was calculated by dividing it by the area of ​​the entire image. The average value of the exclusive area ratio calculated from 10 images was used.

[0131] <Envelope degree> Particle measurements were performed from the measurement menu, and the data of the sampled particles were transferred to a spreadsheet software. The envelopment ratio was calculated from the perimeter and the envelopment perimeter for each of the sampled particles with an equivalent circle diameter of 100 μm or more. The average value of the envelope ratio calculated from 10 images was used. At this time, the sampling number was drawn on the image. This operation made it possible to compare the data of each particle on the image with the data of each sampled particle by sampling number.

[0132] The envelope is defined by the following formula 1.

number

[0133] [Table 3]

[0134] [Table 4]

[0135] The results in Tables 2 to 4 show that a laminate having a resin layer containing a colorant and a resin layer containing plant-derived fibers, wherein in an image of the laminate, the number-average aspect ratio (long diameter / short diameter) of the plant-derived fibers is 1.5 to 15, the number-average long diameter of the plant-derived fibers is 0.2 mm to 3.0 mm, and the number-average short diameter of the plant-derived fibers is 0.03 mm to 1.0 mm, can provide a laminate in a highly designable manner that allows the presence of plant-derived materials to be felt.

[0136] Examples of aspects of the present invention include the following. <1> A laminate having a resin layer containing a colorant and a resin layer containing plant-derived fibers, In the image of the laminate, The plant-derived fibers have a number-average aspect ratio (long axis / short axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, The laminate is characterized in that the number average short diameter of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less. <2> The plant-derived fibers have a number-average aspect ratio (long axis / short axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, The number average minor axis of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less, The plant-derived fibers do not contain fibers having a diameter 2.5 times or more of the number average major axis. <1> 1. The laminate according to claim 1 . <3> The plant-derived fibers have a number-average aspect ratio (long axis / short axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, The number average minor axis of the plant-derived fibers is 0.1 mm or more and 1.0 mm or less, The plant-derived fibers do not contain fibers having a diameter 2.5 times or more of the number average major axis. <1> 1. The laminate according to claim 1 . <4> The plant-derived fibers have a number-average aspect ratio (long axis / short axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 2.0 mm or less, The number average minor axis of the plant-derived fibers is 0.1 mm or more and 0.7 mm or less, The plant-derived fibers do not contain fibers having a diameter 2.5 times or more of the number average major axis. <1> 1. The laminate according to claim 1 . <5> The number-average aspect ratio (major axis / minor axis) of the plant-derived fibers is 1.5 or more and 10 or less, The number average major axis of the plant-derived fibers is 0.3 mm or more and 1.0 mm or less, The number average minor axis of the plant-derived fibers is 0.1 mm or more and 0.3 mm or less, The plant-derived fibers do not contain fibers having a diameter 2.5 times or more of the number average major axis. <1> 1. The laminate according to claim 1 . <6> In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment ratio (envelopment circumference (C PERI) / circumference (PERI)) of 98.0% or more and 99.9 or less, The ratio of the number of particles having an envelopment degree of the plant-derived fiber of 90% or less is 5.0% or less. <1> 1. The laminate according to claim 1 . <7> In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment ratio (envelopment circumference (C PERI) / circumference (PERI)) of 98.0% or more and 99.9 or less, The ratio of the number of particles having an envelopment degree of the plant-derived fiber of 90% or less is 5.0% or less. <2> 1. The laminate according to claim 1 . <8> In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment ratio (envelopment circumference (C PERI) / circumference (PERI)) of 98.0% or more and 99.9 or less, The ratio of the number of particles having an envelopment degree of the plant-derived fiber of 90% or less is 5.0% or less. <3> 1. The laminate according to claim 1 . <9> In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment ratio (envelopment circumference (C PERI) / circumference (PERI)) of 98.0% or more and 99.9 or less, The ratio of the number of particles having an envelopment degree of the plant-derived fiber of 90% or less is 5.0% or less. <4> 1. The laminate according to claim 1 . <10> In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment ratio (envelopment circumference (C PERI) / circumference (PERI)) of 98.0% or more and 99.9 or less, The ratio of the number of particles having an envelopment degree of the plant-derived fiber of 90% or less is 5.0% or less. <5> 1. The laminate according to claim 1 . <11> The above <1> from <10> 1. A synthetic leather comprising the laminate according to any one of claims 1 to 9 and a base fabric. [Explanation of symbols]

