Skin material

Abstract

The purpose of the present invention is to provide a skin material that is produced in a short process time using a mushroom or the mushroom bed thereof.　The present invention provides a skin material including a base material and a surface layer that is arranged on the base material and contains a polymer material and dried and pulverized mushrooms or the dried and pulverized mushroom bed thereof.

Description

Surface material

[0001] The present invention relates to a surface material.

[0002] In various industries, sustainable products and materials are beginning to be actively adopted. One of them is fake leather, which is a material that mimics natural leather (genuine leather) without using animal leather, and includes synthetic leather formed by laminating a resin sheet on a base material (base fabric), artificial leather formed by impregnating a base material with a synthetic resin, and the like.

[0003] In recent years, fake leather using plant-derived materials has also attracted attention from the perspectives of animal protection and environmental consideration. For example, Japanese Patent Application Laid-Open No. 2022-538816 describes a durable sheet material using fungal biomass such as filamentous fungi and a manufacturing method thereof. Specifically, Japanese Patent Application Laid-Open No. 2022-538816 describes a method for manufacturing a durable sheet material including a mother phase preparation step of introducing a fungal inoculation material into a nutrient source on a solid support and incubating to grow biomass, and a step of collecting the grown biomass and adding a solvent, a polymer, a crosslinking agent, etc. to form a web. In this method, in the mother phase preparation step, an inoculum is grown to prepare a mother phase (mycelium) of the surface material, and in the web formation step, a polymer or the like is added as a reinforcing material to improve the strength of the surface material.

[0004] However, in the technology described in Japanese Patent Application Laid-Open No. 2022-538816, there is a problem that the process time is long because mycelium is grown from an inoculum to prepare a mother phase (block-shaped mycelium). Specifically, it may take up to about three weeks to grow mycelium and prepare a mother phase.

[0005] Therefore, an object of the present invention is to provide a surface material that is manufactured in a short process time using mushrooms or their fungal beds.

[0006] The inventors of the present invention conducted intensive studies to solve the above problems. As a result, they found that the above problems can be solved by using a surface material in which a surface layer containing a dried and pulverized product of mushrooms or their fungal beds and a polymer material is disposed on a base material, and thus completed the present invention.

[0007] In other words, one embodiment of the present invention is a surface material comprising a base material and a surface layer disposed on the base material, the surface layer comprising dried and pulverized mushroom or its substrate and a polymer material.

[0008] Figure 1 is a schematic cross-sectional view showing a skin material according to one embodiment of the present invention. Figure 2(a) shows the GC-MS measurement results of volatile components of dried spent mushroom substrate of buna shimeji (drying temperature: 100°C). Figure 2(b) shows the GC-MS measurement results of dried spent mushroom substrate of buna shimeji (drying temperature: 200°C). Figure 3(c) shows the GC-MS measurement results of volatile components of dried spent mushroom substrate of maitake (drying temperature: 100°C). Figure 3(d) shows the GC-MS measurement results of volatile components of dried spent mushroom substrate of maitake (drying temperature: 200°C).

[0009] One embodiment of the present invention is a skin material comprising a base material and a surface layer disposed on the base material, the surface layer comprising dried and pulverized mushroom or its substrate and a polymer material. According to the present invention, a skin material can be obtained that can be manufactured in a short process time. According to the present invention, since dried and pulverized mushroom or its substrate is used as a raw material, there is no need for a process of cultivating mycelium from a spawn to produce a parent phase, as described in Japanese Patent Publication No. 2022-538816. Therefore, the entire process for manufacturing the skin material can be carried out in one to two days, and the process time can be significantly reduced.

[0010] Embodiments of the present invention will be described below with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant explanations are omitted. Also, the dimensional ratios in the drawings are exaggerated for illustrative purposes and may differ from the actual ratios. Furthermore, in this specification, "X to Y" indicating a range includes X and Y, and means "X or more and Y or less". Also, unless otherwise specified, operations and measurements of physical properties, etc., are performed under conditions of room temperature (20 to 25°C) / relative humidity 40 to 50% RH.

[0011] [Skin Material] The skin material of the present invention is not particularly limited as long as it comprises a base material and a surface layer disposed on the base material and comprising dried and pulverized mushroom or its substrate and a polymer material. The surface layer is formed directly on the surface of the base material or via other layers. In a preferred embodiment of the present invention, there is an adhesive layer between the surface layer and the base material. In one embodiment of the present invention, the skin material may have other layers, such as a surface treatment layer, provided on the surface of the surface layer.

[0012] Figure 1 is a schematic cross-sectional view of a skin material according to one embodiment of the present invention. The skin material 1 of this embodiment has an adhesive layer 3, a surface layer 4, and a surface treatment layer 5 in that order on one surface of the base material 2. The surface layer 4 also contains dried and pulverized mushroom or its substrate 4a and a polymer material 4b. The main components of the skin material described above will be explained below. However, the skin material of the present invention is not limited to the form shown in Figure 1.

