Material having consistency between appearance and touch feeling

Abstract

To provide a material having consistency between visual sense (appearance) and tactile sense (touch feeling) that can satisfy satisfaction and ownership desire.SOLUTION: A material of the present invention has a value of n of 3 or more and 50 or less when fitting the specular component of reflectance, measured by observing reflected light at multiple angles upon light incidence on its surface, using Phong's model shown in formula (1). The material surface has a dynamic friction coefficient of 0.40 or more and 1.00 or less when touched by a human hand.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a material that matches the appearance and feel.

Background Art

[0002] In recent years, the development of materials with excellent touch has been widely carried out. For example, in the textile industry, there have been reports of hand towels that are excellent not only in water absorption and strength required for hand towels, but also in touch and usability such as the fluffy feeling of the fibers (Patent Document 1). On the other hand, in recent years, in the field of packaging, in addition to protection, high design quality has been highly required for packaging materials. In particular, packaging materials that can provide a high-class appearance have been the subject of various attempts because of their high appeal to consumers. For example, there have been reports of laminates that exhibit a high-class appearance and high design quality while using inexpensive gold printing (Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The above examples are materials that appeal to consumers for either the feel or the appearance. However, consumers judge the value of a material by looking at it with their eyes and then actually touching it to feel the texture. Thus, there is no report on a material in which both the visual (appearance) and tactile (feel) sensations match.

[0005] As a result of intensive studies by the present inventors, it has been found that by evaluating the tactile sense while evaluating the vision using the Phong reflection model (hereinafter sometimes simply referred to as the "Phong model" or "Phong's model"), a material with a consistent appearance and feel can be obtained. That is, in this embodiment, for example, when the appearance of a material is moist, the tactile sense is also moist when actually touched, so that the senses of vision (appearance) and touch (feel) are consistent and a material that can satisfy the sense of satisfaction and the desire for possession is provided.

Means for Solving the Problems

[0006] This embodiment is based on the above findings by the present inventors, and the means for solving the above problems are as follows. [1] A material in which the specular component of the reflectance obtained by observing the reflected light when light is incident on the material surface from multiple angles is fitted with the Phong model shown in the following formula (1), and the value of n is 3 or more and 50 or less, and the coefficient of kinetic friction when the surface of the material is touched by a human hand is 0.40 or more and 1.00 or less.

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[0007] According to the present embodiment, an object is to provide a material that can satisfy the sense of satisfaction and the desire for possession by matching the visual (appearance) and tactile (feel) sensations. [Brief Description of the Drawings]

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

[0009] (Material with consistent appearance and feel) The material of one embodiment of the present invention is a material with consistent appearance and feel. When the specular component of the reflectance obtained by observing the reflected light at multiple angles when light is incident on the surface of the material is fitted with the Phong model represented by the following formula (1), the value of n is 3 or more and 50 or less, and the coefficient of kinetic friction (sometimes referred to as the "kinetic friction coefficient of the hand") when the surface of the material is touched by a human hand is 0.40 or more and 1.00 or less.

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[0010] Hereinafter, examples in the case where the material is a synthetic leather or a laminate will be described in detail. However, the materials to which the present invention can be applied are not limited to synthetic leather and laminates.

[0011] (Synthetic leather) The material according to the present embodiment may be a synthetic leather (sometimes referred to as the synthetic leather according to the present embodiment). The synthetic leather according to the present embodiment has at least a base material and a layer formed of a urethane resin composition.

[0012] [Base material] As the base material, for example, fibrous base materials made of non-woven fabrics, woven fabrics, knitted fabrics, etc.; resin films, etc. can be used. As the constituent of the fibrous base material, for example, chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers; cotton, hemp, silk, wool, blended fibers thereof, etc. can be used.

[0013] As the resin film, for example, a polyethylene terephthalate film, a polycarbonate film, an acrylic resin film, a COP (cycloolefin polymer) film, a TAC (triacetyl cellulose) film, etc. can be used.

