WO2022075438A1 - 皮革、皮革コーティング剤、及び皮革の製造方法 - Google Patents

皮革、皮革コーティング剤、及び皮革の製造方法 Download PDF

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Publication number
WO2022075438A1
WO2022075438A1 PCT/JP2021/037289 JP2021037289W WO2022075438A1 WO 2022075438 A1 WO2022075438 A1 WO 2022075438A1 JP 2021037289 W JP2021037289 W JP 2021037289W WO 2022075438 A1 WO2022075438 A1 WO 2022075438A1
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Prior art keywords
layer
leather
resin
mass
coating
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PCT/JP2021/037289
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English (en)
French (fr)
Japanese (ja)
Inventor
昇 樽田
美和 多田
正彦 小川
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ミドリオートレザー株式会社
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Priority to JP2022555580A priority Critical patent/JPWO2022075438A1/ja
Publication of WO2022075438A1 publication Critical patent/WO2022075438A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof

Definitions

  • One embodiment of the present invention relates to leather, a leather coating agent, and a method for producing leather, and more specifically, to leather to which antiviral properties have been imparted, a leather coating agent, and a method for producing leather.
  • leathers such as natural leather and synthetic leather are used as automobile interior parts such as automobile seats, and as skin materials for furniture, school bags, bags and the like.
  • Leather is required to have various characteristics such as durability, appearance, texture, and tactile sensation according to these uses, and the leather base material and coating have been improved.
  • leather for automobile seats has been required to have a particularly high standard in terms of physical properties and appearance.
  • a high degree of wear resistance is required because friction is intense due to frequent passengers getting on and off.
  • leather since leather has an aspect of a luxury item, it is required to have a color, gloss, and other appearance that the user prefers.
  • Antifouling properties that make it easy to wipe off dirt adhering to leather during use are also required mainly for light-colored leather.
  • the surface of the leather base is coated with a base coat, a color coat, and a top coat.
  • These coating layers are formed by applying various additives such as a cross-linking agent, a leveling agent, a pigment, and a matting agent to an aqueous dispersion (water-based paint) of a urethane resin or a (meth) acrylic resin as needed. Will be done.
  • the top coat is located in the outermost layer and is important in meeting the various requirements mentioned above. It is made hard to improve wear resistance, but on the other hand, it is also required to have a certain degree of flexibility so that the coating film does not crack when bent. Furthermore, the top coat also plays an important role in adjusting the appearance, has a function of adjusting the gloss by adding a matting agent such as silica, and in some cases, a pigment is added to adjust the color. It is also required to have sufficient light resistance and to suppress discoloration to a certain extent even when exposed to sunlight during use, and caution is required especially for light-colored leather.
  • the tactile sensation various measures such as addition of a silicone compound have been made, and silica used as a matting agent makes the tactile sensation dry, so an alternative matting agent is also being studied.
  • an overcoat may be applied on top of the topcoat.
  • the top coat which has a proven track record in mass production and durability, can be used to appropriately add performance such as antifouling property, tactile sensation, slipperiness, grip, and squeaking noise avoidance. It is useful.
  • Patent Document 1 discloses that an antibacterial leather is provided by applying a resin solution containing zirconium phosphate containing silver to synthetic leather.
  • Patent Document 2 discloses that a resin molded product is provided by directly blending a zirconium pyrophosphate-based inorganic antibacterial agent containing silver into a resin.
  • Patent Document 3 discloses that a zirconium phosphate-based inorganic antibacterial agent containing silver is directly blended with a resin to provide a resin molded product.
  • Patent Document 4 uses zirconium phosphate as two kinds of anti-allergen agents and a homopolymer composed of an aromatic sulfonic acid-based monomer, and uses a copolymer containing styrene acid salt as an antiviral agent.
  • a polyester knit which is a textile product, is immersed in an aqueous dispersion containing an anti-allergen agent and an anti-virus agent, and an anti-allergen agent or the like is attached to the polyester knit.
  • Patent Document 1 has a problem that it is easily discolored by sulfurization because the antibacterial agent contains a considerable amount of silver.
  • natural leather contains a sulfurizing component, it tends to be easily discolored when a silver phosphate compound is used.
  • the purpose is to impart antibacterial properties, and antiviral properties have not been investigated.
  • Antibacterial drugs may also show antiviral properties, but this is not certain.
  • no studies have been conducted to satisfy the physical characteristics and appearance required for the above-mentioned leather for automobile seats.
  • zirconium phosphate containing silver has low compatibility with an aqueous resin, it is applied to leather as a resin solution, and a method of applying it in addition to an aqueous paint has not been studied.
  • Patent Documents 2 and 3 cite leather as an example of applying an antibacterial agent, but have the same problems as Patent Document 1.
  • zirconium phosphate which is an anti-allergen agent, is directly attached to the knit fiber, and the resin content contained in the aqueous dispersion is very small and does not form a coating film. .. Therefore, this method is not immediately applicable to leather.
  • An object of the present invention is to provide a leather having antiviral properties and having good wear resistance and appearance (moderate gloss and light resistance) that can be used for automobile seats. For this purpose, it is desirable to find a high antiviral agent that suppresses discoloration, and to find a method of adding this antiviral agent to the aqueous resin and applying it to the leather surface without impairing the wear resistance. Is done.
  • the gist of the present invention is as follows. [1] Zirconium phosphate particles of 0.5 to 2.0 g / m 2 per unit area, 1.2 to 7.0 g / m 2 of resin, and 0.18 g to 3.5 g / m 2 of cross-linking agent. A leather having a coating layer having a layer thickness of 3.0 ⁇ m to 10.0 ⁇ m as the outermost layer. [2] The leather according to [1], wherein the resin contains at least one selected from the group consisting of urethane resin and (meth) acrylic resin. [3] The leather according to [1], wherein the resin contains a urethane resin and a (meth) acrylic resin.
  • the outermost coating layer includes a resin having a weight of 40.0 to 70.0% by mass and a cross-linking agent having a weight of 6.0 to 35.0% by mass with respect to the total solid content of the coating layer.
  • the present invention it is possible to provide leather to which antiviral property is imparted, durability is excellent, and discoloration is prevented. Further, according to another embodiment, it is possible to provide leather having a good wet feel in addition to the above. Furthermore, according to another embodiment, it is possible to provide a leather coating agent for providing these leathers and a method for producing the leather.
  • a schematic cross-sectional view of leather is shown.
  • a schematic cross-sectional view of leather is shown.
  • a schematic cross-sectional view of leather is shown.
  • a schematic cross-sectional view of leather is shown.
  • the leather according to one embodiment of the present invention contains zirconium phosphate particles of 0.5 to 2.0 g / m 2 per unit area, and has a coating layer having a layer thickness of 3.0 ⁇ m or more as the outermost layer. It is a feature.