[0013] (Base Material) The base material is not particularly limited, and resin film base materials such as polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various types of nylon, and polyolefin resins such as polypropylene, and fibrous base materials can be used, but fibrous base materials are preferred. The fibrous base material is not particularly limited, and examples include fabrics such as knitted fabrics, woven fabrics, and nonwoven fabrics, and natural leather (including split leather). Fabrics may be coated or impregnated with conventionally known solvent-based or solvent-free (including water-based) polymer compounds (e.g., polyurethane resins and their copolymers, and polyvinyl chloride resins), and then dry-coagulated or wet-coagulated. Furthermore, the fabric may be treated with known pretreatment agents (e.g., penetrating agents, water repellents, flame retardants, ultraviolet absorbers, etc.). The fibrous base material may be colored with dyes or pigments. Furthermore, the surface of the fibrous base material may have nap by conventionally known napping treatment.

[0014] The types of fibers constituting the fibrous base material are not particularly limited, and conventionally known fibers such as natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers can be listed, and two or more of these may be combined. Among these, synthetic fibers are preferred from the viewpoint of strength and processability, and polyester fibers are more preferred.

[0015] The thickness of the substrate is not particularly limited, and conventionally known knowledge may be adopted as appropriate, but for example, it may be 1 to 1000 μm. The density of the substrate is also not particularly limited, but when using a fibrous substrate, for example, 0.05 to 5 g / cm³. ３ It is possible.

[0016] (Surface layer) The surface layer is placed on the substrate and includes dried and pulverized mushrooms or their substrates, and a polymer material.

[0017] (Dried and pulverized mushroom or its substrate) The mushroom may be either the fruiting body or the mycelium, or it may contain both. The fruiting body may be the cap or gills of the mushroom, or the stem (including the end of the stem). The mushroom is not particularly limited, but it is preferably a mushroom cultivated on a substrate or its waste material.

[0018] In this specification, "substrate" refers to the substrate culture medium after inoculation. Generally, in mushroom substrate cultivation, first, substrate culture medium raw materials are filled into a container such as a cultivation bottle, and the container is heat-sterilized to obtain the substrate culture medium, into which mushroom spawn is inoculated to create the substrate. The substrate is usually sealed to prevent the entry of unwanted bacteria. Here, sealing means sealing it in a way that does not hinder the respiration of the mushroom but prevents the entry of unwanted bacteria. Next, this substrate is cultured in a culture room until the mycelium has spread throughout the substrate (mature substrate), and then the seal is removed in a growing room and it is cultivated until it is harvested as a fruiting body.

[0019] The mushroom growing medium is not particularly limited, but it contains a culture medium base material, nutrients, etc. Examples of culture medium base materials include sawdust, wood chips, rice straw, and corn cob meal (corn cob). Examples of nutrients include wheat bran, okara (soy pulp), rice bran, and wheat germ. The mushroom growing medium may further contain water and additives such as lime (such as slaked lime), shell fossils, and oyster shells.

[0020] Spent mushroom substrate is the substrate remaining after the fruiting bodies have been harvested, and contains the substrate culture medium, mushrooms (especially the mycelium of the mushrooms), etc. Spent mushroom substrate may further contain decomposition products of the substrate culture medium, autodigested components of the mushrooms (including the fruiting bodies and mycelium), etc. In a preferred embodiment, the dried and pulverized product of the mushrooms or their substrate is the dried and pulverized product of spent mushroom substrate.

[0021] In this embodiment of the surface material, the surface layer may contain either dried and pulverized mushrooms or dried and pulverized mushroom substrate, or both. In a preferred embodiment, the surface material contains at least dried and pulverized mushroom substrate, wherein the substrate is spent substrate.

[0022] The source of the mushrooms or their substrates is not particularly limited. From the viewpoint of reducing environmental impact, it is preferable to use materials discarded from factories that produce edible mushrooms. That is, in a preferred embodiment, the mushrooms or their substrates are derived from mushroom waste, and more preferably from industrially produced mushroom waste. The waste may include both mushrooms (including both fruiting bodies and mycelium) and their substrates, and these may be used as raw materials for the surface material without separation.

[0023] In a preferred embodiment, the mushroom or its substrate includes spent substrate, which may be waste material discarded after harvesting mushrooms from industrial mushroom cultivation facilities such as mushroom production plants. This makes it possible to easily and inexpensively obtain mushroom substrate (spent substrate) as a raw material for the surface material, while also reducing the environmental burden. The spent substrate preferably includes mushroom mycelium and substrate culture medium, and may also include mushroom fruiting bodies.

[0024] There are no particular restrictions on the type of mushroom. Examples of mushrooms include, but are not limited to, buna shimeji, enoki, eringi, nameko, maitake, shiitake, button mushroom, hiratake, kikurage, sakura shimeji, hon shimeji, murasaki shimeji, akaazadake, oshiroi shimeji, shirotamogitake, naratake, naratakemodoki, matsutake, mukitatake, oohoraitake, tamagotake, fukurotake, himematsutake, tsukuritake, tsubafuusentake, shogenji, akayamadori, kiamiashiiguchi, kinoboriiguchi, hanaguchi, yamaiguchi, slime-rich burdock, kalatsutake, kichichitake, anzutake, yamabushitake, esoharitake, kurokawa, kotake, tonbimaitake, and shōro. Multiple types of mushrooms may be used in combination.

