Laminate and synthetic leather

Abstract

The utility model provides a laminated body and synthetic leather with the laminated body, wherein the existence of a plant-derived material can be practically felt in a high-designability manner. A laminate characterized by comprising: a resin layer containing a colorant; and a resin layer containing a plant-derived fiber, the number-average aspect ratio (major diameter / minor diameter) of the plant-derived fiber in an image of the laminate being 1.5-15, the number-average major diameter of the plant-derived fiber being 0.2-3.0 mm, and the number-average minor diameter of the plant-derived fiber being 0.03-1.0 mm, the number-average aspect ratio (major diameter / minor diameter) of the plant-derived fiber being 1.5-15, the number-average major diameter of the plant-derived fiber being 0.2-3.0 mm, and the number-average minor diameter of the plant-derived fiber being 0.03-1.0 mm.

Description

Technical Field

[0001] This utility model relates to laminates and synthetic leather. Background Technology

[0002] Currently, sustainable products have attracted attention, and research is underway to replace some petroleum-based products with plant-based materials. In the field of synthetic leather, various studies have also been conducted, as described below.

[0003] Patent document 1 discloses a method for manufacturing a formulation based on polyurethane and prickly pear cactus mucus used in the manufacture of a flexible coating for artificial skin.

[0004] Patent Document 2 discloses a composition for manufacturing a laminate made of plant material containing cellulose derived from apple waste, a method for manufacturing a laminate made of plant material containing cellulose derived from apple waste, and a laminate manufactured by the method.

[0005] Patent document 3 discloses an artificial leather having a PVC layer containing coconut shell powder modified vermiculite powder.

[0006] Patent document 4 discloses the combined use of coconut fiber and rubber-like adhesive for manufacturing vehicle seat cushions, mattresses, filters or packaging agents.

[0007] Products that utilize the technologies described in Patent Documents 1 and 2 are claimed to be sustainable, but the presence of plant-derived materials cannot be truly perceived by the user.

[0008] Even if the manufacturing methods disclosed in the aforementioned patent documents are used to disperse the plant-derived material in laminates or sheets in a manner that allows the presence of the plant-derived material to be felt, it is impossible to simultaneously achieve both design and performance, and it will not lead to an increase in the value of the product.

[0009] That is, there is currently no laminate or synthetic leather in which the presence of plant-derived materials can be truly felt in a highly designed manner.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Publication No. 2022-544741

[0013] Patent Document 2: U.S. Patent Application Publication No. 2021 / 0189642

[0014] Patent Document 3: Chinese Patent Application Publication No. 112721364

[0015] Patent Document 4: International Publication No. 97 / 005313 Utility Model Content

[0016] The problem to be solved by the utility model

[0017] The objective of this invention is to solve the aforementioned problems and achieve the following objective: to provide laminates and synthetic leathers in which the presence of plant-derived materials can be readily perceived in a highly design-oriented manner.

[0018] Methods for solving problems

[0019] To achieve the above objectives, the inventors of this invention have conducted repeated and in-depth research and discovered that a laminate and synthetic leather can be made to realistically convey the presence of plant-derived materials in a highly design-oriented manner using the following laminate: the laminate has a resin layer containing a colorant and a resin layer containing plant-derived fibers. In the image of the laminate, the number-average aspect ratio (major axis / minor 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, and the number-average minor axis of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less.

[0020] Here, "accompanying a highly designed approach" refers to the way that evokes aesthetic appeal, which means obtaining various forms of design variation through changes in color, dispersion, etc.

[0021] It should be noted that the number-average aspect ratio, number-average major diameter, and number-average minor diameter of the aforementioned plant-derived fibers were obtained by measuring images of laminates or synthetic leather.

[0022] This utility model was obtained by the inventor based on the above-mentioned technical concept, and the means to solve the above-mentioned problem are as follows. That is,

[0023] <1> A laminate comprising: a resin layer containing a colorant; and a resin layer containing plant-derived fibers.

[0024] In the images of the aforementioned laminates, the number-average aspect ratio of the plant-derived fibers is 1.5 or higher and 15 or lower, where aspect ratio is the ratio of the major axis to the minor axis.

[0025] The number-average major diameter of the aforementioned plant-derived fibers is 0.2 mm or more and 3.0 mm or less.

[0026] The number average short diameter of the above-mentioned plant-derived fibers is greater than 0.03 mm and less than 1.0 mm.

[0027] <2> A synthetic leather, characterized in that it has the above-mentioned... <1> The aforementioned laminate and base fabric.

[0028] Effects of the utility model

[0029] According to this invention, the various problems mentioned above can be solved and the above objectives can be achieved. It can provide laminates and synthetic leather in which the presence of plant-derived materials can be truly felt in a highly designed manner. Attached Figure Description

[0030] Figure 1 This is a schematic diagram showing the layered structure of a laminate.

[0031] Figure 2 This is a photograph of the laminate of Example 2.

[0032] Figure 3 It is an image being processed using image processing and analysis software (1).

[0033] Figure 4 It is an image being processed using image processing and analysis software (the second one).

[0034] Figure 5 It is an image being processed using image processing and analysis software (3).

[0035] Figure 6 This is a schematic diagram of a resin layer containing plant-derived fibers, used to illustrate the envelope.

[0036] Figure 7 This is a photograph of a resin layer containing plant-derived fibers, used to illustrate the envelope. Detailed Implementation

[0037] (laminated body)

[0038] The aforementioned laminate has a resin layer containing a colorant and a resin layer containing plant-derived fibers, and may further have other layers.

[0039] The aforementioned laminates can be used for various purposes, including as synthetic leather containing plant-derived fibers.

[0040] <Resin layer containing colorant>

[0041] The aforementioned resin layer containing colorant may include colorant, resin, plasticizer, filler, and other components.

[0042] The resin layer containing the colorant can be manufactured by melting and mixing the above components and then calendering them.

[0043] <<Coloring Agents>>

[0044] There are no particular restrictions on the aforementioned colorants; they can be selected appropriately according to the purpose. Examples include pigments and dyes. They can be used alone or in combination of two or more. Among these, pigments are preferred in terms of tinting strength and hiding power.

[0045] There are no particular restrictions on the pigments mentioned above; they can be selected appropriately according to the purpose, and can be inorganic or organic pigments. They can be used alone or in combination of two or more.

[0046] There are no particular restrictions on the inorganic pigments mentioned above, and they can be selected appropriately according to the purpose. Examples include carbon black, titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow.

[0047] There are no particular restrictions on the organic pigments mentioned above, and they can be selected appropriately according to the purpose. Examples include azo pigments, polycyclic pigments (such as phthalocyanine pigments, perylene pigments, violet ketone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindolinone pigments, isoindolineone pigments, quinolineone pigments, etc.), dye chelates (such as basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc.

[0048] The content of the colorant in the resin layer containing the colorant is not particularly limited and can be appropriately selected according to the purpose. From the perspective of manufacturing laminates and synthetic leather in which the presence of plant-derived materials can be truly felt in a highly designed manner, it is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less.

[0049] There are no particular restrictions on the color of the aforementioned colorant; it can be selected appropriately according to the purpose, with black, white, brown, yellow, red, blue, green, or purple being preferred.

[0050] Carbon black can be cited as an example of the aforementioned black coloring agents.

[0051] As an example of the aforementioned white colorant, Pigment White 6 can be cited.

[0052] As an example of the aforementioned brown coloring agent, Pigment Red 101 can be cited.

[0053] Examples of the aforementioned yellow colorants include Pigment Brown 24 or Pigment Yellow 181.

[0054] Examples of the aforementioned red colorants include Pigment Red 221 or Pigment Red 254.

[0055] As an example of the aforementioned blue colorant, Pigment Blue 15 can be cited.

[0056] As an example of the aforementioned green colorant, Pigment Green 7 can be cited.

[0057] As an example of the purple colorant mentioned above, Pigment Violet 23 can be cited.

[0058] The above reagents can also be mixed to produce gray or beige.

[0059] <<Resin>>

[0060] There are no particular limitations on the resins mentioned above; they can be selected appropriately according to the purpose. Examples 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, and acrylic-silicone resin. One type can be used alone, or two or more can be used in combination.

[0061] Among these, polyvinyl chloride (PVC) (vinyl chloride resin) is preferred due to its durability and ease of various decorative processing.