  • the coating layer may further contain 1.2 to 7.0 g / m 2 of the resin and 0.18 g to 3.5 g / m 2 of the cross-linking agent.
  • the zirconium phosphate particles may be 0.8-2.0 g / m 2 per unit area. According to this, it is possible to provide leather which is imparted with antiviral property, has excellent durability, and is prevented from discoloration.
  • the leather has a leather base material and a coating layer formed on the leather base material.
  • the leather base material may be either natural leather or synthetic leather.
  • FIG. 1 shows a schematic cross-sectional view of leather.
  • the base coat layer 3, the color coat layer 4, and the top coat layer 5 are usually formed on the leather base material 2 in this order, depending on the characteristics required for the leather. Therefore, as shown in FIG. 1C, the color coat layer 4 may be omitted.
  • an overcoat layer 6 may be further formed on the topcoat layer 5, and the color coat layer 4 may be omitted as shown in FIG. 1D depending on the characteristics required for leather. There is.
  • the outermost coating layer may be the top coat layer 5 or the overcoat layer 6 formed on the top coat layer 5.
  • the outermost coating layer contains zirconium phosphate particles. It is preferable that only the outermost coating layer contains zirconium phosphate particles.
  • the layer directly above the layer containing the zirconium phosphate particles may be easily peeled off due to the Lotus effect of the zirconium phosphate particles. From this point of view, it is preferable that only the outermost coating layer contains zirconium phosphate particles, and the coating layer of the intermediate layer does not contain zirconium phosphate particles.
  • the leather of the present invention will be described in order.
  • Top coat layer and overcoat layer The top coat layer is a layer provided on the color coat layer or, if no color coat layer is provided, on the base coat layer, and is located on the outermost layer of leather. However, it is required to have predetermined wear resistance and light resistance. Furthermore, moderate luster and tactile sensation may be required as a function of the top coat layer.
  • the overcoat layer may be formed on the topcoat layer for the purpose of impairing performance such as antifouling property, tactile sensation, slipperiness, grip property, and squeaking noise avoidance. Although there is a drawback that the number of processes is increased by one, it is useful in that a top coat layer that has a proven track record in mass production and durability can be used.
  • the leather of one embodiment can be provided with antiviral properties by containing zirconium phosphate particles as an antiviral agent in the outermost topcoat layer or overcoat layer.
  • the outermost coating layer can be formed by applying a coating agent.
  • the coating agent contains, for example, zirconium phosphate particles, a resin, a cross-linking agent, and water.
  • the resin of the coating agent preferably contains at least one selected from urethane resin and (meth) acrylic resin, more preferably urethane resin, and further preferably containing urethane resin and (meth) acrylic resin. ..
  • the coating agent preferably contains a urethane resin alone, or preferably contains a combination of a urethane resin and an acrylic resin, but may further contain other resins.
  • the coating agent may contain any additive as described below.
  • the coating agent contains water and is preferably applied to leather as an aqueous composition.
  • the amount of water is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total amount of the coating agent.
  • the composition of the coating agent will be described.
  • Antiviral agent In order to solve the above problems, the present inventors first examined the types of antiviral agents. A leather made by mixing an antiviral agent containing a metallic and organic antiviral component with a synthetic leather top coat was prepared, and the appearance, touch, light resistance, and anti-influenza activity value were tested. The results are shown in Table 6. When the leather was left for a long period of time, the zinc-glass compound made the top coat cloudy and deteriorated its appearance. The silver-zirconium compound could not suppress the discoloration within the predetermined range as expected, and the same was true for the monovalent copper compound and tungsten trioxide. The aluminum compound had grains having a diameter of about 20 ⁇ m on the coating film, and had a rough texture.
  • the cationic surfactant had a strong ability to agglomerate the resin and could not be mixed with the coating agent.
  • Triazine, imidazole, thiazole and other organic antiviral agents were good immediately after production, but their antiviral properties decreased after the light resistance test. Only an antiviral agent containing zirconium phosphate particles as a main component exhibits good antiviral properties, exhibits good light resistance, does not deteriorate the appearance and feel, and is an antiviral agent in order to solve the problems of the present invention. It was found that it can be used as an agent. However, zirconium phosphate particles may agglomerate when mixed with a coating agent, which needs to be improved in order to be coated in good condition.
  • Zirconium phosphate particles are a material that exhibits high antiviral properties. Since the zirconium phosphate particles have high adsorptivity, they can be contained in the outermost layer of the coating layer to enhance the adsorptivity of the virus and further impart a deodorizing function to the leather. Examples of commercially available zirconium phosphate particles include "NOVARON IV1000" and “Allelimove ZS-200" manufactured by TG Corporation.
  • the average particle size of the zirconium phosphate particles is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 1.5 ⁇ m or less.
  • the average particle size of the zirconium phosphate particles is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the average particle diameter of the zirconium phosphate particles can be obtained from the average value of the diameters of a predetermined number of zirconium phosphate particles observed in a predetermined region by observing the surface or cross section of the coating layer with a microscope or the like.
  • the diameter is a major axis.
  • the content of the zirconium phosphate particles is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, based on the total amount of the coating agent.
  • the content of the zirconium phosphate particles is preferably 5.0 to 17.0% by mass, more preferably 5.0 to 15.0% by mass, and more preferably 5.0 to 10.0% by mass with respect to the total solid content of the coating agent. % Is more preferable.
  • the topcoat layer or the overcoat layer is applied with an appropriate coating film thickness. If it is more than 17.0% by mass, it may agglomerate with the resin and the coating agent may not be applied.
  • zirconium phosphate particles cueing outward from the surface of the coating layer inhibit the binding of cellular sialic acid to viral hemagglutinin by binding to viral hemagglutinin, and inhibit infection to cells. Is considered to be the main mechanism. Therefore, it is preferable that the zirconium phosphate particles are cueed outward from the surface of the coating layer under appropriate conditions.
  • zirconium phosphate particles have problems that it is difficult to form a coating film due to paint aggregation and that the adhesion between layers is lowered.
  • these problems are latent in antibacterial or antiviral processing.
  • zirconium phosphate particles which have a particularly high deactivating effect on viruses. That is, by blending the zirconium phosphate particles in the coating layer of the outermost layer of the coating film and defining the adhesion amount of the zirconium phosphate particles and the thickness of the coating layer, antiviral property is imparted, durability is excellent, and discoloration is suppressed. You can get the leather that has been made. Leather having this feature can maintain the performance suitable for the durability performance required for vehicles and the like.
  • the coating layer may contain other inorganic or organic antiviral agents, antibacterial agents, or a combination thereof, in addition to the zirconium phosphate particles.
  • an organic antiviral agent or an organic antibacterial agent can be used in combination with zirconium phosphate particles because it does not easily affect the durability of the coating layer.