[0025] The type of mushroom is not particularly limited, but those with a total chitin and chitosan content in the dried product (total chitin and chitosan content in the dried edible portion) of 1.5% by mass or more are preferably used. More preferably, the total chitin and chitosan content in the dried mushroom is 2% by mass or more, even more preferably 3% by mass or more, and even more preferably 4% by mass or more. The upper limit of the total chitin and chitosan content in the dried mushroom is not particularly limited, but for example, it is 12% by mass or less, and preferably 10% by mass or less.

[0026] Chitin and chitosan are found, for example, in the cell walls of mushrooms. Chitin is a polysaccharide in which N-acetyl-D-glucosamine is linearly linked by β-1,4 bonds, while chitosan is a polysaccharide obtained by deacetylating chitin by hydrolysis, in which D-glucosamine is linearly linked by β-1,4 bonds. When the total content of chitin and chitosan in the dried material is within a predetermined range, the strength of the epidermal material can be improved if the surface layer contains polyurethane resin as a polymer material. This is thought to be because chitin and chitosan can act as amine catalysts because they contain amino groups or acetylamino groups. Adding an amine catalyst to polyurethane resin increases the reaction rate of the crosslinking reaction (Proceedings of the Polymer Science, Vol. 57, No. 2, pp. 67-71 (2000)). Therefore, it is thought that when the total content of chitin and chitosan, which are amine compounds, in the dried material is within a predetermined range, the strength of the surface layer containing polyurethane resin is improved, leading to an improvement in the strength of the epidermal material. Furthermore, if the total content of chitin and chitosan in the dried material is within a predetermined range, the cost of post-treatment of the surface material is reduced when the surface layer contains polyvinyl chloride resin as a polymer material. Polyvinyl chloride resin undergoes dehydrochlorination treatment using a base such as NaOH as a post-treatment, and it is known that the presence of amine compounds promotes the dehydrochlorination reaction (Transactions of the Japan Society of Waste Management and Resource Recycling, Vol. 21, No. 1, pp. 19-29, 2010; Organic Synthesis Chemistry, Vol. 27, No. 2 (1969), pp. 111-124). Therefore, it is thought that the dehydrochlorination reaction is promoted when the total content of chitin and chitosan, which are amine compounds in the dried material, is within a predetermined range. In addition, the amount of NaOH used during post-treatment can be reduced. Furthermore, the reaction temperature during post-treatment can be lowered. From these points, it is thought that the cost of post-treatment will be reduced. In addition, it is thought that the environmental burden at the time of disposal will be reduced.

[0027] Furthermore, if the total content of chitin and chitosan in the dried material is 1.5% by mass or more, the total content of amino groups and acetylamino groups in the dried material will be higher than the content of amino groups in dried apples. Therefore, this form of surface material is superior to vegan leather made from dried apples in that it has the above-mentioned effects. The content of amino groups in dried apples can be estimated, for example, from the amino acid content values ​​listed in the Japanese Food Standard Composition Table (8th Revised Edition) Supplement 2023 (Report of the Resource Survey Subcommittee of the Council for Science and Technology, Ministry of Education, Culture, Sports, Science and Technology, April 2023).

[0028] For example, the chitin content in dried mushrooms as described in the Journal of the Japanese Society of Nutrition and Food Science, Vol. 44, No. 4, 293-303, 1991, can be used as the total content of chitin and chitosan in dried mushrooms.

[0029] Examples of mushrooms in which the total content of chitin and chitosan in the dried material is 1.5% by mass or more include buna shimeji, enoki mushrooms (5.8-7.65% by mass), eringi, nameko mushrooms (3.52-4.34% by mass), maitake mushrooms (6.61% by mass), shiitake mushrooms (8.88% by mass), button mushrooms, oyster mushrooms (4.99-6.27% by mass), sakura shimeji mushrooms (5.27% by mass), and hon Shimeji (4.40 mass%), Murasaki Shimeji (10.38 mass%), Akaazadake (7.02 mass%), Oshiroi Shimeji (6.34 mass%), Shirotamogitake (4.87 mass%), Naratake (6.96 mass%), Naratakemodoki (5.77 mass%), Matsutake (5.22 mass%), Mukitake (3.20 mass%), Oohoraitake (12.10 mass%), Tamagotake (9.9 4% by mass, straw mushroom (2.40% by mass), dwarf matsutake (6.86% by mass), tsukuritake (10.34-10.54% by mass), tsubafusentake (7.26% by mass), shogenji (9.59% by mass), akayamadori (6.11% by mass), kiamiashiiguchi (7.01% by mass), kinoboriiguchi (6.09% by mass), hanaiguchi (7.52% by mass), yamaiguchi (8. Examples include 60% by mass, slimy bolete (5.97% by mass), karatoshitake (6.30% by mass), kichichitake (8.34% by mass), chanterelle (7.70% by mass), lion's mane (6.96% by mass), esoalberry (1.88% by mass), black bark mushroom (5.71% by mass), red mushroom (6.36% by mass), black maitake (7.05% by mass), and scallop (4.38% by mass).