[0062] The aforementioned polyvinyl chloride (PVC) can be manufactured through the polymerization reaction of vinyl chloride. Commercially available polyvinyl chloride (PVC) can be used.

[0063] There are no particular limitations on the above polymerization reactions, and they can be appropriately selected according to the purpose. Examples include suspension polymerization and emulsion polymerization.

[0064] There are no particular limitations on the properties of the polyvinyl chloride (PVC) mentioned above, and they can be appropriately selected according to the purpose. Polyvinyl chloride (PVC) with an average degree of polymerization of 800 or more and 2500 or less is preferred.

[0065] The polyvinyl chloride (PVC) mentioned above can be modified polyvinyl chloride (PVC).

[0066] Commercially available polyvinyl chloride (PVC) products include, for example, the TE series and TH series manufactured by Taiyo PVC Co., Ltd., the TK series manufactured by Shin-Etsu Chemical Co., Ltd., and the PSH series and PSM series manufactured by Kaneka Co., Ltd.

[0067] Plasticizers

[0068] There are no particular restrictions on the plasticizers mentioned above, and they can be selected appropriately according to the purpose. Examples include phthalates such as dialkyl phthalates, adipates, and trimellites. They can be used alone or in combination of two or more.

[0069] The plasticizer in the resin layer containing the colorant is not particularly limited in content relative to the resin, and can be appropriately selected according to the purpose. From the perspective of manufacturing synthetic leather with strength and durability, it is preferably 50% by mass or more and 150% by mass or less, more preferably 80% by mass or more and 120% by mass or less.

[0070] <<Filling>>

[0071] There are no particular restrictions on the fillers mentioned above, and they can be selected appropriately according to the purpose. Examples include alumina, titanium dioxide, zinc oxide, cerium dioxide, calcium carbonate, silicon dioxide, talc, magnesium hydroxide, mica, barium sulfate, silicic acid, ammonium polyphosphate, aluminum dialkylphosphinate, melamine polyphosphate, carbon black, carbon nanotubes, and carbon fibers. One of them can be used alone, or two or more can be used in combination.

[0072] The filler in the resin layer containing the colorant is not particularly limited in content relative to the resin, and can be appropriately selected according to the purpose. From the perspective of manufacturing synthetic leather with strength and durability, it is preferably 3% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less.

[0073] <<Other Ingredients>>

[0074] There are no particular restrictions on the other ingredients mentioned above, and they can be selected appropriately according to the purpose; for example, stabilizers can be mentioned.

[0075] There is no particular limitation on the thickness of the resin layer containing the colorant, which can be appropriately selected according to the purpose. From the perspective of strength and durability, it is preferred to be 20 μm or more and 1000 μm or less, more preferably 100 μm or more and 500 μm or less, further preferably 150 μm or more and 350 μm or less, and particularly preferably 200 μm or more and 300 μm or less.

[0076] <Resin layer containing plant-derived fibers>

[0077] The resin layer containing plant-derived fibers may include plant-derived fibers, resin, plasticizer, filler, and other components.

[0078] The resin layer containing plant-derived fibers may contain colorants.

[0079] The content of the aforementioned colorant is 0% by mass or more and 5% by mass or less, preferably 0% by mass or more and 3% by mass or less.

[0080] By also coloring the resin layer containing plant-derived fibers, the plant-derived fibers are not unnecessarily overly prominent, potentially resulting in a more natural impression. Furthermore, it also increases the coloring power and masking power of the laminate as a whole.

[0081] The aforementioned colorant is as described in the above-mentioned <Resin Layer Containing Colorant>.

[0082] The resin layer containing plant-derived fibers can be manufactured by melting and blending the above components and then calendering them.

[0083] Among these, from the perspective of preventing the reabsorption of moisture and deterioration during transportation, it is preferable to dry the above-mentioned plant-derived fibers, and immediately after drying, melt and mix the above-mentioned plant-derived fibers and the above-mentioned resin and other material powders, and then granulate them.

[0084] Regarding the above-mentioned granulation, the material powder is mixed and then processed using a twin-screw extruder.

[0085] There is no particular limitation on the proportion of the above-mentioned plant-derived fibers in the granules, which can be appropriately selected according to the purpose, preferably 30% by mass or more and 60% by mass.

[0086] During granule preparation, plasticizers, stabilizers, lubricants, and gelation accelerators can be added as needed. These gelation accelerators help to form a pseudo-crosslinked state with resin molecules, imparting melt elasticity. Acrylic polymers are used as gelation accelerators for polyvinyl chloride (PVC).

[0087] The resin, plasticizer, filler and other components are as described in the above <Resin Layer Containing Colorant>.

[0088] <<Plant-derived Fibers>>

[0089] There are no particular restrictions on the aforementioned plant-derived fibers. Fibers made from plant materials can be appropriately selected according to the purpose. They can be used alone or in combination of two or more types.

[0090] Although not necessarily an academic classification, plants are broadly divided into woody and herbaceous groups.

[0091] Woody plant group: The plant group that grows by accumulating cells in the xylem year by year.

[0092] Herbaceous group: Plants that lack xylem and wither within one to several years.

[0093] Any fibrous material that meets the range of aspect ratio, major diameter, and minor diameter of this utility model can be used, whether it is woody or herbaceous. For reasons such as ease of procurement, ease of processing, non-edible parts, and difficulty in using it for fuel or other purposes, the fibrous materials of leaves, stems, and petals of herbaceous plants, and leaves, fruits, and petals of woody plants other than woody parts are preferred.

[0094] In particular, the fibers of leaves, stems, and petals of herbaceous plants, and leaves, fruits, and petals of woody plants (excluding wood), are not only easy to crush, but also have a consistent fiber direction. Therefore, the long and short diameters of the fibers can be freely adjusted according to the processing conditions, making it preferable in terms of obtaining fibrous materials that meet the aspect ratio, long diameter, and short diameter range of this utility model.

[0095] Specifically, herbaceous plants include, for example, the leaves of grasses such as rice, wheat, barley, and rye; the husks of threshed rice; the leaves, husks, and tassels (pistil) of corn; the petals of ornamental plants; and perennial evergreen herbs such as the genera *Erianthus* and *Miscanthus*.

[0096] The fibrous material of woody plants, other than wood, includes leaves, fruits, petals, etc. Examples include pine needles, cherry blossoms or cherry leaves, fruit peels (coffee bean shells, apple, mandarin orange, banana peels, peanut shells and thin skins, walnut shells), bamboo leaves, bamboo leaves, and coconut fruits.

[0097] Among these, the fiber derived from coconuts, and more preferably from the fruit of the coconut, is preferred. This fiber is often discarded in large quantities because it is difficult to use for other purposes, and it is said to produce greenhouse gases such as methane when it decomposes.

[0098] The coconut fiber mentioned above comes from plants belonging to the palm family.

[0099] There are no particular restrictions on the plants belonging to the palm family mentioned above; they can be selected appropriately according to the purpose. For example, plants belonging to the subfamily Palmoideae, subfamily Palmoideae, subfamily Palmoideae, subfamily Lepidophyticae, and subfamily Pachyphyta can be cited.

[0100] Among these, plants belonging to the subfamily Palmoideae are preferred from the perspective of creating lamellae that allow one to truly feel the presence of plant-derived materials.

[0101] There are no particular restrictions on the species belonging to the subfamily Palmocoideae. Plants can be selected appropriately according to their purpose. For example, plants belonging to the Arecaceae, Cocosae, Cocosaceae, Lowland Palmae, South American Palmae, Fiber Palmae, Poison Palmae, Phoenix Tail Palmae, Convex Palmae, Window Palmae, Royal Palmae, and Hard-seed Palmae families can be cited.

[0102] Among these, plants belonging to the coconut family are preferred, based on the goal of creating laminates in which the presence of plant-derived materials can be truly felt.

[0103] There are no particular restrictions on the plants belonging to the coconut family mentioned above. They can be selected appropriately according to the purpose. For example, coconut palms, oil palms, and peach palms can be cited.

[0104] Among these, coconut palms are preferred from the perspective of creating laminates in which the presence of plant-derived materials can be truly felt.

[0105] There are no particular restrictions on the parts of the plant that belong to the palm family. They can be selected appropriately according to the purpose. From the perspective of creating a laminate in which the presence of plant-derived material can be truly felt, the fruit is preferred, and the outer skin of the fruit (coconut fiber) is even more preferred.