  • examples of the organic antiviral agent or the organic antibacterial agent include "Pacific Beam Mold DS" manufactured by MIC.
  • the total amount of the organic antiviral agent and the organic antibacterial agent is preferably 0.5 to 10% by mass with respect to the total solid content of the coating agent. It is preferable not to use a discoloring component such as a silver compound or a zinc compound as an inorganic or organic antiviral agent.
  • the coating layer can be formed into a coating film using a coating agent containing zirconium phosphate particles, a resin, a cross-linking agent, and water, but there is a problem that aggregation occurs when the zirconium phosphate particles are mixed with an aqueous composition containing resin and water. There is.
  • the coating film having the characteristics according to one embodiment is formed into a coating film using a coating agent, the generation of aggregation is suppressed in the mixing of the zirconium phosphate particles, the resin and water, and the dispersion stability of the coating agent is maintained.
  • a coating film can be formed.
  • the type of resin may be appropriately used in the formulation of an aqueous coating agent. By selecting it, it is possible to prevent the occurrence of aggregation.
  • the water-diluted solution of zirconium phosphate particles is strongly acidic, and ordinary water-based paints for leather are weakly alkaline, but when zirconium phosphate particles are mixed with water-based paints, the aggregation itself depends on the type of resin rather than the paint pH. Tend.
  • the coating agent can be uniformly applied to the surface of the leather by using a spray coat, and the distribution of zirconium phosphate particles can be made more uniform on the surface of the leather. .. Generally, in the case of synthetic leather that is not spray-coated, it can be uniformly coated with a roll coat (gravure coating, casting coating).
  • the coating layer further contains a resin.
  • the resin include urethane resin, (meth) acrylic resin, (meth) acrylic-vinyl acetate resin, styrene-butadiene resin, (meth) acrylonitrile-butadiene resin, butadiene- (meth) acrylic resin, vinylidene chloride resin and the like. Can be mentioned. These may be used alone or in combination of two or more. It was found that when the zirconium phosphate particles were added to a topcoat coating agent for automobile seats having an existing composition, they acted on the resin to cause aggregation, making it difficult to form a coating film and reducing the adhesion between layers.
  • the resin preferably comprises at least one selected from the group consisting of urethane resin and (meth) acrylic resin.
  • the coating film strength of the coating film can be sufficiently obtained, the zirconium phosphate particles can be exposed from the surface of the coating film with an appropriate coating film strength, and the zirconium phosphate particles are less likely to fall off from the coating layer. Can be done.
  • the resin more preferably contains a urethane resin, for example, it is preferable to contain the urethane resin alone or a combination of the urethane resin and the (meth) acrylic resin. In either case, other resins may be further added.
  • the combination of the urethane resin and the (meth) acrylic resin may be a mixture of the urethane resin and the (meth) acrylic resin, or a copolymer of the urethane resin and the acrylic resin.
  • the urethane resin may be a two-component polyurethane resin.
  • the urethane resin examples include polyester-based polyurethane, polyether-based polyurethane, polycarbonate-based polyurethane, polyester / polyether-based polyurethane, and the like.
  • the urethane resin is preferably water-dispersible or water-soluble.
  • urethane resins examples include STAHL “Mating MT”, “D-2019”, “Novomatt GG”, “Novomatt DD”, “Promul 59", “Top 2007”, “WT-43492”; LANXESS. "Finish 85UD” manufactured by; “UW Clear # 7" manufactured by Tohpe Corporation, “UW Matt Clear # 7” and the like can be mentioned.
  • the (meth) acrylic resin may be a methacrylate, an acrylate, a methacrylic acid, an acrylic acid, or a homopolyma or a copolymer of two or more combinations thereof. Furthermore, it may be a copolymer with other monomers or oligomers. These may be used alone or in combination of two or more.
  • the (meth) acrylic resin is preferably water-dispersible or water-soluble.
  • Examples of commercially available (meth) acrylic resins include “Matting EO” and “Protector SR” manufactured by STAHL; and “A2000L” manufactured by LANXESS.
  • acrylic resins examples include "LEPTON ULTRASOFT NT” manufactured by STAHL; "SB300, HYDRHOLACCR-15, HYDRHOLACAD-1, OPTI-MAT TA-1000, OPTI-MAT UD4" manufactured by LANXESS. Can be mentioned.
  • the combination of the urethane resin and the (meth) acrylic resin may be a mixture of the urethane resin and the (meth) acrylic resin, or may be a copolymer of the urethane resin and the (meth) acrylic resin.
  • Examples of commercially available products in which a urethane resin and a (meth) acrylic resin are combined include "CT-43375" manufactured by STAHL.
  • STAHL's “Matting MT, Novomatt GG, Matting EO, CT-43375", etc., are among the above-mentioned examples of commercially available products.
  • LANXESS "Finish 85UD” or the like can be preferably used alone or in combination.
  • the resin can be divided into a clear resin, a matte-containing resin, and a low-gloss resin according to its matte function, and the combination can be examined and used according to the required glossiness and tactile sensation.
  • the resin can be classified based on the Gloss value of the resin coating film.
  • the resin to be evaluated is applied to the substrate (using a # 14 rod) with a Wet mass of 32 g / m 2 using a bar coater, and dried and cured to prepare the resin coating film.
  • a concealment rate test paper (B type / black) manufactured by TP Giken Co., Ltd. is used as the base material.
  • the Gloss value of the resin coating film is measured and obtained by using "Gloss Checker IG-320" manufactured by HORIBA, Ltd.
  • the clear resin it is preferable to use a resin in which the Gloss value of the resin coating film exceeds 2.0%.
  • the matting agent-containing resin it is preferable to use a resin having a Gloss value of the resin coating film of 2.0% or less.
  • the low-gloss resin it is preferable to use a resin having a Gloss value of the resin coating film of 2.0% or less.
  • the clear resin is a resin that does not have a matte function, and has a strong luster when formed into a coating film.
  • LANXESS "Finish 85UD (Gloss value of resin coating 78.0%), UW Clear # 7 (Gloss value of resin coating 77.0%)", LANXESS “AQUAQDERM Finish HAT” (resin)
  • CT-43375 Gloss value of resin coating film 2.1%) manufactured by STAHL can be mentioned.
  • the content of the clear resin is 0 to 70% by mass, more preferably 20 to 50% by mass, based on the total solid content of the coating agent, from the viewpoint of obtaining an appropriate luster.
  • the matting agent-containing resin is a resin mixed with a matting agent such as silica in advance in order to impart a matte function.
  • the content of the matting agent is about 1 to 30% by mass, preferably 1 to 10% by mass, based on the total solid content of the matting agent-containing resin.
  • urethane resin "Matting MT (Gloss value of resin coating film 1.4%)” made by STAHL, "UW Matte Clear # 7" made by Tohpe, etc.