[0030] In particular, the mushroom is preferably one or more selected from the group consisting of buna shimeji, enoki, eringi, nameko, maitake, shiitake, button mushroom, and oyster mushroom. These mushrooms can be artificially cultivated and produced in factories. Therefore, the mushrooms or their substrates (especially discarded mushrooms or their substrates) that serve as raw materials for the surface material can be easily obtained. Furthermore, the mushroom production plant and the processing plant for manufacturing the surface material can be set up adjacent to each other. This significantly reduces the cost of transporting the mushrooms or their substrates from the production plant to the processing plant.

[0031] While techniques for producing vegan leather using apples, cacti, and other materials are known, these cannot be manufactured in factories. Therefore, it is difficult to build processing plants adjacent to apple orchards or cactus fields, resulting in high transportation costs. In addition, transportation generates CO2. ２ The amount of waste generated can become quite large. Even if a processing plant is set up nearby, the large cultivation area means that collection costs will be high.

[0032] The dried and pulverized mushroom or mushroom substrate contained in the surface layer is not particularly limited, but it is preferable that the moisture content is 10% by mass or less. The effects of the present invention can be obtained even more significantly when the moisture content is within this range. In addition, the odor of the surface material can be reduced more effectively. The moisture content of the dried and pulverized material can be confirmed using a heat-drying type moisture meter. The lower limit of the moisture content of the dried and pulverized material is not particularly limited, but for example, it is 0.01% by mass or more.

[0033] The dried and pulverized mushroom or its substrate contained in the surface layer is not particularly limited, but it is preferably 100 μm or less in maximum particle size, and more preferably less than 100 μm. When the maximum particle size of the dried and pulverized material is 100 μm or less, the resulting surface material has excellent tactile properties. Furthermore, a surface material with high strength can be obtained. There is no particular lower limit to the maximum particle size of the dried and pulverized material, but for example, it is 10 μm or more. In this specification, the maximum particle size refers to the particle size at which the cumulative value shows 100% in the particle size distribution measured by a particle size distribution analyzer using the laser diffraction / scattering method. The maximum particle size of the dried and pulverized material can be adjusted by appropriately selecting the grinding means and grinding conditions, and performing classification as necessary.

[0034] The ratio of the dried and pulverized mushroom or mushroom substrate content to the total content of dried and pulverized mushroom or mushroom substrate in the surface layer is not particularly limited, but is, for example, 1 to 40% by mass (on a solid content basis), preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and even more preferably 6 to 12% by mass. A ratio of 1% by mass or more is preferable from an environmental standpoint, such as reducing petroleum usage and plastic waste. Furthermore, a ratio of 40% by mass or less provides excellent strength for the surface material.

[0035] The content of dried and pulverized mushrooms or their substrates in the surface layer is not particularly limited, but is, for example, 1 to 40% by mass (in terms of solid content) relative to the total amount of the surface layer, preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and even more preferably 6 to 12% by mass. A content of 1% by mass or more of dried and pulverized material is preferable from an environmental standpoint. Furthermore, a content of 40% by mass or less of dried and pulverized material provides excellent strength to the surface material.

[0036] (Polymer Material) The surface material of this embodiment contains a polymer material in its surface layer. The polymer material is not particularly limited and examples include polyurethane resin (PU), polyvinyl chloride resin (PVC), acrylic resin, fluororesin, and polyester resin. Among these, polyurethane resin and polyvinyl chloride resin are preferred because they are widely used in synthetic leather materials and can produce surface materials with excellent strength, flexibility, abrasion resistance.

[0037] While there are no particular limitations on the polyurethane resin, examples include polycarbonate polyurethane resin, polyester polyurethane resin, and polyether polyurethane resin, which can be used individually or in combination of two or more. Among these, polycarbonate polyurethane resin is preferred due to its excellent abrasion resistance and weather resistance. Furthermore, the polyurethane resin can be solvent-free, hot-melt, solvent-based, or water-based, and can be either one-component or two-component curing type, and should be appropriately selected according to the purpose and application.

[0038] The weight-average molecular weight of the polyurethane resin is not particularly limited, but is preferably 15,000 to 150,000. In this specification, the weight-average molecular weight (Mw) value shall be the value obtained by gel permeation chromatography (GPC) on a standard polystyrene basis. The polyurethane resin may be used alone or in the form of a mixture of two or more types.

[0039] Polyvinyl chloride resin is vinyl chloride (CH ２ This resin is primarily composed of constituent units derived from HCl (containing more than 50 mol% of these constituent units). Any PVC commonly used for surface materials can be used as the polyvinyl chloride resin without particular restrictions. For example, a polyvinyl chloride resin with an average degree of polymerization of 600 to 2000, preferably 650 to 1800, can be suitably used. An average degree of polymerization of 600 or higher provides excellent abrasion resistance and flexural resistance, while an average degree of polymerization of 2000 or lower provides excellent moldability. The average degree of polymerization of the polyvinyl chloride resin refers to the average degree of polymerization measured in accordance with JIS K-6720-2: "Test Methods for Polyvinyl Chloride Resins".