[0106] There are no particular restrictions on the manufacturing methods of the aforementioned plant-derived fibers, and appropriate methods can be selected according to the purpose. For example, the following methods can be cited: using a cutting and grinding machine to process the outer skin of the fruit of plants belonging to the palm family (coconut fiber). The sieve (with a mesh size) crushes fibrous raw materials (long fibers) that are tens of centimeters in length, then passes them through a sieve with the required mesh size, and then dries them.

[0107] There is no particular limitation on the drying temperature after the above-mentioned pulverization, and it can be appropriately selected according to the purpose. From the perspective of preventing the deterioration of the above-mentioned plant-derived fibers, it is preferably 50°C or higher and 100°C or lower, more preferably 50°C or higher and 80°C or lower, and particularly preferably 50°C or higher and 70°C or lower.

[0108] There is no particular limitation on the drying time after the above-mentioned pulverization, and it can be appropriately selected according to the purpose. From the perspective of manufacturing a laminate that does not retain moisture, it is preferably 2 hours or more and 100 hours or less, more preferably 10 hours or more and 80 hours or less.

[0109] The water content of the aforementioned plant-derived fiber is preferably 2.0% by mass or less, and particularly preferably 1.5% by mass or less.

[0110] The water content of the above-mentioned plant-derived fibers was measured using an infrared moisture meter FD-600 (manufactured by KETT Scientific Research Institute Co., Ltd.).

[0111] The water content of the plant-derived fibers can be reduced by appropriately adjusting the drying conditions and drying time. However, plant-derived fibers reabsorb water very quickly even at room temperature. Therefore, it is necessary to control the reabsorption of water after drying and before it is put into the melt-blending process.

[0112] The number-average aspect ratio (major axis / minor axis) of the plant-derived fibers in the image of the aforementioned laminate is not particularly limited as long as it is 1.5 or more and 15 or less. It can be appropriately selected according to the purpose. From the perspective of producing a laminate in which the presence of plant-derived materials is obvious and aesthetically pleasing, as well as synthetic leather, it is preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, further preferably 3 or more and 8 or less, and particularly preferably 3 or more and 5 or less.

[0113] If the number-average aspect ratio (major axis / minor axis) of the aforementioned plant-derived fibers exceeds 15, they will overlap and entangle, creating a foreign body sensation.

[0114] If the number-average aspect ratio (major diameter / minor diameter) of the aforementioned plant-derived fibers is less than 1.5, the natural fiber material will feel weaker and produce a foreign body sensation.

[0115] The number average major diameter of the plant-derived fibers in the image of the aforementioned laminate is not particularly limited as long as it is 0.2 mm or more and 3.0 mm or less. It can be appropriately selected according to the purpose. From the perspective of producing a laminate in which the presence of plant-derived materials is obvious and aesthetically pleasing, as well as synthetic leather, it is preferred to be 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.

[0116] In the image of the aforementioned laminate, the plant-derived fibers preferably do not contain fibers whose major diameter is more than 2.5 times the number average major diameter. If such fibers are included, even if the average length meets the aforementioned range, the aesthetic impression will be compromised.

[0117] In the images of the aforementioned laminates, the number-average minor diameter (thickness) of the plant-derived fibers 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 breakage along the fiber direction when pulverized. Therefore, in order to obtain plant-derived fibers in the aforementioned long diameter range, it is preferable to prepare them with an average minor diameter (thickness) of 1.0 mm or less. From the perspective of manufacturing laminates and synthetic leather in which the presence of plant-derived materials can be truly felt in a highly design-oriented manner, a number-average minor diameter (thickness) of 0.05 mm or more and 0.7 mm or less is preferred, more preferably 0.1 mm or more and 0.3 mm or less is preferred, and particularly preferably 0.1 mm or more and 0.2 mm or less is preferred.

[0118] In the image of the aforementioned laminate, the combination of the average aspect ratio, average major diameter, and average minor diameter of the plant-derived fibers is preferred from the perspective of creating a laminate with a clear presence of plant-derived materials and aesthetic appeal, as well as synthetic leather. The preferred combination is an average major diameter of 0.2 mm or more and 2.0 mm or less, an average minor diameter of 0.05 mm or more and 0.7 mm or less, and an average aspect ratio of 1.5 or more and 15 or less. The preferred combination is an average major diameter of 0.3 mm or more and 1.0 mm or less, an average minor diameter of 0.1 mm or more and 0.3 mm or less, and an average aspect ratio of 2 or more and 10 or less. The most desirable combination is an average major diameter of 0.4 mm or more and 0.8 mm or less, an average minor diameter of 0.1 mm or more and 0.3 mm or less, and an average aspect ratio of 2 or more and 8 or less.

[0119] Regarding the number-average major and minor axes of the plant-derived fibers in the raw materials, the plant-derived fibers were pulverized and passed through a sieve with a mesh size of the required range. The resulting sample was dried and then confirmed using an optical microscope.

[0120] The number-average major axis and number-average minor axis of the plant-derived fibers in the above-mentioned laminate images were determined by observing the prepared laminate using an optical microscope.

[0121] All measurements were taken using photographs of particle images taken at 30x magnification. For 300 particles, the major and minor axes were measured by comparing them with scale lines, and the arithmetic mean of the major and minor axes and aspect ratio of the 300 particles was calculated. At this point, flaky dust particles with a diameter less than 0.10 mm and an aspect ratio less than 1.5 were excluded from the measurement.

[0122] The aforementioned major axis refers to the length of the perpendicular line connecting the two parallel lines when the distance between the two parallel lines is the largest among the two parallel lines that connect to the outline of the aforementioned plant-derived fiber particle image.

[0123] The aforementioned minor axis refers to the length between the two points where the following straight line intersects the outline of the aforementioned plant-derived fiber particle image, the straight line being a line parallel to the aforementioned two parallel lines that passes through a point halfway along the aforementioned perpendicular line.

[0124] As a method for adjusting the number-average major diameter and number-average minor diameter of the aforementioned plant-derived fibers, if a micro-pulverizer with a grading mechanism (usually a jet mill or similar pulverizer with a target size of less than 10 μm) is used to reduce the particle size, the number of processing times in the pulverizer increases, thus tending to have an aspect ratio close to 1. However, the plant-derived fibers of the present invention with an aspect ratio of 1.5 or higher and 15 or lower, a number-average major diameter of 0.2 mm or higher and 3.0 mm or lower, and a number-average minor diameter of 0.03 mm or higher and 1.0 mm or lower can be produced without using a micro-pulverizer such as a jet mill by adjusting the sieve size of a cutting and grinding machine and the gap between the sieve and the rotor.

[0125] Since fibrous materials easily pass through the sieve openings along their long axis, a coarsely ground material with a large long axis can be obtained by widening the gap between the sieve openings and the rotor. Alternatively, a coarsely ground material with a large long axis can also be obtained by using a sieve with a larger mesh size.

[0126] Due to the nature of plant-derived fibers, they are prone to breakage along the fiber direction during pulverization. Therefore, by increasing the number of processing cycles using a cutting and grinding machine, the minor diameter (coarseness) tends to decrease.

[0127] Therefore, in order to obtain fibrous particles with the desired long axis, whether by using a single coarse crushing process or by processing in two stages to progressively narrow the gap between the sieve and the rotor, the latter case can reduce the short axis (coarseness) even for the same long axis.

[0128] Through this multi-stage process of gradually changing the gap between the sieve aperture and the rotor, fibrous particles with various combinations of long and short diameters (coarseness) can be obtained.

[0129] A grading process can be set up, in which the coarsely crushed material is classified using a classifier such as an air classifier or an elbow jet classifier to remove fine dust and to distinguish them according to size. The grading process can be set between multiple crushing processes.

[0130] Since plant-derived fibers are prone to breakage along the fiber direction, it is preferable to prepare them with an average short diameter (thickness) 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.

[0131] Furthermore, by passing the pulverized or graded fibrous particles through a sieve, coarse particles can be removed. Since fibrous materials readily pass through the sieve openings along their long axis, they may contain large particles with a large long axis. However, by adjusting the frequency and amplitude of the vibration during passage through the sieve, these large particles can be removed. In this case, multiple sieves with different mesh sizes can also be used.

[0132] As described above, fibrous particles with the desired aspect ratio, major axis, and minor axis can be obtained. Furthermore, fibers with a major axis greater than 2.5 times the number average major axis can also be removed.