  • acrylic resin "Matting EO, Protector SR” made by STAHL, etc. Can be mentioned.
  • the content of the matting agent-containing resin is 0 to 70% by mass, more preferably 20 to 50% by mass, based on the total solid content of the coating agent.
  • the low-gloss resin is a resin in which the resin itself has a matte function. When dried, the surface becomes rough and diffusely reflects light, which reduces the glossiness of the coating film.
  • the low-gloss resin means a resin having a matting function without substantially containing a matting agent. Therefore, the low-gloss resin is preferably a resin having a matting agent content of 5% by mass or less, and more preferably a resin containing no matting agent.
  • Examples of the (meth) acrylic resin include "OPTI-MAT UD4" manufactured by LANXESS (Gloss value of the resin coating film is 0.5%).
  • Silica used as a matting agent gives a dry touch to the touch, so the content is limited in products that require a wet touch. In this respect, since the low-gloss resin has a wet touch, it is expected that silica will be supplemented to reduce the glossiness. It turns out to be easy to use, and the amount used is limited.
  • the content of the low-gloss resin is preferably 0 to 25% by mass, more preferably 10 to 25% by mass, and further preferably 10 to 20% by mass with respect to the total solid content of the coating agent.
  • it is 10% by mass or more, an appropriate glossiness and a wet touch can be obtained in a well-balanced manner by reducing the amount of the matting agent-containing resin and silica used. If it exceeds 25% by mass, it may aggregate with the zirconium phosphate particles and the coatability of the coating agent may be deteriorated.
  • the above-mentioned resins may be used alone or in combination of two or more.
  • the total amount of the resin is the solid content, preferably 40 to 90% by mass, more preferably 50 to 80% by mass, based on the total amount of the coating layer. More preferably, the total content of the resin is 40.0 to 70.0% by mass, preferably 45.0 to 65.0% by mass, based on the total amount of the coating layer. Is more preferable.
  • the urethane resin has a solid content of preferably 30 to 100% by mass, more preferably 40 to 70% by mass, based on the total amount of the resin components contained in the coating layer.
  • the solid content of the (meth) acrylic resin is preferably 10 to 70% by mass, more preferably 30 to 50% by mass, based on the total amount of the resin components contained in the coating layer.
  • the copolymer of the urethane resin and the (meth) acrylic resin has a solid content of preferably 10 to 70% by mass, more preferably 30 to 50% by mass, based on the total amount of the resin components contained in the coating layer.
  • the antiviral leather coating agent is characterized by containing zirconium phosphate particles, a resin, and water.
  • the leather coating agent is preferably a resin having a solid content of 40.0 to 70.0% by mass, a cross-linking agent having a content of 6.0 to 35.0% by mass, and 5.0 to 17.0. Includes zirconium phosphate particles in mass%.
  • the resin of the leather coating agent preferably contains at least one selected from the group consisting of urethane resin and (meth) acrylic resin, more preferably contains urethane resin, and more preferably urethane resin and (meth) acrylic resin. It is a combination of.
  • this coating agent has stable dispersibility, it is possible to prevent the occurrence of agglomeration of components and improve the coatability on leather. Since the zirconium phosphate particles act as an antiviral agent, a silver-based antiviral agent is unnecessary or the blending amount thereof can be reduced, and the occurrence of discoloration derived from silver can be prevented.
  • the total amount of the resin components is the solid content, preferably 5 to 50% by mass, more preferably 10 to 30% by mass, still more preferably 10 to 20% by mass, based on the total amount of the coating agent composition.
  • the urethane resin has a solid content of preferably 30 to 100% by mass, more preferably 40 to 70% by mass, based on the total amount of the resin components contained in the coating agent.
  • the solid content of the (meth) acrylic resin is preferably 10 to 70% by mass, more preferably 30 to 50% by mass, based on the total amount of the resin components contained in the coating agent.
  • the low-gloss resin has a solid content of 1 to 10% by mass, more preferably 2 to 6% by mass, based on the total amount of the resin components contained in the coating agent.
  • Cross-linking agent for example, an isocyanate-based cross-linking agent, a carbodiimide-based cross-linking agent, or the like can be used.
  • the coating layer contains a urethane resin
  • the coating film property can be further improved by combining with an isocyanate-based cross-linking agent.
  • the carbodiimide-based cross-linking agent can particularly effectively improve the coating film property when a carboxy group is introduced at the end of the urethane resin or the (meth) acrylic resin.
  • a two-component polyurethane resin is used, the curing of the coating film can be further promoted by combining it with a multivalent isocyanate such as diisocyanate.
  • the content of the solid content of the cross-linking agent is preferably 6.0 to 35.0% by mass with respect to the total solid content of the coating agent, and in the case of a top coat for automobile seats where a high degree of wear resistance is required, the content is preferably 6.0 to 35.0% by mass. It is preferably 20% by mass or more. If it is less than 6.0% by mass, the desired wear resistance cannot be obtained, and if it exceeds 35.0% by mass, the coating film becomes hard and may be easily cracked at the time of bending.
  • Examples of commercially available isocyanate-based cross-linking agents include “Hardener CN”, “IW.80”, “XR5540” manufactured by STAHL, “AQUADERM XL50” manufactured by LANXESS; and “UW Fix HD” manufactured by Tohpe Corporation.
  • Examples of commercially available carbodiimide-based cross-linking agents include “XR-13906, XR-5525” manufactured by STAHL.
  • the coating layer can contain any additive. Any additive may be a component that can be added to ordinary coating agents. Examples of the additive include a tactile agent, a leveling agent, a thickener, a matting agent, a pigment and the like. These may be used alone or in combination of two or more. In addition to the zirconium phosphate particles, the coating agent may contain other inorganic particles such as silica.
  • the tactile agent is a component that adjusts the tactile sensation of leather in the finished state of the coating layer. It also has the effect of making the surface of the coating film slippery and improving wear resistance.
  • a silicone-based tactile agent such as hydroxypolydimethylsiloxane or aminopolydimethylsiloxane can be used.
  • examples of commercially available silicone-based tactile agents include "WAX DS”, “WF-5227”, “WF-5226con”, “HM-13377” manufactured by STAHL; "Rosilk LA2229, Rosilk 2000” manufactured by LANXESS. ..
  • the leveling agent has the effect of spreading evenly on the surface of the base material layer when the coating agent is applied.
  • Examples of commercially available products include “AMOLLAN SW” (polyether silicon) manufactured by STAHL, “LA-76153", “LV-03”; and “Fluid H” manufactured by LANXESS.
  • the thickener increases the viscosity of the coating agent so that it does not flow too much on the surface of the base material layer, and examples of commercially available products include “UW Additive RO” manufactured by Tohpe Corporation.