[0040] The polyvinyl chloride resin may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride and other monomers copolymerizable thereto. Examples of other monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene, and styrene, (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate, and methyl methacrylate, maleic acid diesters such as dibutyl maleate and diethyl maleate, fumaric acid diesters such as dibutyl fumarate and diethyl fumarate, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl halides such as vinylidene chloride and vinyl bromide, and vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. The above polyvinyl chloride resin may be used alone or in the form of a mixture of two or more.

[0041] The ratio of the content of the polymer material to the total content of the dried and pulverized product of the mushroom or its mycelium bed in the surface layer is not particularly limited, but is, for example, 60 to 99% by mass (in terms of solid content), preferably 70 to 97% by mass, more preferably 80 to 95% by mass, and still more preferably 88 to 94% by mass. When the above ratio is 60% by mass or more, the strength of the skin material is excellent. Also, when the above ratio is 99% by mass or less, it is suitable from the viewpoint of environmental consideration.

[0042] The content of the polymer material in the surface layer is not particularly limited, but is, for example, 60 to 99% by mass (in terms of solid content) with respect to the total amount of the surface layer, preferably 70 to 97% by mass, more preferably 80 to 95% by mass, and still more preferably 88 to 94% by mass. When the content of the polymer material is 60% by mass or more, the strength of the skin material is excellent. Also, when the content of the polymer material is 99% by mass or less, it is suitable from the viewpoint of environmental consideration.

[0043] The surface layer may optionally contain known additives such as plasticizers, heat stabilizers, fillers, pigments, flame retardants, conductivity imparting agents, antistatic agents, moisture permeability improvers, water repellents, oil repellents, water absorbers, moisture absorbers, deodorants, defoamers, pigment dispersants, hydrolysis inhibitors, crosslinking agents, thickeners, etc.

[0044] In addition, although the skin material of this form is not particularly limited, it is preferably free of materials derived from mycelia grown from inoculum on a fibrous substrate placed on a growth medium. Also, although the skin material of this form is not particularly limited, it is preferably free of any materials derived from strawberries, cacti, grapes, apples, and pineapples. Further, although not particularly limited, in the skin material of this form, the content of materials derived from plants other than the dried product, pulverized product, and dried and pulverized product of the mushroom and / or its mycelium bed in the surface layer is preferably 5% by mass or less, and more preferably 3% by mass or less, based on the total mass of the surface layer.

[0045] The thickness of the surface layer (thickness when dry) is not particularly limited, but is, for example, 1 to 1000 μm, preferably 10 to 900 μm. If the thickness is 1 μm or more, the abrasion resistance is excellent. Also, a thickness of 1000 μm or less is preferable because it has an excellent texture.

[0046] (Adhesive layer) The above-mentioned base material and the surface layer may be directly laminated, or may be bonded via an adhesive layer. Bonding via an adhesive layer is preferable because it suppresses excessive penetration of the resin constituting the surface layer into the base material.

[0047] The adhesive for forming the adhesive layer is not particularly limited. Examples thereof include adhesives containing resins such as polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, and acrylic resin. A commercially available adhesive may be used to form the adhesive layer. The thickness of the adhesive layer (thickness when dry) is also not particularly limited, but is, for example, 1 to 200 μm.

[0048] (Surface treatment layer) The skin material of this embodiment may include a surface treatment layer on the surface layer for the purpose of improving the appearance, touch, abrasion resistance, etc. of the skin material. The material of the surface treatment layer is not particularly limited, and examples thereof include polyurethane resin, acrylic resin, fluororesin, vinyl chloride resin, etc. It is preferable to use polyurethane resin from the viewpoint of improving abrasion resistance and texture. As the polyurethane resin, polycarbonate polyurethane resin, polyester polyurethane resin, polyether polyurethane resin, etc. can be preferably used.

[0049] The surface treatment layer may contain other components. Here, the other components are not particularly limited, and examples thereof include pigments, crosslinking agents (curing agents), touch agents, leveling agents, thickening agents, ultraviolet absorbers, etc. The thickness of the surface treatment layer (thickness when dry) is also not particularly limited, but is, for example, 1 to 200 μm.

[0050] (Manufacturing method of the skin material) The manufacturing method of the skin material of this embodiment is not particularly limited. As an example, a method including the following steps can be used: (1) A drying step of drying the mushroom or its mycelium bed to obtain a dried product, (2) A pulverizing step of pulverizing the dried product to obtain a dried pulverized product, (3) A classification step of classifying the dried pulverized product, (4) An epidermalization step of forming a surface layer containing the dried pulverized product and a polymer material that has undergone the classification step on the base material.

[0051] According to the method described above, the surface material can be manufactured in a short process time. The steps are described below. The process may include a step of preparing the raw material, which is the mushroom or its substrate, before the drying step. From the viewpoint of reducing environmental impact, it is preferable to obtain and use as raw material waste from industrially produced edible mushrooms, such as waste from mushroom factories.