[0014] The surface of the base material may be subjected to treatments such as antistatic processing, mold release processing, water repellent processing, water absorption processing, antibacterial and deodorant processing, bacteriostatic processing, ultraviolet blocking processing, etc. as necessary.

[0015] [Urethane resin composition] The layer formed by the urethane resin composition according to this embodiment is preferably formed using the urethane resin composition described in detail below. The following urethane resin composition is one embodiment of the urethane resin composition for forming the layer formed by the urethane resin composition. The urethane resin composition according to this embodiment contains a urethane resin (X) having a polyol (A) containing a polycarbonate polyol (a1), a chain extender (B) other than the polyol (A), and a polyisocyanate (C) as essential raw materials, the polyisocyanate (C) contains an aliphatic polyisocyanate (c1) and an aromatic polyisocyanate (c2), and the content of the aliphatic polyisocyanate (c1) is in the range of 1 to 45% by mass in the polyisocyanate (C).

[0016] The polycarbonate polyol (a1) is an essential component for obtaining excellent heat resistance. However, since the polycarbonate polyol (a1) has a rigid structure, it is difficult to have flexibility, and considering that the required level has been increasing in recent years, the use of the polycarbonate polyol has been considered difficult. However, in order to ensure excellent heat resistance, the use of the polycarbonate polyol is essential, and improvements have been studied for other components.

[0017] As the polycarbonate polyol (a1), for example, polycarbonate polyols using propanediol, butanediol, pentanediol, hexanediol, decanediol, caprolactone, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, neopentyl glycol, isosorbide, etc. as raw materials can be used. These raw materials may be used alone as raw materials having a hydroxyl group or in combination of two or more thereof. Among these, from the viewpoint of further improving the balance between low-temperature flexibility and heat resistance, those using hexanediol as a raw material, those using butanediol and hexanediol as raw materials, those using butanediol and decanediol as raw materials, and those using pentanediol and hexanediol as raw materials It is preferable to use one or more polycarbonate polyols selected from the group consisting of

[0018] Specifically, as the polycarbonate diol (a1), those obtained by reacting the above raw materials with a carbonic ester and / or phosgene by a known method can be used.

[0019] As the carbonic ester, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used. These compounds may be used alone or in combination of two or more thereof.

[0020] The number average molecular weight of the polycarbonate diol (a1) is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 4,000, from the viewpoint of obtaining further excellent heat resistance and mechanical strength. The number average molecular weight of the polycarbonate polyol (a1) indicates a value measured by the gel permeation chromatography (GPC) method.

[0021] The content of the polycarbonate polyol (a1) is preferably 50% by mass or more, more preferably 70% by mass or more in the polyol (A), from the viewpoint of further improving the balance between low-temperature flexibility and heat resistance.

[0022] As the polyol (A), other polyols can be used in combination in addition to the polycarbonate polyol (a1).

[0023] As the other polyols, for example, polyether polyols, polyester polyols, polyacrylic polyols, etc. can be used. Among these, when stronger low-temperature flexibility is required, it is preferable to use a polyether polyol, and polytetramethylene glycol is more preferable.

[0024] The number average molecular weight of the other polyols is, for example, in the range of 500 to 100,000. The number average molecular weight of the other polyols indicates the value measured by the gel permeation chromatography (GPC) method.

[0025] The amount of the polyol (A) used is, for example, in the range of 50 to 95% by mass in the total of the raw materials constituting the urethane resin (X), and preferably in the range of 70 to 90% by mass.

[0026] The chain extender (B) is other than the polyol (A), for example, having a molecular weight of 50 or more and less than 500, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, trimethylolpropane, glycerin and other chain extenders having a hydroxyl group; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine and other chain extenders having an amino group can be used. These chain extenders may be used alone or in combination of two or more.