  • the matting agent has the effect of reducing the gloss of the coating layer, and silica is mainly used. It has the effect of making the tactile sensation dry, and it is desirable to reduce the amount used when a wet tactile sensation is desired.
  • the matting agent preferably has a solid content of 0 to 20% by mass, more preferably 0 to 10% by mass, based on the coating layer.
  • a solid content of 0 to 20% by mass more preferably 0 to 10% by mass, based on the coating layer.
  • "Dull # 1A" solid content 16% by mass
  • the solid content of any additive is preferably 0 to 25.0% by mass, more preferably 5.0 to 15.0% by mass, based on the total solid content of the coating agent.
  • the color coat layer is a layer formed on the base coat layer and having a colorant for coloring leather.
  • the coating agent for the color coat layer contains a coloring material and a resin as main components.
  • the solid content of the resin is preferably 15 to 30% by mass, more preferably 20 to 25% by mass, based on the total amount of the coating agent. Further, with respect to the total amount of the solid content of the coating agent, 50 to 90% by mass is preferable, and 60 to 80% by mass is more preferable.
  • the resins are urethane resin, acrylic resin, copolymer of urethane resin and acrylic resin, (meth) acrylic-vinyl acetate resin, styrene-butadiene resin, (meth) acrylonitrile-butadiene resin, butadiene- (meth) acrylic resin, chloride.
  • Examples include vinylidene resin. These may be used alone or in combination of two or more. It may be a urethane resin, a mixture of a urethane resin and an acrylic resin, a copolymer of a urethane resin and an acrylic resin, or a two-component polyurethane resin.
  • the coating agent for the color coat layer may further contain a cross-linking agent.
  • the color coat layer may be formed with a curable ink.
  • the color coat layer can be formed by applying an ink paint containing a polymerizable compound and a coloring material.
  • the polymerizable compound include a two-component polyurethane resin, urethane acrylate, epoxy acrylate, polyester acrylate and the like.
  • the ink paint for forming the color coat layer may further contain a reactive diluent.
  • the coloring material may be either a pigment or a dye, and a coloring material having a color according to the intended use may be used.
  • the coating agent for the color coat layer may further contain additives such as a tactile sensation agent and a leveling agent, or a combination thereof.
  • the color coat layer needs to be finished to have a softness between the base coat layer and the top coat layer so that the coating layer adheres well, and is adjusted by the selection of the resin and the amount of the cross-linking agent.
  • the base coat layer is a coating layer provided on the base material layer, and is provided for the purpose of enhancing the adhesion between the soft base material layer and the hard top coat layer or the color coat layer, and these layers are provided. It is finished softer than.
  • the coating agent for the base coat layer contains resin and water, and may contain a cross-linking agent if necessary. Examples of the resin and the cross-linking agent include the components exemplified in the above-mentioned color coat layer.
  • the solid content of the resin is preferably 15 to 25% by mass, more preferably 20 to 25% by mass, based on the total amount of the coating agent in the base coat layer.
  • the base coat layer may further contain an auxiliary agent, a tactile agent, a pigment, or a combination thereof.
  • the base material layer of leather may be either natural leather or synthetic leather.
  • the natural leather those manufactured by a conventionally known method can be used. For example, it is a method of manufacturing raw hides of cows and pigs through a pretreatment step, a tanning step, a retanning step, a dyeing step, a greasing step, a drying step and the like.
  • any treatment such as surface buffing may be applied.
  • synthetic leather a dry method manufactured by a transfer coating method and a wet method manufactured by a wet manufacturing machine are known as manufacturing methods, but synthetic leather manufactured by either method can be used. Further, the dry method includes a calendar method using a paste-like resin material and a casting method using a liquid resin material, and any method may be used.
  • the coating agent of the color coat layer is applied to the surface of the cured base coat layer in the same manner as the base coat layer, and dried under the same conditions as the base coat. Coating of the color coat layer may be omitted when covering such as black color (concealing the color of the base material so as not to appear) is not required, or when high wear requirements are not required.
  • the coating agent for the top coat layer and the overcoat layer can be obtained, for example, by mixing a resin, a cross-linking agent, water, and an arbitrary component, and adding zirconium phosphate particles while stirring the mixed solution.
  • the details of the composition of the coating agent are as described above.
  • the coating agent is applied on the cured color coat layer, or on the dried base coat layer when the color coat layer is omitted, and dried.
  • the method of coating and drying is the same as that of the base coat layer and the color coat layer.
  • the amount of the coating agent applied to the leather of the outermost layer may be appropriately adjusted in order to obtain the amount of the zirconium phosphate particles adhered to the leather in the above-mentioned coating layer per unit area.
  • the amount of the outermost coating agent applied to the leather varies depending on the ratio of the solid content of the zirconium phosphate particles and the like, but is preferably 10 to 50 g / m 2 and more preferably 20 to 30 g / m 2 , for example.
  • the method for producing leather according to one embodiment can include applying a coating agent containing zirconium phosphate particles, a urethane resin, a cross-linking agent, and water to the leather base material.
  • each coating layer gradually proceeds in the drying step, and is finally completed after about 2 weeks have passed at room temperature after the outermost coating layer is dried. If it is desired to accelerate the curing, the temperature may be as high as about 80 ° C.
  • the coating layer is cured by cross-linking by the reaction between the hydroxyl group of the resin and the cross-linking agent and by forming a network by bonding the cross-linking agents with each other through water.
  • the coating layer is mainly cured by cross-linking due to the reaction between the carboxyl group of the resin and the cross-linking agent.
  • the leather on which the coating layer is formed will be described below.
  • the leather can be formed by laminating a base coat layer, a color coat layer, and a top coat layer in this order on a leather base as a base material layer. Further, an overcoat layer may be further provided on the topcoat layer.
  • the base coat layer, the color coat layer, the top coat layer, and the overcoat layer may be a single layer or a plurality of layers having different components from each other. Further, the color coat layer may be omitted depending on the characteristics required for the leather.
  • the outermost coating layer of the coating film is 0.5 to 2.0 g / m 2 zirconium phosphate particles, 1.2 to 7.0 g / m 2 resin, and 0. .Contains 18 g to 3.5 g / m 2 of cross-linking agent.
  • the amount of zirconium phosphate particles adhered to the outermost coating film of the coating film is 0.5 to 2.0 g / m 2 , more preferably 0.8 to 2.0 g / m 2 , it has good antiviral properties. Can be obtained, discoloration due to light irradiation can be suppressed, and peeling of the coating film can be avoided.
  • the resin and the cross-linking agent are necessary for imparting wear resistance, and if the value is less than the lower limit, sufficient wear resistance cannot be obtained. If the upper limit is exceeded, the surface may become hard and the texture may be impaired, or the surface may be easily cracked due to bending.
  • the cross-linking agent is bonded to the resin to form a cross-linked structure.