[0137] 1. Laminate 2 Base fabric 3. Resin layer containing colorant 4. Resin layer containing plant-derived fibers 5 Surface treatment layer 6 Adhesive layer 7 Skin Layer 8A Separated plant-based fibres 8B Overlapping plant-based fibers

Claims

1. A laminate having a resin layer containing a colorant and a resin layer containing plant-derived fibers, In the image of the laminate, The plant-derived fibers have a number-average aspect ratio (major axis / minor axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, A laminate characterized in that the number average minor axis of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less.

2. The plant-derived fibers have a number-average aspect ratio (major axis / minor axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, The number average minor axis of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less, The laminate according to claim 1 , wherein the plant-derived fibers do not contain fibers having a major axis that is 2.5 times or more the number average major axis.

3. The plant-derived fibers have a number-average aspect ratio (major axis / minor axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 3.0 mm or less, The number average minor axis of the plant-derived fibers is 0.1 mm or more and 1.0 mm or less, The laminate according to claim 1 , wherein the plant-derived fibers do not contain fibers having a major axis that is 2.5 times or more the number average major axis.

4. The plant-derived fibers have a number-average aspect ratio (major axis / minor axis) of 1.5 or more and 15 or less, The number average major axis of the plant-derived fibers is 0.2 mm or more and 2.0 mm or less, The number average minor axis of the plant-derived fibers is 0.1 mm or more and 0.7 mm or less, The laminate according to claim 1 , wherein the plant-derived fibers do not contain fibers having a major axis that is 2.5 times or more the number average major axis.

5. The plant-derived fibers have a number-average aspect ratio (major axis / minor axis) of 1.5 or more and 10 or less, The number average major axis of the plant-derived fibers is 0.3 mm or more and 1.0 mm or less, The number average minor axis of the plant-derived fibers is 0.1 mm or more and 0.3 mm or less, The laminate according to claim 1 , wherein the plant-derived fibers do not contain fibers having a major axis that is 2.5 times or more the number average major axis.

6. In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment degree (envelopment perimeter (C PERI) / perimeter (PERI)) of 98.0% or more and 99.9 or less, 2. The laminate according to claim 1, wherein the ratio of particles having an envelopment degree of 90% or less of the plant-derived fibers is 5.0% or less.

7. In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment degree (envelopment perimeter (C PERI) / perimeter (PERI)) of 98.0% or more and 99.9 or less, The laminate according to claim 2 , wherein the ratio of the number of particles of the plant-derived fibers having an envelopment degree of 90% or less is 5.0% or less.

8. In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment degree (envelopment perimeter (C PERI) / perimeter (PERI)) of 98.0% or more and 99.9 or less, The laminate according to claim 3 , wherein the ratio of particles having an envelopment degree of 90% or less of the plant-derived fibers is 5.0% or less.

9. In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment degree (envelopment perimeter (C PERI) / perimeter (PERI)) of 98.0% or more and 99.9 or less, The laminate according to claim 4 , wherein the ratio of particles having an envelopment degree of 90% or less of the plant-derived fibers is 5.0% or less by number.

10. In the image of the resin layer containing the plant-derived fiber, the average value of the exclusive area ratio of the plant-derived fibers (100 × area of ​​the part where the plant-derived fibers are present / total area of ​​the part where the plant-derived fibers are present and other parts) is 3.0% or more and 8.0% or less, The plant-derived fiber has an average envelopment degree (envelopment perimeter (C PERI) / perimeter (PERI)) of 98.0% or more and 99.9 or less, The laminate according to claim 5 , wherein the ratio of particles having an envelopment degree of 90% or less of the plant-derived fibers is 5.0% or less.

11. 11. Synthetic leather comprising the laminate according to claim 1 and a base fabric.

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