[0133] The content of the plant-derived fibers in the resin layer containing plant-derived fibers is not particularly limited and can be appropriately selected according to the purpose. The preferred content is 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, based on the premise that the presence of plant-derived fibers with an average aspect ratio of 1.5 or more and 15 or less, an average major diameter of 0.2 mm or more and 3.0 mm or less, and an average minor diameter of 0.03 mm or more and 1.0 mm or less can create an aesthetically pleasing and natural impression without creating a messy or chaotic impression.

[0134] In the above-mentioned image of the resin layer containing plant-derived fibers, the average value of the area ratio of the plant-derived fibers (area of ​​the portion containing plant-derived fibers / total area of ​​the portion containing plant-derived fibers and other portions × 100%) is not particularly limited and can be appropriately selected according to the purpose. It is preferred to be 3.0% or more and 8.0% or less, more preferably 4.0% or more and 6.0% or less, from the perspective of being able to evoke aesthetics and give a natural impression.

[0135] In the above-mentioned image containing a resin layer of plant-derived fibers, the lower limit of the average value of the envelopment degree of the plant-derived fibers (an indicator of the cohesion state of the plant-derived fibers: (envelopment perimeter (C PERI) (Convex Perimeter: the perimeter when the protruding parts of the pattern are connected) / (perimeter (PERI) (Perimeter: the perimeter of the pattern)) is not particularly limited, and can be appropriately selected according to the purpose. It is preferred to be 98.0% or more, and more preferably 99.0% or more, from the perspective of being able to evoke an aesthetic feeling and give a natural impression.

[0136] In the above-mentioned image containing a resin layer of plant-derived fibers, there is no particular upper limit to the average value of the envelopment degree of the plant-derived fibers (an indicator of the cohesion state of the plant-derived fibers: (envelopment perimeter (C PERI) (Convex Perimeter: perimeter when the protruding parts of the pattern are connected) / perimeter (PERI) (Perimeter: perimeter of the pattern)). It can be appropriately selected according to the purpose, and preferably 99.9% or less from the perspective of eliciting aesthetics and giving a natural impression.

[0137] Among these, from the perspective of being able to evoke a sense of beauty and give an impression of nature, it is preferred to be 98.0% or more and 99.9% or less.

[0138] In the above-mentioned image of the resin layer containing plant-derived fibers, the proportion of particles with an average envelopment degree of 90% or less of the plant-derived fibers is preferably 5.0% or less, more preferably less than 5.0%, and even more preferably does not contain such particles.

[0139] The images of the resin layer were obtained under the following (image capture conditions), and the area ratio and envelopment of the plant-derived fibers were measured under the following (image processing conditions).

[0140] (Image shooting conditions)

[0141] Digital Image Acquisition Optical Microscope: Digital Microscopes Manufactured by Keyence

[0142] Shooting magnification:

[0143] When measuring the area ratio, the magnification is 30 times.

[0144] When measuring envelope, at a magnification of 50x.

[0145] (Image processing conditions)

[0146] Processing image size:

[0147] When measuring the area ratio (magnification 30x), the dimensions are 7.35mm × 9.80mm.

[0148] When measuring the envelope (at 50x magnification), the image size is 4.41mm × 5.88mm.

[0149] The following calculations were performed using WinROOF CLOUD, an image analysis software manufactured by Mitani Corporation, for image processing and analysis.

[0150] <Sampling>

[0151] 1. Monochrome Image Conversion

[0152] If the image is in color, convert it to monochrome.

[0153] From the menu of the WinROOF CLOUD image analysis software manufactured by Mitani Corporation, select monochrome image processing or RGB (red, green, blue) separation processing to perform monochrome image processing.

[0154] 2. Noise Removal

[0155] Next, in order to remove minute noise invisible to the naked eye, processing is performed using a noise removal mode. At this time, processing is performed under the condition of removing noise smaller than 50 μm.

[0156] 3. Concentration Conversion (Binarization)

[0157] Next, the image density is adjusted by density conversion in such a way that the outline of the portion containing plant-derived fibers becomes clear. Visually confirm that (1) the portion of the original image containing plant-derived fibers completely overlaps with the outline of (2) the density-converted image (where the portion containing the measured sample (plant-derived fibers) is shown in white). If there is no complete overlap during density conversion (e.g., if the outline of (2) is larger than that of (1), or if the outline of (1) is larger than that of (2), adjust the range of the input image density for density conversion in such a way that the outline of the original image containing plant-derived fibers completely overlaps with that of the density-converted image.

[0158] 4. Binarization

[0159] Next, binarization processing is performed. The portion containing plant-derived fibers is binarized with other portions. It is visually confirmed that (1) the portion containing plant-derived fibers in the original image completely overlaps with the outline of (2) the binarized image (the portion containing the measured sample (plant-derived fibers) is represented in green). In cases where there is no complete overlap in the automatic binarization mode (e.g., when the outline of (2) is larger than that of (1), or when the outline of (1) is larger than that of (2), the brightness range of the sample is adjusted so that the outline of the portion containing plant-derived fibers in the original image completely overlaps with the outline of the binarized image.

[0160] Figure 3 The image shown is the original image magnified 50 times during processing using image processing and analysis software.

[0161] Figure 4 The image shown is processed using image processing and analysis software, including 1. monochrome image conversion, 2. noise removal, and 3. density conversion (binarization).

[0162] Figure 5The image shown is the binarized image from step 4 of the image processing analysis software.

[0163] <Area Ratio>

[0164] The particle measurements were performed using the measurement menu of WinROOF CLOUD, an image analysis software manufactured by Mitani Corporation. The sampled particle data was then transferred to the table calculation software to calculate the total area of ​​particles with an equivalent circle diameter of 50μm or more. This area was then divided by the overall area of ​​the image to perform the calculation.

[0165] Use the average of the area ratios calculated from 10 images.

[0166] <Envelope>

[0167] The particle measurements were performed using the measurement menu of WinROOF CLOUD, the image analysis software manufactured by Mitani Corporation. The sampled particle data was then transferred to the table calculation software. For each sampled particle with an equivalent circle diameter of 100μm or more, the envelope was calculated based on the perimeter and envelope perimeter.

[0168] The average of the envelope calculated from 10 images is used.

[0169] At this point, the sampling number is plotted on the image.

[0170] This operation allows for the comparison of data between each particle in the image and the sampled particles using the sampling number.

[0171] The envelope is defined by Equation 1 below.

[0172] [Number 1]

[0173] Envelope = Envelope perimeter (C PERI) / Perimeter (PERI) (Equation 1)

[0174] Here, the denominator and numerator of Equation 1 will be explained.

[0175] Perimeter (PERI)

[0176] The perimeter (PERI) mentioned above is the perimeter of the graphic.

[0177] <Envelope Perimeter (C PERI)>

[0178] The envelope perimeter (C PERI) mentioned above is the perimeter (ConvexPerimeter) when the convex parts of the graphic are connected.

[0179] Regarding the envelope, when all particles are in a separated state, the envelope is 100% (maximum value); if the number of overlapping particles increases, the envelope becomes a smaller value.

[0180] For example, in Figure 6 In the particle group shown, when the particles are separated (the two particles on the left), the perimeter is the same as the envelope perimeter, so the envelope degree of each particle is 100%; when the particles are overlapped (the two particles on the right overlap), the envelope perimeter is the length of the dashed line, which is a value smaller than the perimeter, so the envelope degree is a value lower than 100%.

[0181] Figure 7 In the particle with an equivalent circle diameter of 401 μm shown, the two fibers are in contact, and the envelope is 69.5%.

[0182] Thus, if two particles come into contact or even overlap, the perimeter increases compared to the envelope perimeter, and the envelope value decreases. Such particles with low envelope detract from the aesthetic appeal and give the non-natural fibrous material a foreign, unnatural feel.

[0183] In order to make the envelope close to 100, that is, close to a non-overlapping state, when diluting the granules containing plant-derived fibers in the resin melt, it is preferable to dilute them uniformly. As such granules, it is preferable to use granules that have been plasticized by containing plasticizer in the range of 50 parts by weight or more and 200 parts by weight relative to 100 parts by weight of resin.