[0052] <Drying Process> In the drying process, the mushrooms or their substrates are dried to obtain a dried product. When both mushrooms and their substrates are used, it is preferable to perform the drying process and the following steps without separating them. The drying method is not particularly limited, and known hot air dryers, hot nitrogen dryers, far-infrared dryers, etc., can be used. The drying temperature is not particularly limited, but from the viewpoint of effectively removing 1-octen-3-ol, which is the main odor component of mushrooms, and obtaining an outer layer material with reduced odor intensity, it is preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher. The upper limit of the drying temperature is not particularly limited, but for example, it is 300°C or lower, preferably 260°C or lower, more preferably 240°C or lower, even more preferably 220°C or lower, and even more preferably 210°C or lower.

[0053] The drying time is not particularly limited, but is, for example, 8 to 24 hours, preferably 12 to 20 hours, and more preferably 14 to 18 hours. A drying time of 8 hours or more is excellent in reducing odor intensity. A drying time of 24 hours or less is excellent in shortening the process time. The moisture content of the dried product obtained through the drying process is not particularly limited, but is preferably 10% by mass or less, and more preferably 0.01 to 10% by mass. It is also preferable that the moisture content of the dried pulverized product after the pulverization and classification processes described later is within the above range.

[0054] <Grinding Process> Next, the dried material obtained above is ground to obtain a dried pulverized material. There are no particular restrictions on the grinder used during grinding, but known mechanical grinding devices such as hammer mills, pin mills, jet mills, bevel impactors, turbo mills, knife hammer mills, rotary cutter mills, and roll crushers can be used. The grinding process can be carried out for a process time of, for example, 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

[0055] <Classification Process> The dried pulverized material obtained above is classified and adjusted to a specific particle size. The classification method is not particularly limited, but for example, it can be carried out by passing it through a sieve having a predetermined mesh size. It is preferable to use a sieve with a mesh size of 20 to 200 μm, and these may be used in a multi-stage system. It is preferable to adjust the maximum particle size of the final powder to be 100 μm or less. The classification process can be carried out for a process time of, for example, 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

[0056] <Skin Formation Process> Next, a surface layer containing the dried pulverized material that has undergone the classification process and a polymer material is formed on the substrate. The specific means of forming the surface layer are not particularly limited. For example, a coating composition may be prepared by mixing the dried pulverized material that has undergone the classification process and the polymer material with additives, solvents, etc. as needed, and this may be applied directly to the substrate to form the surface layer. Alternatively, the surface layer may be prepared first and then adhered to the substrate to obtain the skin material. In this case, the surface layer can be prepared, for example, by applying the above coating composition onto a release material such as release paper. Examples of solvents that can be used to prepare the coating composition include dimethylformamide (DMF), methyl ethyl ketone (MEK), isopropyl alcohol (IPA), toluene, etc., and mixed solvents obtained by mixing two or more of these.

[0057] Various conventionally known methods can be used to apply the coating composition to a substrate or a release-type substrate, and are not particularly limited. For example, methods using equipment such as a reverse roll coater, spray coater, roll coater, knife coater, and comma coater can be used. Among these, application by a reverse roll coater, roll coater, spray coater, or comma coater is preferred because it enables the formation of a uniform thin film layer.

[0058] The release material is not particularly limited and can be any material that has release properties to polymer materials, or a material that has been treated with a release agent. Examples include release paper, release treated cloth, water-repellent treated cloth, olefin sheets or films made of polyethylene resin or polypropylene resin, fluororesin sheets or films, and plastic films with release paper. As for the release paper, either release paper for mold transfer or smooth release paper can be used. By using release paper for mold transfer, an uneven pattern called a molded pattern can be formed on the surface of the surface layer.

[0059] After applying the coating composition, heat treatment is performed as needed. The heat treatment is performed to evaporate the solvent in the coating composition and dry the polymer material. In cases where a crosslinking agent that causes a crosslinking reaction by heat treatment is used, or when a two-component curing type resin is used, the heat treatment is performed to promote the reaction and form a film with sufficient strength. There are no particular restrictions on the heat treatment temperature or heat treatment time.

[0060] When a surface layer is formed on a release-type substrate, the surface layer is then bonded to the substrate. Bonding may be done via an adhesive layer or directly. The means for forming the adhesive layer are not particularly limited, but a method of preparing an adhesive and applying it to the surface layer or substrate can be used. Various known methods can be used for applying the adhesive, and are not particularly limited. For example, methods using equipment such as a reverse roll coater, spray coater, roll coater, gravure coater, kiss roll coater, knife coater, or comma coater can be used. After applying the adhesive, heating and drying may be performed as needed.

[0061] If necessary, a surface treatment layer may be provided on the surface opposite to the substrate of the surface layer. In this case, for example, after peeling off the release substrate from the surface layer, a coating solution containing the resin constituting the surface treatment layer, and optionally other components and solvents, can be applied to the surface layer to form the surface treatment layer. Various known methods can be used to apply the coating solution, and are not particularly limited. For example, methods using equipment such as a reverse roll coater, spray coater, roll coater, gravure coater, kiss roll coater, knife coater, and comma coater can be used. After applying the coating solution, heating and drying may be performed as necessary.