[0027] As the amount of the chain extender (B) used, for example, the range of 0.1 to 30% by mass in the total of the raw materials constituting the urethane resin (X) can be mentioned, and from the viewpoint of obtaining more excellent heat resistance, the range of 1 to 20 parts by mass is preferable.

[0028] The polyisocyanate (C) contains an aliphatic polyisocyanate (c1) and an aromatic polyisocyanate (c2) in order to obtain excellent low-temperature flexibility, and the content of the aliphatic polyisocyanate (c1) is in the range of 1 to 60% by mass in the polyisocyanate (C), which is essential.

[0029] The aromatic polyisocyanate (c2) is strong in heat resistance, but the glass transition temperature (Tg) at the time of urethanization is high, which is disadvantageous for low-temperature characteristics. On the other hand, the aliphatic polyisocyanate (c1) generally has a low glass transition temperature and is inferior in heat resistance but is advantageous for low-temperature flexibility. In the present invention, by using both of them in a specific range, even when the polycarbonate polyol (a1) is used, heat resistance and low-temperature flexibility can be achieved at a high level.

[0030] As the content rate of the aliphatic polyisocyanate (c1), from the viewpoint of further improving the balance between heat resistance and low-temperature flexibility, it is preferably in the range of 5 to 40% by mass in the polyisocyanate (C).

[0031] As the aliphatic polyisocyanate (c1), for example, hexamethylene diisocyanate, pentamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, etc. can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the balance between heat resistance and low-temperature flexibility, it is preferable to use one or more polyisocyanates selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and pentamethylene diisocyanate.

[0032] As the aromatic polyisocyanate (c2), for example, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, etc. can be used. These polyisocyanates may be used alone or in combination of two or more.

[0033] As the usage amount of the polyisocyanate (C), for example, the range of 5 to 50% by mass in the total of the raw materials constituting the urethane resin (X) can be mentioned.

[0034] As a method for producing the urethane resin (X), for example, there is a method in which the polyol (A), the chain extender (B), and the polyisocyanate (C) are charged and reacted all at once. The reaction is preferably carried out, for example, at a temperature of 30 to 100°C for 3 to 10 hours. Further, the reaction may be carried out in a solvent described later.

[0035] The total molar ratio of the hydroxyl groups of the polyol (A) and the hydroxyl groups or amino groups of the chain extender (B) and the molar ratio of the isocyanate groups of the polyisocyanate (C) [(isocyanate groups) / (hydroxyl groups and amino groups)] is preferably in the range of 0.5 to 4.0, and more preferably in the range of 0.6 to 2.0.

[0036] The number average molecular weight of the urethane resin (X) obtained by the above method is preferably in the range of 5,000 to 1,000,000, and more preferably in the range of 10,000 to 500,000 from the viewpoint of further improving the mechanical strength and heat resistance of the film. The number average molecular weight of the urethane resin (X) indicates a value measured by the gel permeation chromatography (GPC) method.

[0037] The urethane resin composition contains the urethane resin (X) as an essential component, but may contain other components as necessary.

[0038] Examples of the other components include solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, fungicides, antibacterial agents, ultraviolet absorbers, antioxidants, weather stabilizers, fluorescent brighteners, anti-aging agents, thickeners, etc. These components may be used alone or in combination of two or more.

[0039] Examples of the solvent include ketone solvents such as water, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, and sec-butyl acetate; and alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol. These solvents may be used alone or in combination of two or more.

[0040] From the viewpoints of workability and viscosity, the content of the solvent is preferably in the range of 10 to 90% by mass in the urethane resin composition.

[0041] [Method for manufacturing synthetic leather] The method for manufacturing synthetic leather according to this embodiment includes a step of forming a layer of the urethane resin composition on at least one surface of the base material. Examples of the method for forming the layer of the urethane resin composition include applying the urethane resin composition using an applicator, a bar coater, a knife coater, a T-die coater, a roll coater, etc., and drying at a temperature of, for example, 50 to 140°C for 30 seconds to 10 minutes.