[0184] Typically, when producing granular masterbatches for the purpose of dispersing colorants in a rigid resin, the use of plasticizers to enable strong shear is not performed. However, in order to obtain the following laminate, it is preferable to prepare relatively soft plasticized granules by including plasticizers during granulation, thereby uniformly diluting them in the resin melt. The laminate is the present invention's laminate containing plant-derived fibers, in which the average value of the inclusion degree (%) of the plant-derived fibers in the above-mentioned resin layer containing plant-derived fibers is 98.0% or more and 99.9% or less, and the proportion of particles with an inclusion degree of 90% or less is 5.0% or less.

[0185] There is no particular limitation on the thickness of the resin layer containing plant-derived fibers, which can be appropriately selected according to the purpose. From the perspective of strength and durability, it is preferred to be 20 μm or more and 1000 μm or less, more preferably 100 μm or more and 500 μm or less, further preferably 150 μm or more and 400 μm or less, and particularly preferably 200 μm or more and 300 μm or less.

[0186] <Other Layers>

[0187] There are no particular restrictions on the other layers mentioned above, and they can be selected appropriately according to the purpose. Examples include base fabric, adhesive layer, surface treatment layer, and outer skin layer (also known as "surface layer").

[0188] <<Kib>>

[0189] There are no particular restrictions on the base fabrics mentioned above; they can be selected appropriately according to the purpose. For example, non-woven fabrics, woven fabrics, and braided fabrics can be cited.

[0190] There are no particular restrictions on the materials used as the base fabric; they can be selected appropriately according to the purpose. Examples include polyester, polyethylene, nylon, acrylic resin, polyurethane, ester acetate, rayon, polylactic acid, cotton, linen, silk, wool, and fiberglass. One type can be used alone, or two or more can be used in combination.

[0191] Of these, polyester is preferred.

[0192] The base fabric can be composed of a fabric (fiber aggregate) formed by shaping fibers into nonwoven, woven, or braided forms. Among these, woven or braided fabrics are preferred for their low cost. In addition, not only the above-mentioned materials can be used as the base fabric, but also sheets with a porous structure obtained by impregnating the fabric with synthetic resins such as polyurethane resins.

[0193] The base fabric serves to support and reinforce the layers formed on its surface. By incorporating the base fabric, the strength and shape stability of the laminated sheet can be improved. The base fabric can be bonded to the layers formed on its surface using adhesives.

[0194] There are no particular limitations on the thickness of the base fabric, which can be appropriately selected according to the purpose. Preferably, it is 300 μm or more and 1,300 μm or less, and most preferably, it is 400 μm or more and 700 μm or less.

[0195] In the above-mentioned laminate, the resin layer containing the colorant may be provided on the base fabric, and the resin layer containing plant-derived fibers may be provided on the side of the resin layer containing the colorant opposite to the base fabric side.

[0196] The base fabric and the resin layer containing the colorant can be directly bonded together, or the adhesive layer can be provided between the base fabric and the resin layer containing the colorant.

[0197] <<Adhesive Layer>>

[0198] The adhesive layer can be disposed between the base fabric and the resin layer containing the colorant.

[0199] The adhesive layer described above may contain an adhesive.

[0200] The adhesive layer described above can bond the base fabric to the resin layer containing the colorant.

[0201] There is no particular limitation on the thickness of the adhesive layer mentioned above, and it can be appropriately selected according to the purpose, preferably 80 μm or less.

[0202] <<Surface Treatment Layer>>

[0203] In the above-described laminate, the surface treatment layer may be provided on the side opposite to the base fabric side of the resin layer containing plant-derived fibers.

[0204] The surface treatment layer and the resin layer containing plant-derived fibers can be directly bonded together, or the outer skin layer can be provided between the base fabric and the resin layer containing plant-derived fibers.

[0205] The aforementioned surface treatment layer may contain polyurethane.

[0206] There is no particular limitation on the content of the polyurethane in the above-mentioned surface treatment layer, and it can be selected appropriately according to the purpose.

[0207] There is no particular limitation on the thickness of the surface treatment layer described above, and it can be appropriately selected according to the purpose. Preferably, it is 5 μm or more and 20 μm or less, and more preferably 10 μm or more and 20 μm or less.

[0208] <<Outer cortex>>

[0209] The aforementioned outer skin layer can be disposed between the aforementioned resin layer containing plant-derived fibers and the aforementioned surface treatment layer.

[0210] The outer skin layer may contain polyvinyl chloride or polyurethane.

[0211] There are no particular restrictions on the content of the aforementioned polyvinyl chloride or polyurethane in the outer skin layer, and it can be selected appropriately according to the purpose.

[0212] There is no particular limitation on the thickness of the outer skin layer, which can be appropriately selected according to the purpose, preferably 15 μm or more and 30 μm or less.

[0213] Figure 1 This is a schematic diagram illustrating the layer structure of a laminate 1 according to one embodiment. The laminate 1 may sequentially have a base fabric 2, an adhesive layer 6, a resin layer 3 containing a colorant, a resin layer 4 containing plant-derived fibers, an outer skin layer 7, and a surface treatment layer 5.

[0214] (Manufacturing method of laminated materials)

[0215] There are no particular restrictions on the manufacturing method of the above-mentioned laminated body, and it can be appropriately selected according to the purpose. For example, rolling and casting methods can be used.

[0216] There are no particular limitations on the above calendering method, and it can be appropriately selected according to the purpose. For example, the following methods can be used: plant-derived fibers, plasticizers, fillers, etc. are added to the resin obtained by suspension polymerization (suspension polymerization), and the resulting resin composite is calendered using calendering rollers to laminate the resulting resin layer with the base fabric.

[0217] Specifically, the following methods can be used: an adhesive is applied to one surface of the resin layer containing plant-derived fibers, and then bonded to a base fabric to obtain a composite having a resin layer containing plant-derived fibers, an adhesive layer, and a base fabric in sequence; a surface layer is applied to the surface of the resin layer containing plant-derived fibers on the side opposite to the adhesive layer of the obtained composite, and then dried; further, a surface treatment layer is applied to the surface of the surface layer on the side opposite to the resin layer containing plant-derived fibers, and then dried.

[0218] In the case of the laminate of this invention, the following manufacturing method is preferred.

[0219] (1) Prepare the above-mentioned resin layer containing colorant and the above-mentioned resin layer containing plant-derived fiber in advance.

[0220] It should be noted that when adjusting the resin layer containing plant-derived fibers using granules containing material powder, the granules and resin can be melt-blended together in the early stage of this process and diluted to a desired concentration of the composition containing resin and plant-derived fibers.

[0221] (2) Apply the adhesive to the base fabric.

[0222] (3) The base fabric coated with the above adhesive is bonded to the above resin layer containing the colorant, and further overlapped with the above resin layer containing plant-derived fibers, and then bonded by heating with calendering rollers in this state.

[0223] There are no particular limitations on the above casting method, and it can be selected appropriately according to the purpose. For example, the following methods can be used: plant-derived fibers, plasticizers, fillers, etc. are added to the resin obtained by emulsion polymerization (paste polymerization), the resulting resin paste sol is coated on release paper, etc., and heated to gel, so that the resulting resin layer and the layer containing colorant are laminated with the base fabric.

[0224] Even if casting is performed, the laminate of this invention can be produced by sequentially layering it with release paper, etc., but for efficient mass production, the specific calendering method described above is preferred.

[0225] (Synthetic leather)

[0226] The synthetic leather of this invention comprises the laminate of this invention and a base fabric.

[0227] The above-mentioned laminate (the laminate of this utility model) is as described in the above (Laminated Material).

[0228] The aforementioned base fabric is as described in the <<Base Fabric>> of <Other Layers> of the above (Laminated Body).

[0229] (Sheets for vehicles)

[0230] The vehicle sheet of this invention is formed by the laminate of this invention. When the laminate of this invention performs at the same level as the benchmark vehicle sheet (a benchmark vehicle sheet having a polyvinyl chloride (PVC) layer without plant-derived fibers) in the bending resistance test, it can be appropriately used as a vehicle sheet.

[0231] The above-mentioned laminate (the laminate of this utility model) is as described in the above (Laminated Material).

[0232] Example

[0233] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments in any way.

[0234] <Manufacturing Example 1: Manufacturing of Plant-Derived Fibers>

[0235] Coconut fiber raw materials (long fibers) several tens of centimeters in length are cut and ground using a cutting and grinding machine. The material is processed by a screenpass method, which further allows it to pass through a 455μm mesh screen twice.