  • the crosslinked resin is specified as the total amount of the resin and the crosslinking agent, and therefore, it is preferably contained at 1.38 to 10.5 g / m 2 .
  • Antiviral properties are such that zirconium phosphate particles cueing outward from the surface of the outermost coating layer bind to viral hemagglutinin, thereby inhibiting the binding of cellular sialic acid to viral hemagglutinin and inhibiting infection to cells. It is considered to be the main mechanism. Therefore, it is preferable that the zirconium phosphate particles are cueed outward from the surface of the coating layer under appropriate conditions. As one of the conditions for cueing, it is preferable to control the thickness of the coating layer containing the zirconium phosphate particles to 3.0 ⁇ m or more. If the coating layer has a thickness of less than 3.0 ⁇ m, the arrangement of the zirconium phosphate particles is not stable, and sufficient antiviral properties may not be obtained.
  • the zirconium phosphate particles are preferably 0.5 g / m 2 or more, more preferably 0.8 g / m 2 or more, and even more preferably 1.0 g / m 2 or more per unit area of the outermost coating layer. As a result, the zirconium phosphate particles are exposed from the surface of the coating layer at a sufficient ratio, and the antiviral property can be further enhanced.
  • the zirconium phosphate particles are preferably 2.0 g / m 2 or less, more preferably 1.5 g / m 2 or less per unit area of the outermost coating layer.
  • the mass of zirconium phosphate particles per unit area of the outermost coating layer can be measured by elemental analysis by SEM-EDX (energy dispersive X-ray analyzer). As another method, it can be calculated from the formulation of the coating agent forming the coating layer, the mass of the zirconium phosphate particles in the solid content, the film thickness of the coating layer, and the like.
  • the thickness of the outermost coating layer is preferably 3.0 ⁇ m or more, more preferably 4.0 ⁇ m or more.
  • the zirconium phosphate particles are exposed from the surface of the coating layer at a sufficient ratio, and the antiviral property can be further enhanced. Since the zirconium phosphate particles are exposed from the surface of the coating layer, when the virus adheres to the coating layer, the zirconium phosphate particles exposed from the coating surface come into contact with the virus, and the inactivation of the virus can be further promoted. .. In addition, the durability of the coating layer itself can be ensured.
  • the thickness of the outermost coating layer is preferably 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less, still more preferably 7.0 ⁇ m or less. This makes it possible to further maintain the texture and bending resistance of the leather.
  • the method for measuring the thickness of the coating layer is to cut the leather to expose the cross section, observe the cross section with a microscope or the like, and measure the thickness of the coating layer.
  • it can be calculated from the formulation of the coating agent forming the coating layer from the mass of the solid content, the specific gravity of the solid content, the coating amount of the coating agent, and the like.
  • the outermost coating layer is a resin having a content of 40.0 to 70.0% by mass, a cross-linking agent having a content of 6.0 to 35.0% by mass, and 5.0 to 17 with respect to the total solid content of the coating layer. It is preferable to contain zirconium phosphate particles in an amount of 0.0% by mass.
  • the other side surface of the outermost coating layer is a crosslinked resin in an amount of 46.0 to 95.0% by mass and zirconium phosphate particles in an amount of 5.0 to 17.0% by mass based on the total solid content of the coating layer. It is preferable to include and.
  • the low-gloss resin is contained in an amount of 10 to 25% by mass with respect to the total solid content.
  • a leather base as a base material layer, a base coat layer, a color coat layer, a top coat layer, and an overcoat layer are provided in this order, and the overcoat layer is a coating layer according to an embodiment.
  • This leather can be preferably used as leather for vehicles.
  • the coating layer is formed as the overcoat layer, for example, the resin is 50 to 70% by mass, the zirconium phosphate particles are 7 to 21% by mass, and the tactile agent is 10 to 15% by mass with respect to the total amount of the coating layer. It is preferably 7 to 20% by mass, the cross-linking agent is 7 to 20% by mass, and the total amount of other components such as the leveling agent and the thickener is 5% by mass or less.
  • An example of the coating layer as the overcoat layer preferably contains a polyester-based urethane resin and a (meth) acrylic resin.
  • the polyurethane resin and the (meth) acrylic resin are preferably 3: 7 to 7: 3 in mass ratio, and more preferably 4: 6 to 6: 4.
  • Other examples of the coating layer as the overcoat layer preferably include a polyether urethane resin, a polycarbonate urethane resin, and a (meth) acrylic resin.
  • the ratio of the polyether urethane resin and the polycarbonate urethane resin is preferably 1: 8 to 3: 7, and the mass ratio of the urethane resin and the (meth) acrylic resin is 4: 6 to 9. 1 is preferable.
  • the leather base as the base material layer, the base coat layer, the color coat layer, and the top coat layer are provided in this order, and the top coat layer is the coating layer according to the embodiment. ..
  • This leather can be preferably used as leather for furniture.
  • the coating layer is formed as the top coat layer, for example, the resin is 40 to 60% by mass, the zirconium phosphate particles are 10 to 30% by mass, and the tactile agent is 2 to 15 with respect to the total amount of the coating layer. It is preferably 10% by mass, the cross-linking agent is 10 to 20% by mass, and the total amount of other components such as the leveling agent and the thickener is 5% by mass or less.
  • An example of the coating layer as the overcoat layer preferably contains a polyether urethane resin.
  • the amount of the polyether urethane resin is preferably 0.9 parts by mass or more with respect to 1 part by mass of the resin contained in the coating layer, and the resin contained in the coating layer may consist only of the polyether urethane resin.
  • the thickness of the base coat layer may be 5 to 50 ⁇ m, 10 to 35 ⁇ m, or 7 to 10 ⁇ m.
  • the thickness of the color coat layer may be 5 to 25 ⁇ m and may be 7 to 10 ⁇ m.
  • the thickness of the topcoat layer may be 5 to 50 ⁇ m, 10 to 25 ⁇ m, or 10 to 15 ⁇ m.
  • the base coat layer, the color coat layer, and the top coat layer described above do not contain zirconium phosphate particles. However, this does not apply when the top coat layer is used as the coating layer.
  • the zirconium phosphate particles are 0.5% by mass or less, preferably 0.1% by mass or less, and preferably not detected with respect to the total amount of each layer. It is preferable that the zirconium phosphate particles are contained only in the outermost layer because the layer containing the zirconium phosphate particles may have a reduced adhesiveness with the layer directly above due to the Lotus effect.
  • the base coat layer, the color coat layer, and the top coat layer described above may contain other inorganic or organic antiviral agents or antibacterial agents, or a combination thereof.
  • an organic antiviral agent or an antibacterial agent can be used because it does not easily affect the durability of each layer. This makes it possible to impart antiviral or antibacterial properties not only to the surface of the leather but also to the inside of the leather as a whole.