[0062] The epidermal formation process can be carried out, for example, in a process time of 5 minutes to 5 hours, preferably 10 minutes to 2 hours.

[0063] (Applications) The surface material of the present invention can be manufactured in a short process time and offers excellent productivity. It is also an environmentally friendly material. The surface material of the present invention can be used in a variety of products, including interior materials for vehicles such as automobiles, interior products such as sofas, shoes, and bags. In particular, the surface material of the present invention can be suitably used in interior materials such as steering wheels, seats, doors, instrument panels, assist grips, and grips for automobiles. That is, one embodiment of the present invention is an interior material for vehicles that includes the above-mentioned surface material.

[0064] The following items are also included in the scope of the present invention: Item 1: A skin material comprising: a base material; a surface layer disposed on the base material and comprising: dried and pulverized mushroom or its substrate; and a polymer material. Item 2: The skin material according to Item 1, wherein the mushroom has a total content of chitin and chitosan in the dried material of 1.5% by mass or more. Item 3: The skin material according to Item 1 or 2, wherein the mushroom is one or more selected from the group consisting of buna shimeji, enoki mushroom, eringi mushroom, nameko mushroom, maitake mushroom, shiitake mushroom, button mushroom, and oyster mushroom. Item 4: The skin material according to any one of Items 1 to 3, wherein the dried and pulverized material has a maximum particle size of 100 μm or less. Item 5: The skin material according to any one of Items 1 to 4, wherein the polymer material is polyurethane resin or polyvinyl chloride resin. Item 6: The skin material according to any one of Items 1 to 5, wherein the mushroom or its substrate is derived from mushroom waste. Item 7: A method for producing a surface material, comprising: a drying step of drying a mushroom or its substrate to obtain a dried product; a grinding step of grinding the dried product to obtain a dried pulverized product; a classification step of classifying the dried pulverized product; and a surface formation step of forming a surface layer on a substrate containing the dried pulverized product that has undergone the classification step and a polymer material. Item 8: A method for producing a surface material according to any one of items 1 to 6, comprising: a drying step of drying a mushroom or its substrate to obtain a dried product; a grinding step of grinding the dried product to obtain a dried pulverized product; a classification step of classifying the dried pulverized product; and a surface formation step of forming a surface layer on a substrate containing the dried pulverized product that has undergone the classification step and a polymer material. Item 9: The method according to item 7 or 8, wherein the drying temperature in the drying step is 180°C or higher. Item 10: The method according to item 7 or 8, wherein the drying temperature in the drying step is 200°C or higher. Item 11: A surface material according to any one of items 1 to 6, used in interior materials for vehicles.

[0065] The effects of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following examples, unless otherwise specified, the operations were carried out at room temperature (25°C). Unless otherwise specified, "%" and "parts" mean "mass%" and "parts by mass," respectively.

[0066] [Example 1] <Material Procurement> Spent mushroom substrate of buna shimeji mushrooms, which is discarded from a mushroom factory, was prepared. This spent substrate is the substrate remaining after the fruiting bodies of grown buna shimeji mushrooms have been harvested from industrial cultivation of buna shimeji mushrooms, and contains buna shimeji mycelium and substrate culture medium.

[0067] <Drying> The spent mushroom substrate described above was dried using a hot air dryer. The drying temperature was set to 100°C, and the material was dried for approximately 16 hours to obtain the dried product. The moisture content of the dried product was confirmed to be 10% by mass or less using a heated drying moisture meter.

[0068] <Grinding> The dried material obtained above was ground using a bevel impactor to obtain a dried pulverized product. The grinding process took approximately 10 minutes.

[0069] <Classification> The dried pulverized material was collected and classified using a sieve with a mesh size of 100 μm to obtain dried pulverized material with a maximum particle size of less than 100 μm (classified dried pulverized material). The classification process took approximately 10 minutes.

[0070] <Surface Formation> A solvent was mixed with 12 parts by mass of the dried pulverized material after classification and 88 parts by mass of polyvinyl chloride (PVC, a homopolymer of vinyl chloride) to obtain a surface resin composition. The obtained surface resin composition was printed onto release paper and dried to produce a surface sheet.

[0071] An adhesive layer was obtained by applying an adhesive to the surface layer obtained above and drying it. A substrate was then bonded to the coated surface to obtain a sheet-like surface material.

[0072] [Example 2] The surface material of this example was prepared in the same manner as in Example 1, except that the drying temperature was changed to 200°C in the <drying> step described above.

[0073] [Example 3] The surface material for this example was prepared in the same manner as in Example 1, except that the <Material Procurement> was changed as follows: <Material Procurement> Spent maitake mushroom substrate discarded from a mushroom factory was prepared. This spent substrate is the substrate remaining after industrial cultivation of maitake mushrooms and harvesting the grown maitake fruiting bodies, and contains maitake mycelium and substrate culture medium.

[0074] [Example 4] The surface material of this example was prepared in the same manner as in Example 3, except that the drying temperature was changed to 200°C in the <drying> step of Example 3.