[0236] The number-average major diameter (number-average major diameter of plant-derived fibers in the raw material) of the obtained particles was 2.67 mm, and the number-average minor diameter (number-average minor diameter of plant-derived fibers in the raw material) was 0.39 mm.

[0237] <Example 1-1: Manufacturing of Resin Layer 1 Containing Plant-Derived Fibers>

[0238] All the following materials are simultaneously added to a double roller set at 150°C and heated until the temperature stabilizes, and the melt mixing begins.

[0239] The plant-derived fibers used in Manufacturing Example 1 have a number-average major diameter (number-average major diameter of the plant-derived fibers in the raw material) of 2.67 μm and a number-average minor diameter (number-average minor diameter of the plant-derived fibers in the raw material) of 0.39 mm.

[0240] After being added, the mixture is melt-blended at a set temperature of 150°C for 5 minutes, and then calendered using a calendering device to produce a resin layer 1 (250 μm thick) containing plant-derived fibers.

[0241]

[0242] <Examples 1-2: Manufacturing of Resin Layer A Containing Colorant>

[0243] The resin layer A (250 μm thick) containing the colorant was manufactured using the same materials as in Examples 1-1.

[0244]

[0245] <Examples 1-3: Fabrication of Laminated Structures>

[0246] Prepare resin layer 1 containing plant-derived fibers and resin layer A containing colorant. Combine the base fabric (polyester fabric), the resin layer containing plant-derived fibers, and the resin layer A containing colorant into a roll (grey fabric).

[0247] In the following processes, the fabric is supplied and processed continuously.

[0248] Adhesive is applied to the surface of the base fabric, and resin layer A containing colorant is bonded together. Next, resin layer 1 containing plant-derived fibers is further overlapped on the surface of the resin layer A containing colorant. Two additional rollers are added, and heating and pressure are applied (resin layer A containing colorant and resin layer 1 containing plant-derived fibers are bonded together by heating and pressure without the use of adhesive).

[0249] The above operations yield a composite having, in sequence, a resin layer 1 containing plant-derived fibers, a resin layer A containing colorants, an adhesive layer, and a base fabric.

[0250] A surface layer (polyurethane) is applied to the surface of the resin layer 1 containing plant-derived fibers of the obtained laminate, opposite to the adhesive layer, and dried at 80°C to 100°C. A surface treatment layer (polyurethane) is then applied to the surface of the surface layer, opposite to the resin layer 1 containing plant-derived fibers, and dried to produce the laminate 1.

[0251] The base fabric has a thickness of 490 μm, the resin layer 1 containing plant-derived fibers has a thickness of 250 μm, the resin layer A containing colorant has a thickness of 250 μm, the surface layer has a thickness of 20 μm, and the surface treatment layer has a thickness of 10 μm.

[0252] <Example 2>

[0253] The laminate was manufactured in the same manner as in Example 1, except that the resin layer B containing the colorant described below was used instead of the resin layer A containing the colorant used in Example 1.

[0254] A photograph of the laminate from Example 2 is shown below. Figure 2 .

[0255] Similar to Examples 1-1, a resin layer B (250 μm thick) containing a colorant was manufactured using the following materials.

[0256]

[0257] <Manufacturing Example 2-1: Manufacturing of Plant-Derived Fibers>

[0258] The plant-derived fibers manufactured in Example 1 are further processed using a cutting and grinding machine to... The material is processed using a sieve-like method, and then passed through a sieve with two 318μm mesh screens.

[0259] The number-average major diameter (number-average major diameter of plant-derived fibers in the raw material) of the obtained particles was 0.65 mm, and the number-average minor diameter (number-average minor diameter of plant-derived fibers in the raw material) was 0.21 mm.

[0260] <Manufacturing Example 2-2: Granule Manufacturing>

[0261] Granule 1 is manufactured using the following materials.

[0262] PVC TK-1300 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 100 parts by weight

[0263] 100 parts by weight of plasticizer dialkyl phthalate

[0264] 200 parts by weight of plant-derived fiber manufactured in Example 2

[0265] (equivalent to 50% by mass)

[0266] Plant-derived fibers are immersed in plasticizer, and polyvinyl chloride (PVC) powder is added while stirring. The mixture is then melt-blended using a twin-screw extruder (Bausano MD-30 / 19) at 150°C. After being discharged from the extruder, the mixture is immediately cut and cooled to obtain PVC granules containing plant-derived fibers.

[0267] <Manufacturing Examples 3-20: Manufacturing of Plant-Derived Fibers and Granules>

[0268] By changing the screen mesh size of the cutting and grinding machine and gradually narrowing the gap between the screen mesh and the rotor, plant-derived fibers with different number-average major diameters and number-average minor diameters were obtained, similar to Manufacturing Example 2.

[0269] Similar to Manufacturing Example 2, the plant-derived fibers with different average major diameters (the average major diameter of the plant-derived fibers in the raw material) and average minor diameters (the average minor diameter of the plant-derived fibers in the raw material) were granulated.

[0270] A list of granules 2 to 19 is shown in Table 1.

[0271] [Table 1]

[0272]

[0273] <Example 3>

[0274] Except that the resin layer containing plant-derived fibers described below is used instead of the resin layer 1 containing plant-derived fibers used in Example 1, the laminate is manufactured in the same manner as in Example 1.

[0275] Manufacturing of Resin Layer 2 Containing Plant-Derived Fibers

[0276] All the following materials are simultaneously added to a double roller set at 150°C and heated until the temperature stabilizes, and the melt mixing begins.

[0277] After being added, the mixture is melt-blended at a set temperature of 150°C for 5 minutes, and then calendered using a calendering device to produce a resin layer (250 μm thick) containing plant-derived fibers.

[0278]

[0279] <Examples 4-19>

[0280] Except that the pellets 1 in Example 3 are replaced with pellets 2 to 17 respectively, the laminates are manufactured in the same manner as in Example 3.

[0281] <Example 20>

[0282] Except that 3.82 parts by weight of granules 1 were used and the laminate was prepared with a plant-derived fiber content of 0.94% by weight, the laminate was manufactured in the same manner as in Example 3.

[0283] <Example 21>

[0284] Except that 16.7 parts by weight of granules 1 were used and the laminate was prepared with a plant-derived fiber content of 3.85% by weight, the laminate was manufactured in the same manner as in Example 3.

[0285] <Example 22>

[0286] Except that the plant-derived fiber manufactured in Example 2 was used in 16.7 parts by weight and prepared to have a plant-derived fiber content of 3.85% by weight, the laminate was manufactured in the same manner as in Example 2.

[0287] <Example 23>

[0288] Except that the plant-derived fiber manufactured in Example 2 was used in 49 parts by weight and prepared to have a plant-derived fiber content of 9.98% by weight, the laminate was manufactured in the same manner as in Example 2.

[0289] <Comparative Example 1>

[0290] Except that wood chips (number-average aspect ratio 1.1, number-average major diameter 0.22 mm, number-average minor diameter 0.20 mm) pulverized using a jet mill were used instead of the plant-derived fibers used in Example 1, the laminate was manufactured in the same manner as in Example 1.

[0291] <Comparative Example 2>

[0292] The laminate was manufactured in the same manner as in Example 1, except that a transparent layer without colorant was used instead of the colorant-containing resin layer A used in Example 1.

[0293] <Comparative Example 3>

[0294] Except that white plastic sheets (material made by cutting a 0.09 mm thick white PET film into sections with an average aspect ratio of 7.0, an average major diameter of 2.8 mm, and an average minor diameter of 0.4 mm) were used instead of the plant-derived fibers used in Example 1, the laminate was manufactured in the same manner as in Example 1.

[0295] <Comparative Example 4>

[0296] Except that plant-derived fibers with a number-average major diameter of 0.26 mm and a number-average minor diameter of 0.03 mm were used instead of the plant-derived fibers used in Example 3, the pellets 18 were manufactured in the same manner as in Example 3, and the laminates were manufactured in the same manner as in Example 3.

[0297] <Comparative Example 5>

[0298] Except that plant-derived fibers with a number-average major diameter of 0.41 mm and a number-average minor diameter of 0.03 mm were used instead of the plant-derived fibers used in Example 3, the granules 19 were manufactured in the same manner as in Example 3, and the laminates were manufactured in the same manner as in Example 3.