[0042] The thickness of the layer formed by the urethane resin composition is appropriately determined according to the intended use, and is, for example, in the range of 0.001 to 10 mm.

[0043] The layer formed by the urethane resin composition is excellent in heat resistance and low-temperature flexibility, and Touch Since the feeling can be adjusted, it is used as the surface layer and the surface treatment layer of synthetic leather.

[0044] (Laminate) The material according to this embodiment may be a laminate (sometimes referred to as the laminate according to this embodiment). The laminate according to this embodiment has a surface layer (laminated film) formed using an ultraviolet-curable varnish composition. That is, the laminate according to this embodiment has a laminated film obtained by coating and drying an ultraviolet-curable varnish composition.

[0045] [Laminated Film and Forming Method] The laminated film constituting the laminate according to this embodiment is a surface layer (also referred to as a laminated film) formed by coating the ultraviolet-curable varnish composition on a base material or on the surface of an article using the ultraviolet-curable varnish composition. Examples of the coating method of the ultraviolet-curable varnish composition include bar coater coating, roll coater coating, spray coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method, etc., and any method may be used. Regarding the coating amount of the ultraviolet-curable varnish composition, in the case of a paint directly coated on a base material, it is 5 to 20 g / m 2 , preferably, it is used under coating conditions of 8 to 15 g / m 2 . Also, when used as an overprint varnish for films, it is 3 to 12 g / m 2 , preferably, it is used under coating conditions of 5 to 10 g / m 2 .

[0046] The ultraviolet-curable composition can be cured by irradiation with energy rays such as ultraviolet rays. Regarding the irradiation energy of energy rays such as ultraviolet rays, from the viewpoint of ultraviolet curability, it is preferably in the range of 0.1 to 10 J / cm 2 , more preferably in the range of 0.2 to 5 J / cm 2 , and even more preferably in the range of 0.25 to 3 J / cm 2 . Regarding the illuminance of energy rays such as ultraviolet rays, from the viewpoints of adhesiveness and curability, it is preferably in the range of 0.001 to 2 W / cm2, more preferably in the range of 0.01 to 1.5 W / cm 2 , and even more preferably in the range of 0.05 to 1 W / cm 2 . As the ultraviolet light source, for example, known lamps such as xenon lamps, xenon-mercury lamps, metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, and LEDs can be used. Note that the irradiation energy and illuminance of ultraviolet light are based on the values measured in the wavelength range of 320 to 390 nm using a UV checker; UV Power PucK (II) (manufactured by Electronic Instrumentation and Technology).

[0047] <Ultraviolet curable varnish composition> The ultraviolet curable varnish composition used to form the surface layer (laminated film) constituting the laminate according to the present embodiment is not particularly limited, but preferably contains urethane (meth) acrylate (A), epoxy resin (B), a filler (C) containing resin beads and / or inorganic beads, polyethylene wax (D), and silicone (E).

[0048] <Urethane (meth) acrylate (A)> Urethane (meth) acrylate (A) is effective as a component for imparting flexibility to the coating film and maintaining the properties of the filler. As urethane (meth) acrylate (A), for example, those obtained by reacting a polyol (a1), a polyisocyanate (a2), and a (meth) acrylic compound (a3) having a hydroxyl group or an isocyanate group can be used.

[0049] In the present invention, "urethane (meth) acrylate" means urethane acrylate and / or urethane methacrylate, "(meth) acrylic compound" means methacrylic compound and / or acrylic compound, "(meth) acrylate" means methacrylate and / or acrylate, "(meth) acryloyl group" means methacryloyl group and / or acryloyl group, and "(meth) acrylic acid" means methacrylic acid and / or acrylic acid.

[0050] As the polyol (a1), for example, polyether polyol, polyester polyol, polycarbonate polyol, etc. can be used. These polyols may be used alone or in combination of two or more. The polyol (a1) is appropriately determined according to the type of the substrate as the adherend, but when a polycarbonate substrate with increasing demand as the substrate is used, it is preferable to use polycarbonate polyol from the viewpoint of adhesion.