  • the organic antiviral agent or antibacterial agent include "Pacific Beam Mold DS" manufactured by MIC.
  • the total amount of the organic antiviral agent and the antibacterial agent is preferably 2 to 5% by mass with respect to the total amount of each layer.
  • the leather to which the coating agent is applied is a leather in which a base coat layer, a color coat layer, and a top coat layer are laminated in this order on a leather base as a base material layer, and the coating agent is applied on the top coat layer.
  • the overcoat layer can be formed as a coating layer.
  • leather suitable for vehicle use can be provided.
  • the leather to which the coating agent is applied is a leather in which a base coat layer and a color coat layer are laminated in this order on a leather base as a base material layer, and a coating agent is applied on the color coat layer to provide a coating layer.
  • the top coat layer can be formed as. In this method, leather suitable for furniture applications can be provided. It should be noted that whether or not to form an overcoat is determined by the required performance, so it is not always applicable only to the intended use.
  • the leather according to one embodiment is formed by exposing zirconium phosphate particles to the outermost layer, and since the zirconium phosphate particles exert antiviral properties against various viruses, enveloped viruses and non-enveloped viruses. It can exert antiviral properties in any of the above.
  • the virus for which the leather according to one embodiment is effective include an influenza virus such as influenza A virus and influenza B virus; a virus having an envelope such as coronavirus, a calicivirus such as norovirus and cat calicivirus; and a rotavirus.
  • the leather according to [1], comprising a base material layer, a base coat layer, a color coat layer, a top coat layer, and an overcoat layer as the coating layer in this order.
  • the leather according to [1], comprising a base material layer, a base coat layer, a color coat layer, and a top coat layer as the coating layer in this order.
  • a base material layer, a base coat layer, a top coat layer, and an overcoat layer as the coating layer may be provided in this order.
  • a base material layer, a base coat layer, and a top coat layer as the coating layer may be provided in this order.
  • the coating layer further contains at least one selected from the group consisting of urethane resin and (meth) acrylic resin.
  • the coating layer contains a urethane resin.
  • the coating layer contains a urethane resin and a (meth) acrylic resin.
  • the coating layer contains 50 to 70% by mass of a resin, 7 to 21% by mass of zirconium phosphate particles, and 7 to 20% by mass of a cross-linking agent with respect to the total amount of the coating layer.
  • the coating layer contains 50 to 70% by mass of a resin, 7 to 21% by mass of zirconium phosphate particles, and 7 to 20% by mass of a cross-linking agent with respect to the total amount of the coating layer.
  • the coating layer contains 40 to 60% by mass of a resin, 10 to 30% by mass of zirconium phosphate particles, and 10 to 20% by mass of a cross-linking agent with respect to the total amount of the coating layer.
  • the coating layer includes a resin having a content of 40.0 to 70.0% by mass, a cross-linking agent having a content of 6.0 to 35.0% by mass, and 5.0 to 17 with respect to the total solid content of the coating layer. It may contain zirconium phosphate particles in an amount of 0.0% by mass.
  • the resin may be a low-gloss resin in an amount of 10 to 25% by mass based on the total solid content of the coating layer.
  • Still another embodiment is a resin having a solid content of 40.0 to 70.0% by mass, a cross-linking agent having a content of 6.0 to 35.0% by mass, and a cross-linking agent having a content of 5.0 to 17.0% by mass.
  • Still another embodiment is a method of forming a coating layer on a base material layer to produce leather, and the outermost coating layer is provided with the above leather coating agent to have a layer thickness of 3.0 ⁇ m to 10
  • the topcoat coating agent and overcoat coating agent of the formulations shown in Table 1 were prepared. Specifically, components other than the antiviral agent (zirconium phosphate) were mixed, and the antiviral agent was added while stirring the obtained mixed solution. All of the formulations shown in Table 1 did not aggregate after the addition of the antiviral agent and could be used as a coating agent. The presence or absence of agglomeration was determined by whether or not agglomeration occurred in the mixed solution when the antiviral agent was added.
  • Zirconium Phosphate "NOVARON IV1000” manufactured by TG Corporation, zirconium phosphate / silver zirconium phosphate compound (solid content 100%). Particulate matter with an average particle size of about 1 ⁇ m. Contains silver atoms but less than 0.5% by weight.
  • Acrylic resin Acrylic resin, STAHL “Protector SR” (solid content 22% by mass, silica content about 1.5% by mass).
  • Urethane resin Polyester urethane resin, STAHL “Matting MT” (solid content 31% by mass, silica content about 2.5%).
  • Urethane resin Polyether-based urethane resin, "UW Matt Clear # 7" manufactured by Toupe Co., Ltd. (solid content 34% by mass, silica content about 7.5%). The silica content is shown as a percentage of the total solid content.
  • Urethane resin Polycarbonate urethane resin, STAHL “WT-43492” (solid content 25% by mass).
  • Urethane resin Polyester-based urethane resin, "Novomatt DD” manufactured by STAHL (solid content 25% by mass).
  • [Crosslinking agent] Isocyanate cross-linking agent: "Hardener CN” manufactured by STAHL (solid content 70% by mass). “XR5540” manufactured by STAHL (solid content 50% by mass). “UW Fix HD” manufactured by Tohpe Corporation (solid content 80% by mass). Carbodiimide-based cross-linking agent: “XR-5525” manufactured by STAHL (solid content 80% by mass).
  • the method for preparing the coating agent used as the top coat or overcoat is as follows.
  • the solid content composition of the coating agent is as shown in Table 1.
  • [Prescription 8-2] It was prepared in the same manner as in Formulation [8-1] except that 100 parts by mass of "HM-13377” was used instead of 70 parts by mass of "Rosilk 2229". The total solid content of the coating agent is 32.0% by mass.
  • [Prescription 8-3] It was prepared in the same manner as in Formulation [8-1] except that "Finish 85UD” was 150 parts by mass, “Matting MT” was added by 200 parts by mass, and "Dull # 1A” was not used. The total solid content of the coating agent is 34.7% by mass.
  • [Prescription 8-4] It was prepared in the same manner as in [Prescription 8-3] except that 100 parts by mass of "HM-13377” was used instead of 70 parts by mass of "Rosilk 2229". The total solid content of the coating agent is 33.3% by mass.
  • Natural leather was prepared using the coating agent of Formulation A and its antiviral property was evaluated.
  • a leather (“Avante” manufactured by Midori Auto Leather Co., Ltd.) was prepared in which a base coat layer, a color coat layer, and a top coat layer were laminated in this order on a natural leather base as a base material layer.
  • the coating agent of Formulation A was applied to leather by a spray method under the conditions shown in Table 3-1 and dried at 80 ° C. to form an overcoat layer as a coating layer.
  • the amount of zirconium phosphate applied per unit area was calculated from the amount of overcoating agent applied.