[0299] The number-average major axis and number-average minor axis of the plant-derived fibers in the images of the laminates of Examples 1-23 and Comparative Examples 1-5 were measured by observing the laminates using an optical microscope.

[0300] Based on a photograph of the particle image taken at 30x magnification, for 300 particles, the number-average major diameter (number-average major diameter of the plant-derived fibers in the image of the laminate) and the number-average minor diameter (number-average minor diameter of the plant-derived fibers in the image of the laminate) were measured by comparing with the scale lines. The arithmetic mean of the number-average major diameter (number-average major diameter of the plant-derived fibers in the image of the laminate), the number-average minor diameter (number-average minor diameter of the plant-derived fibers in the image of the laminate), and the aspect ratio (length-to-diameter ratio of the plant-derived fibers in the image of the laminate) of the 300 particles was calculated. At this time, if there were flaky dust particles with a diameter less than 0.10 mm and an aspect ratio less than 1.5, they were excluded from the measurement.

[0301] The aforementioned major axis refers to the length of the perpendicular line connecting the two parallel lines when the distance between the two parallel lines is the largest among the two parallel lines that connect to the outline of the aforementioned plant-derived fiber particle image.

[0302] The aforementioned minor axis refers to the length between the two points where the following straight line intersects the outline of the aforementioned plant-derived fiber particle image, the straight line being a line parallel to the aforementioned two parallel lines that passes through a point halfway along the aforementioned perpendicular line.

[0303] The results are shown in Table 2.

[0304] [Table 2]

[0305]

[0306]

[0307] For the laminates of Examples 1 to 23 and Comparative Examples 1 to 5, images of the resin layer containing plant-derived fibers were obtained, and the area ratio and envelopment of the plant-derived fibers were measured.

[0308] The results are shown in Table 3.

[0309] In addition, 40 administrative staff members were selected as group members to conduct a quirky sensory test on (1) whether the presence of added powder was detected in the laminate and (2) whether the aesthetics of the laminate were perceived.

[0310] The results are shown in Table 4.

[0311] The images of the resin layer were obtained under the following (image capture conditions), and the area ratio and envelopment of the plant-derived fibers were measured under the following (image processing conditions).

[0312] (Image shooting conditions)

[0313] Digital Image Acquisition Optical Microscope: Digital Microscopes Manufactured by Keyence

[0314] Shooting magnification:

[0315] When measuring the area ratio, the magnification is 30 times.

[0316] When measuring envelope, at a magnification of 50x.

[0317] (Image processing conditions)

[0318] Processing image size:

[0319] When measuring the area ratio (magnification 30x), the dimensions are 7.35mm × 9.80mm.

[0320] When measuring the envelope (at 50x magnification), the image size is 4.41mm × 5.88mm.

[0321] The following calculations were performed using WinROOF CLOUD, an image analysis software manufactured by Mitani Corporation, for image processing and analysis.

[0322] <Sampling>

[0323] 1. Monochrome Image Conversion

[0324] If the image is in color, convert it to monochrome.

[0325] From the menu of the WinROOF CLOUD image analysis software manufactured by Mitani Corporation, select monochrome image processing or RGB (red, green, blue) separation processing to perform monochrome image processing.

[0326] 2. Noise Removal

[0327] Next, in order to remove minute noise invisible to the naked eye, processing is performed using a noise removal mode. At this time, processing is performed under the condition of removing noise smaller than 50 μm.

[0328] 3. Concentration Conversion (Binarization)

[0329] Next, the image density is adjusted by density conversion in such a way that the outline of the portion containing plant-derived fibers becomes clear. Visually confirm that (1) the portion of the original image containing plant-derived fibers completely overlaps with the outline of (2) the density-converted image (where the portion containing the measured sample (plant-derived fibers) is shown in white). If there is no complete overlap during density conversion (e.g., if the outline of (2) is larger than that of (1), or if the outline of (1) is larger than that of (2), adjust the range of the input image density for density conversion in such a way that the outline of the original image containing plant-derived fibers completely overlaps with that of the density-converted image.

[0330] 4. Binarization

[0331] Next, binarization processing is performed. The portion containing plant-derived fibers is binarized with other portions. It is visually confirmed that (1) the portion containing plant-derived fibers in the original image completely overlaps with the outline of (2) the binarized image (the portion containing the measured sample (plant-derived fibers) is represented in green). In cases where there is no complete overlap in the automatic binarization mode (e.g., when the outline of (2) is larger than that of (1), or when the outline of (1) is larger than that of (2), the brightness range of the sample is adjusted so that the outline of the portion containing plant-derived fibers in the original image completely overlaps with the outline of the binarized image.

[0332] <Area Ratio>

[0333] The particle measurements are performed according to the measurement menu. The sampled particle data is then transmitted to the table calculation software. The total area of ​​particles with an equivalent circle diameter of 50μm or more is calculated and divided by the area of ​​the entire image.

[0334] Use the average of the area ratios calculated from 10 images.

[0335] <Envelope>

[0336] The particles are measured according to the measurement menu, and the sampled particle data is transmitted to the table calculation software. For each sampled particle with an equivalent circle diameter of 100μm or more, the envelope degree is calculated based on the perimeter and envelope perimeter.

[0337] The average of the envelope calculated from 10 images is used.

[0338] At this point, the sampling number is plotted on the image.

[0339] This operation allows for the comparison of data between each particle in the image and the sampled particles using the sampling number.

[0340] The envelope is defined by Equation 1 below.

[0341] [Number 2]

[0342] Envelope = Envelope perimeter (C PERI) / Perimeter (PERI) (Equation 1)

[0343] [Table 3]

[0344]

[0345] [Table 4]

[0346]

[0347] As can be seen from the results in Tables 2 to 4, the following molded body can provide a laminate in which the presence of plant-derived materials can be realistically felt in a highly designable manner. The laminate is a laminate having a resin layer containing a colorant and a resin layer containing plant-derived fibers. The laminate is characterized in that the number-average aspect ratio (major axis / minor axis) of the plant-derived fibers in the image of the laminate 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, and the number-average minor axis of the plant-derived fibers is 0.03 mm or more and 1.0 mm or less.

[0348] Examples of embodiments of this invention include the following.

[0349] <1> A laminate, characterized in that it comprises: a resin layer containing a colorant; and a resin layer containing plant-derived fibers.

[0350] In the image of the aforementioned layered volume,

[0351] The number-average aspect ratio (major axis / minor axis) of the aforementioned plant-derived fibers is 1.5 or higher and 15 or lower.

[0352] The number-average major diameter of the aforementioned plant-derived fibers is 0.2 mm or more and 3.0 mm or less.

[0353] The number average short diameter of the above-mentioned plant-derived fibers is greater than 0.03 mm and less than 1.0 mm.

[0354] <2> According to the above <1> The aforementioned laminate, wherein,

[0355] The number-average aspect ratio (major axis / minor axis) of the aforementioned plant-derived fibers is 1.5 or higher and 15 or lower.

[0356] The number-average major diameter of the aforementioned plant-derived fibers is 0.2 mm or more and 3.0 mm or less.

[0357] The number-average minor diameter of the aforementioned plant-derived fibers is ≥0.03 mm and ≤1.0 mm.

[0358] The aforementioned plant-derived fibers do not include fibers with a major diameter more than 2.5 times the number average major diameter.

[0359] <3> According to the above <1> The aforementioned laminate, wherein,

[0360] The number-average aspect ratio (major axis / minor axis) of the aforementioned plant-derived fibers is 1.5 or higher and 15 or lower.

[0361] The number-average major diameter of the aforementioned plant-derived fibers is 0.2 mm or more and 3.0 mm or less.

[0362] The number-average minor diameter of the aforementioned plant-derived fibers is 0.1 mm or more and 1.0 mm or less.

[0363] The aforementioned plant-derived fibers do not include fibers with a major diameter more than 2.5 times the number average major diameter.

[0364] <4> According to the above <1> The aforementioned laminate, wherein,

[0365] The number-average aspect ratio (major axis / minor axis) of the aforementioned plant-derived fibers is 1.5 or higher and 15 or lower.

[0366] The number-average major diameter of the aforementioned plant-derived fibers is 0.2 mm or more and 2.0 mm or less.

[0367] The number-average minor diameter of the aforementioned plant-derived fibers is 0.1 mm or more and 0.7 mm or less.