[0075] [Gas Chromatography-Mass Spectrometry (GC-MS) Measurement of Dried Materials] Gas chromatography-mass spectrometry (GC-MS) measurements were performed on the dried material samples obtained by the above-mentioned <drying> process. Specifically, the odor components generated by heating the sample were collected in a collection tube filled with an adsorbent, and then introduced into a GC-MS analyzer using a thermal desorption device for analysis. The results are shown in Figures 2 and 3. Figure 2(a) shows the GC-MS measurement results of volatile components of dried spent mushroom substrate of buna shimeji (drying temperature: 100°C), and Figure 2(b) shows the GC-MS measurement results of volatile components of dried spent mushroom substrate of buna shimeji (drying temperature: 200°C). As shown in Figure 2(a), when the drying temperature is 100°C, 1-octen-3-ol is present as a volatile component, but as shown in Figure 2(b), this component is not observed when the drying temperature is 200°C. 1-octen-3-ol is the main odor component of mushrooms, but it has been confirmed that drying spent mushroom substrate at 200°C effectively removes this component, leading to a reduction in odor.

[0076] Furthermore, Figure 3(c) shows the GC-MS measurement results of volatile components in dried spent maitake mushroom substrate (drying temperature: 100°C), and Figure 3(d) shows the GC-MS measurement results of volatile components in dried spent maitake mushroom substrate (drying temperature: 200°C). As shown in Figure 3(c), when the drying temperature is 100°C, 1-octen-3-ol is present as a volatile component, but as shown in Figure 3(d), this component is not observed when the drying temperature is 200°C. Therefore, it was confirmed that drying the spent mushroom substrate at 200°C can effectively remove 1-octen-3-ol, leading to a reduction in odor.

[0077] [Measurement of Odor Intensity of Dried Material] The odor intensity of the dried material samples obtained through the above-mentioned drying process was measured. Specifically, the odor components generated by heating the sample were collected in a collection tube filled with an adsorbent, and a sensory evaluation was performed by an odor expert. The odor intensity was evaluated using the odor intensity of an aqueous 1-butanol solution placed in an odor bag as the scale. The results are shown in Table 1 below. In Table 1 below, the evaluation value of odor intensity follows the following criteria. If the evaluation value is 3 or less, the odor intensity will be appropriate when used as a surface material, and it can be used without any problems.

[0078] (Odor intensity evaluation scale) 0: Equivalent to the odor intensity of a 1-butanol aqueous solution with a concentration of 0, 1: Equivalent to the odor intensity of a 1-butanol aqueous solution with a concentration of 30 μL / L, 2: Equivalent to the odor intensity of a 1-butanol aqueous solution with a concentration of 300 μL / L, 3: Equivalent to the odor intensity of a 1-butanol aqueous solution with a concentration of 1000 μL / L, 4: Equivalent to the odor intensity of a 1-butanol aqueous solution with a concentration of 3000 μL / L, 5: Equivalent to the odor intensity of a 1-butanol aqueous solution with a concentration of 10000 μL / L.

[0079]

[0080] From the results in Table 1 above, it was found that when the drying temperature is 200°C, the odor intensity is reduced more significantly compared to when it is 100°C.

[0081] (Examples 5-8) Except for changing the amount of dried pulverized material added after classification to 6 parts by mass and the amount of polyvinyl chloride (PVC) added to 94 parts by mass in the <skin formation> step of Examples 1-4, the skin materials of Examples 5-8 were prepared using the same method. In all of Examples 5-8, skin materials were obtained in the same manner as in Examples 1-4.

[0082] 1. Outer layer material, 2. Base material, 3. Adhesive layer, 4. Surface layer, 4a. Dried and pulverized mushroom or its substrate, 4b. Polymer material, 5. Surface treatment layer.

Claims

1. A surface material comprising a base material, and a surface layer disposed on the base material, the surface layer comprising dried and pulverized mushroom or its substrate, and a polymer material.

2. The surface material according to claim 1, wherein the mushroom has a total content of chitin and chitosan in the dried product of 1.5% by mass or more.

3. The surface material according to claim 1, wherein the mushroom is one or more selected from the group consisting of buna shimeji, enoki mushroom, king oyster mushroom, nameko mushroom, maitake mushroom, shiitake mushroom, button mushroom, and oyster mushroom.

4. The surface material according to claim 1, wherein the dried pulverized material has a maximum particle size of 100 μm or less.

5. The surface material according to claim 1, wherein the polymer material is a polyurethane resin or a polyvinyl chloride resin.

6. The surface material according to claim 1, wherein the mushroom or its substrate is derived from mushroom waste.

7. A method for producing a surface material, comprising: a drying step of drying a mushroom or its substrate to obtain a dried product; a grinding step of grinding the dried product to obtain a dried pulverized product; a classification step of classifying the dried pulverized product; and a surface formation step of forming a surface layer on a substrate containing the dried pulverized product obtained through the classification step and a polymer material.

8. The manufacturing method according to claim 7, wherein the drying temperature in the drying step is 180°C or higher.

9. The manufacturing method according to claim 7, wherein the drying temperature in the drying step is 200°C or higher.

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