  • the amount of zirconium phosphate compounded in leather 4 and leather 6 is doubled, leather 5 is tripled, leather 7 is quadrupled, and leather 9 is 1. I quadrupled it.
  • the antiviral activity was evaluated by the following procedure.
  • the antiviral activity value was evaluated as good at 2.0 or higher based on the antiviral standard of SIAA (Antibacterial Product Technology Council) with 2.0 as the standard.
  • the results are shown in Table 3-1.
  • the antiviral test was performed according to the plaque method of ISO 21702 "Measurement of antiviral activity on plastics and other non-porous surfaces”.
  • Feline calicivirus (ATCC-VR782) and influenza virus (ATCC-VR1679) were used as test viruses.
  • the anti-feline calicivirus activity could be sufficiently obtained, so that the thickness of the coating layer was 3.0 ⁇ m or more, and the amount of zirconium phosphate applied was 0.8 to 2.
  • Synthetic leather In the following procedure, synthetic leather 8 using the base cloth as a base was produced by a casting method. A synthetic leather was produced by adhering a film formed by applying a polyurethane resin skin layer 1 and a skin layer 2 (intermediate layer) and an adhesive layer on a release paper and a base cloth. Then, a surface treatment layer to which an antiviral agent was added was applied to the synthetic leather peeled off from the release paper for finishing. A base coat, a color coat, a top coat, and an overcoat layer containing zirconium phosphate based on Formula A were laminated in the same manner as in the case of natural leather described above. The conditions for overcoating are shown in Table 3-2. Leathers 10, 11, 12, 13, 8, and 14 correspond to the conditions of leathers 1, 2, 3, 4, 5, and 9, respectively. Synthetic leather corresponding to leathers 6 and 7 has not been produced, but it is presumed that it does not have sufficient antiviral properties due to its thin film thickness.
  • the anti-influenza virus activity was evaluated by the following procedure. Based on the SIAA certification criteria, the anti-influenza virus activity value was evaluated as good at 2.0 or higher based on 2.0. The results are shown in Table 3-2.
  • the antiviral test was performed according to the plaque method of ISO 21702 "Measurement of antiviral activity on plastics and other non-porous surfaces”. Influenza virus (ATCC-VR1679) was used as the test virus. Since good anti-influenza activity values were obtained for leathers 11, 13, 8 and 14, a good anti-influenza activity value was obtained when the zirconium phosphate coating amount was 0.5 g / m 2 or more and the film thickness was 3.0 ⁇ m or more. It is considered to be a condition of.
  • any base material layer can be obtained by providing the overcoat layer under the conditions of a zirconium phosphate coating amount of 0.5 g / m 2 or more and a film thickness of 3.0 ⁇ m or more.
  • a zirconium phosphate coating amount of 0.5 g / m 2 or more and a film thickness of 3.0 ⁇ m or more.
  • the conditions of the zirconium phosphate coating amount of 0.8 g / m 2 or more and the film thickness of 3.0 ⁇ m or more, good antiviral properties against both feline calicivirus and influenza virus are exhibited in natural leather, which is more widespread. It is possible to provide effective anti-virus leather for various virus species. If the amount of zirconium phosphate applied exceeds 2.0 g / m 2 , problems will occur in terms of discoloration at high temperature and high humidity and during
  • the anti-influenza virus (ATCC-VR1679) activity value of synthetic leather 8 was measured by the same procedure as the above-mentioned anti-virus evaluation. Using synthetic leather 8, a light resistance test was conducted under the same conditions as above, and then the activity value of the anti-influenza virus was measured by the same procedure as above.
  • the light resistance test was performed under the condition of irradiation equivalent to 84 MJ. The light resistance test was evaluated using a gray scale for discoloration and fading.
  • the evaluation of the Tabor wear test was the same as that of no additive, and the evaluation was 4, and the grade was slightly lower in the light resistance test. It sufficiently retained the durability required for vehicle leather.
  • the tabor wear test grade 4 was the same as that without addition up to a zirconium phosphate coating amount of 2.5 g / m 2 .
  • the evaluation result of the light resistance test although a slight decrease was observed with the addition of 1.0 g / m 2 , the grade 3 which was the acceptance standard was maintained up to 2.0 g / m 2 .
  • the leather coated with the present invention has sufficient wear resistance and light resistance as leather for automobile seats in the range where the amount of zirconium phosphate added is 2.0 g / m 2 or less. Understand.
  • Formulation 8-5 was evaluated using natural leather with an overcoat formed under the conditions of a zirconium phosphate coating amount of 1.0 g / m 2 and a film thickness of 4.0 ⁇ m. As a result, Tabor wear evaluation grade 4 was performed. The result of the light resistance evaluation grade 4 was obtained, and it was found that the leather for automobile seats had sufficient wear resistance and light resistance as in the formulas A and B.
  • the prescription B' is a product obtained by removing the low-gloss resin from the prescription B and increasing the amount of the clear resin instead.
  • Formulation B' was 2.4% and Formulation B was 1.5%, showing the effect of the low gloss resin.
  • the durability of the leather on which the top coat was formed by using the coating agents of Formulations 8-1, 8-2, 8-3 and 8-4 was evaluated.
  • the coating agents of Formulations 8-1, 8-2, 8-3 and 8-4 were applied to the leather by a spray method so as to have zirconium phosphate particles 1.0 g / m 2 and a film thickness of 4.0 ⁇ m, and the temperature was 80 ° C. To form a topcoat layer as a coating layer.

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PCT/JP2021/037289 2020-10-08 2021-10-08 皮革、皮革コーティング剤、及び皮革の製造方法 WO2022075438A1 (ja)

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JP2013064111A (ja) * 2011-09-15 2013-04-11 Rohm & Haas Co 皮革に使用するためのポリ（エチレンオキシド）含有低光沢水性コーティング組成物
JP2013103971A (ja) * 2011-11-11 2013-05-30 Midori Hokuyo Kk 皮革表面の傷による凹凸が隠蔽されている自動車シート用天然皮革及びその製造方法
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CN111607974A (zh) * 2020-05-14 2020-09-01 加通汽车内饰(常熟)有限公司 一种耐磨性好、具有类肤手感的人造革及其制备方法

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JPH08157900A (ja) * 1994-12-12 1996-06-18 Aroota:Kk 皮革、毛皮及び天然繊維並びに該天然繊維を主体とした繊維製品の処理剤とそれによる処理方法
WO2007080973A1 (ja) * 2006-01-16 2007-07-19 Idemitsu Technofine Co., Ltd. 抗菌性成形体、積層体、断熱材、および、合成皮革製品
JP2013064111A (ja) * 2011-09-15 2013-04-11 Rohm & Haas Co 皮革に使用するためのポリ（エチレンオキシド）含有低光沢水性コーティング組成物
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