[0368] The aforementioned plant-derived fibers do not include fibers with a major diameter more than 2.5 times the number average major diameter.

[0369] <5> According to the above <1> The aforementioned laminate, wherein,

[0370] The number-average aspect ratio (major axis / minor axis) of the aforementioned plant-derived fibers is 1.5 or higher and 10 or lower.

[0371] The number-average major diameter of the aforementioned plant-derived fibers is 0.3 mm or more and 1.0 mm or less.

[0372] The number-average minor diameter of the aforementioned plant-derived fibers is 0.1 mm or more and 0.3 mm or less.

[0373] The aforementioned plant-derived fibers do not include fibers with a major diameter more than 2.5 times the number average major diameter.

[0374] <6> According to the above <1> The aforementioned laminate, wherein,

[0375] In the above images of resin layers containing plant-derived fibers,

[0376] The average area percentage of plant-derived fibers (100% × area of ​​portion containing plant-derived fibers / total area of ​​portion containing plant-derived fibers and other portions) is 3.0% or more and 8.0% or less.

[0377] The average inclusion ratio (envelope circumference (C PERI) / circumference (PERI)) of the above-mentioned plant-derived fibers was above 98.0% and below 99.9%.

[0378] The proportion of particles with an inclusion degree of less than 90% in the above-mentioned plant-derived fibers is less than 5.0%.

[0379] <7> According to the above <2> The aforementioned laminate, wherein,

[0380] In the above images of resin layers containing plant-derived fibers,

[0381] The average area percentage of plant-derived fibers (100% × area of ​​portion containing plant-derived fibers / total area of ​​portion containing plant-derived fibers and other portions) is 3.0% or more and 8.0% or less.

[0382] The average inclusion ratio (envelope circumference (C PERI) / circumference (PERI)) of the above-mentioned plant-derived fibers was above 98.0% and below 99.9%.

[0383] The proportion of particles with an inclusion degree of less than 90% in the above-mentioned plant-derived fibers is less than 5.0%.

[0384] <8> According to the above <3> The aforementioned laminate, wherein,

[0385] In the above images of resin layers containing plant-derived fibers,

[0386] The average area percentage of plant-derived fibers (100% × area of ​​portion containing plant-derived fibers / total area of ​​portion containing plant-derived fibers and other portions) is 3.0% or more and 8.0% or less.

[0387] The average inclusion ratio (envelope circumference (C PERI) / circumference (PERI)) of the above-mentioned plant-derived fibers was above 98.0% and below 99.9%.

[0388] The proportion of particles with an inclusion degree of less than 90% in the above-mentioned plant-derived fibers is less than 5.0%.

[0389] <9> According to the above <4> The aforementioned laminate, wherein,

[0390] In the above images of resin layers containing plant-derived fibers,

[0391] The average area percentage of plant-derived fibers (100% × area of ​​portion containing plant-derived fibers / total area of ​​portion containing plant-derived fibers and other portions) is 3.0% or more and 8.0% or less.

[0392] The average inclusion ratio (envelope circumference (C PERI) / circumference (PERI)) of the above-mentioned plant-derived fibers was above 98.0% and below 99.9%.

[0393] The proportion of particles with an inclusion degree of less than 90% in the above-mentioned plant-derived fibers is less than 5.0%.

[0394] <10> According to the above <5> The aforementioned laminate, wherein,

[0395] In the above images of resin layers containing plant-derived fibers,

[0396] The average area percentage of plant-derived fibers (100% × area of ​​portion containing plant-derived fibers / total area of ​​portion containing plant-derived fibers and other portions) is 3.0% or more and 8.0% or less.

[0397] The average inclusion ratio (envelope circumference (C PERI) / circumference (PERI)) of the above-mentioned plant-derived fibers was above 98.0% and below 99.9%.

[0398] The proportion of particles with an inclusion degree of less than 90% in the above-mentioned plant-derived fibers is less than 5.0%.

[0399] <11> A synthetic leather, characterized in that it has the above-mentioned... <1> to <10> The laminate and base fabric as described in any one of the following.

[0400] Explanation of reference numerals in the attached figures

[0401] 1 layered body

[0402] 2. Base fabric

[0403] 3. Resin layer containing colorant

[0404] 4. Resin layer containing plant-derived fibers

[0405] 5 Surface treatment layer

[0406] 6. Adhesive layer

[0407] 7. Outer layer

[0408] 8A Isolated plant-derived fibers

[0409] 8B Overlapping plant-derived fibers

Claims

1. A laminate, characterized in that, have: A resin layer containing colorants; and A resin layer containing plant-derived fibers. In the image of the layer, The plant-derived fibers have a number-average aspect ratio of 1.5 or higher and 15 or lower, where the aspect ratio is the ratio of the major axis to the minor axis. The plant-derived fibers have a number-average major diameter of 0.2 mm or more and 3.0 mm or less. The number-average minor diameter of the plant-derived fibers is greater than 0.03 mm and less than 1.0 mm.

2. The laminate according to claim 1, wherein, The plant-derived fibers do not contain fibers with a major diameter more than 2.5 times the number average major diameter.

3. The laminate according to claim 1, wherein, The number-average minor diameter 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 with a major diameter more than 2.5 times the number average major diameter.

4. The laminate according to claim 1, wherein, The number-average major diameter of the plant-derived fibers is 0.2 mm or more and 2.0 mm or less. The number-average minor diameter 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 with a major diameter more than 2.5 times the number average major diameter.

5. The laminate according to claim 1, wherein, The number-average aspect ratio of the plant-derived fibers is 1.5 or higher and 10 or lower. The plant-derived fibers have a number-average major diameter of 0.3 mm or more and 1.0 mm or less. The number-average minor diameter 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 with a major diameter more than 2.5 times the number average major diameter.

6. The laminate according to claim 1, wherein, In the image of the resin layer containing plant-derived fibers. The average area percentage of plant-derived fibers is between 3.0% and 8.0%. Area ratio = (Area containing plant-derived fibers / Total area of ​​plant-derived fibers and other areas) × 100% The average infiltration degree of the plant-derived fibers is above 98.0% and below 99.9%. Envelope degree = envelope perimeter / perimeter The proportion of particles with an inclusion degree of less than 90% in the plant-derived fiber is less than 5.0%.

7. The laminate according to claim 2, wherein, In the image of the resin layer containing plant-derived fibers. The average area percentage of plant-derived fibers is between 3.0% and 8.0%. Area ratio = (Area containing plant-derived fibers / Total area of ​​plant-derived fibers and other areas) × 100% The average infiltration degree of the plant-derived fibers is above 98.0% and below 99.9%. Envelope degree = envelope perimeter / perimeter The proportion of particles with an inclusion degree of less than 90% in the plant-derived fiber is less than 5.0%.

8. The laminate according to claim 3, wherein, In the image of the resin layer containing plant-derived fibers. The average area percentage of plant-derived fibers is between 3.0% and 8.0%. Area ratio = (Area containing plant-derived fibers / Total area of ​​plant-derived fibers and other areas) × 100% The average infiltration degree of the plant-derived fibers is above 98.0% and below 99.9%. Envelope degree = envelope perimeter / perimeter The proportion of particles with an inclusion degree of less than 90% in the plant-derived fiber is less than 5.0%.

9. The laminate according to claim 4, wherein, In the image of the resin layer containing plant-derived fibers. The average area percentage of plant-derived fibers is between 3.0% and 8.0%. Area ratio = (Area containing plant-derived fibers / Total area of ​​plant-derived fibers and other areas) × 100% The average infiltration degree of the plant-derived fibers is above 98.0% and below 99.9%. Envelope degree = envelope perimeter / perimeter The proportion of particles with an inclusion degree of less than 90% in the plant-derived fiber is less than 5.0%.

10. The laminate according to claim 5, wherein, In the image of the resin layer containing plant-derived fibers. The average area percentage of plant-derived fibers is between 3.0% and 8.0%. Area ratio = (Area containing plant-derived fibers / Total area of ​​plant-derived fibers and other areas) × 100% The average infiltration degree of the plant-derived fibers is above 98.0% and below 99.9%. Envelope degree = envelope perimeter / perimeter The proportion of particles with an inclusion degree of less than 90% in the plant-derived fiber is less than 5.0%.

11. A synthetic leather, characterized in that, It comprises a laminate and a base fabric as described in any one of claims 1 to 10.

Images