[0051] As the polyisocyanate (a2), for example, aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanatomethylcyclohexane, tetramethylxylylene diisocyanate, etc. can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, from the viewpoint of further improving adhesion, it is preferable to use alicyclic polyisocyanate, and it is more preferable to use one or more polyisocyanates selected from the group consisting of 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate and diisocyanatomethylcyclohexane.

[0052] The (meth)acrylic compound (a3) having an isocyanate group or a hydroxyl group is used for the purpose of introducing a (meth)acryloyl group into the urethane (meth)acrylate (A).

[0053] In addition, examples of the (meth)acrylic compound having an isocyanate group that can be used as the (meth)acrylic compound (a3) include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, and the like. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint of easy availability of raw materials, it is preferable to use 2-(meth)acryloyloxyethyl isocyanate, and from the viewpoint of curability, it is more preferable to use 2-acryloyloxyethyl isocyanate.

[0054] Examples of the (meth)acrylic compound having a hydroxyl group that can be used as the (meth)acrylic compound (a3) include (meth)acrylic acid alkyl esters having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and hydroxyethyl acrylamide; polyfunctional (meth)acrylates having a hydroxyl group such as trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like. These compounds may be used alone or in combination of two or more. Among these, from the viewpoints of easy availability of raw materials, curability, and adhesion, it is preferable to use (meth)acrylic acid alkyl esters having a hydroxyl group, and it is more preferable to use 2-hydroxyethyl acrylate and / or 4-hydroxybutyl acrylate.

[0055] As a method for producing urethane (meth)acrylate (A) when using a (meth)acrylic compound (a3) having an isocyanate group as the (meth)acrylic compound, for example, in the absence of a solvent, a polyol (a1) and a polyisocyanate (a2) are charged and reacted to obtain a urethane prepolymer having a hydroxyl group. Then, a (meth)acrylic compound (a3) having an isocyanate group is supplied, mixed, and reacted to produce it. The above reaction is preferably carried out, for example, under the conditions of 20 to 120 °C for 30 minutes to 24 hours.

[0056] As a method for producing urethane (meth)acrylate (A) when using a (meth)acrylic compound (a3) having a hydroxyl group as the (meth)acrylic compound, for example, in the absence of a solvent, after charging a polyol (a1) and a (meth)acrylic compound (a3) into the reaction system, a polyisocyanate (a2) is supplied, mixed, and reacted to produce it; in the absence of a solvent, a polyol (a1) and a polyisocyanate (a2) are reacted to obtain a urethane prepolymer having an isocyanate group, and then a (meth)acrylic compound (a3) having a hydroxyl group is supplied, mixed, and reacted to produce it. The above reaction is preferably carried out, for example, under the conditions of 20 to 120 °C for 30 minutes to 24 hours.

[0057] When producing urethane (meth)acrylate (A), a polymerization inhibitor, a urethanization catalyst, etc. may be used as necessary.

[0058] As the polymerization inhibitor, for example, 3,5-bis-tert-butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoxyquinone), paratert-butylcatechol methoxyphenol, 2,6-di-tert-butylcresol, phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene, etc. can be used. These polymerization inhibitors may be used alone or in combination of two or more.

[0059] As the urethanization catalyst, for example, nitrogen-containing compounds such as triethylamine, triethylenediamine, and N-methylmorpholine; metal salts such as potassium acetate, zinc stearate, and tin octylate; and organometallic compounds such as dibutyltin laurate and zirconium tetraacetylacetonate can be used. These urethanization catalysts may be used alone or in combination of two or more.

[0060] In addition, when producing urethane (meth)acrylate (A), finally, for the purpose of deactivating the isocyanate groups remaining in urethane (meth)acrylate (A), an alcohol such as methanol may be added.

[0061] The weight average molecular weight of urethane (meth)acrylate (A) is preferably in the range of 500 to 50,000, more preferably in the range of 3,000 to 40,000, from the viewpoints of flexibility and suppression of curing shrinkage. The weight average molecular weight of urethane (meth)acrylate (A) indicates the value measured under the following conditions by the gel permeation chromatography (GPC) method.

[0062] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve is created using the following standard polystyrene.

[0063] 〔Standard polystyrene〕 "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0064] As the urethane (meth)acrylate (A), from the viewpoint of reducing the crosslinking density and further suppressing the curing shrinkage, it is preferably a so-called bifunctional urethane (meth)acrylate having two (meth)acryloyl groups.

[0065] From the viewpoint of the feel of the coating film, the glass transition point of the urethane (meth)acrylate (A) is preferably in the range of 30 to 60°C.

[0066] <Epoxy resin (B)> Examples of the epoxy resin (B) include various commercially available epoxy resins such as epi-bis type, novolac type, β-methyl epichlorohydrin type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, aminoglycidyl type, resorcinol type, etc. Among these, epi-bis type epoxy resin is preferably used because of its good scratch resistance of the coating film.

[0067] Examples of commercially available products of the epoxy resin (B) include bisphenol A (BPA) type products such as Epicoat (EPIKOAT) 1001, Epicoat (EPIKOAT) 1004, EP ICLON N-865, EPICLON N-870, etc. Examples of the modified novolac type epoxy resin, as examples of the epoxy resin (C-1) not containing bisphenol A, include phenol novolac type epoxy resins such as EPICLON N-730, EPICL ON N-740, EPICLON N-770, etc. manufactured by DIC Corporation, and cresol novolac type epoxy resins such as EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, AER ECN-1273 manufactured by Asahi Kasei Epoxy Co., Ltd., AER ECN-1299 manufactured by the same company, etc. Furthermore, as long as it is an epoxy resin not containing bisphenol A, it is preferable especially for hygienic and food applications because unreacted bisphenol A does not elute. Note that the epoxy resin not containing bisphenol A means an epoxy resin not containing a structure derived from the bisphenol A skeleton.

[0068] From the viewpoint of promoting crosslinking and maintaining scratch resistance, the epoxy resin (B) is preferably a bifunctional epoxy resin.

[0069] <Filler (C)> As the filler (C), it may be an inorganic filler, an organic filler or resin beads. Any one of these may be used, or two or more of them may be used in combination. The average particle diameter of the filler (C) is preferably 50 μm or less. There is no lower limit. When the particle diameter is 50 μm or more, problems such as poor abrasion resistance, product stability (sedimentation), and coating unevenness occur, and the desired tactile sensation cannot be exhibited. The upper limit of the addition amount of the filler (C) is not present, but it is preferably 50% by weight or less, and preferably 5% or more. When the addition amount of the filler is small, n becomes high and the sticky feeling becomes stronger than the moist feeling. When the addition amount of the filler exceeds 50%, product stability and coating unevenness occur, and it becomes difficult to exhibit the desired tactile sensation.

[0070] Examples of the organic filler or resin beads include organic fillers or resin beads selected from acrylic resin, urethane resin, nylon resin, polypropylene resin, or urea-based resin. Examples of the inorganic filler include inorganic fillers selected from silica (silicon dioxide), clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine silica powder.

[0071] <Polyethylene wax (D)> The ultraviolet curable varnish composition of the present invention contains polyethylene wax. From the viewpoints of the lubricity, scratch resistance, and touch feeling of the coating film, polyethylene wax is preferably used. The average particle diameter of the polyethylene wax is preferably in the range of, for example, 2 to 8 μm. When the average particle diameter of the polyethylene wax is 2 μm or more, the area of the polyethylene wax floating on the coating film surface decreases, and it is possible to prevent the problem that sufficient scratch resistance and lubricity cannot be obtained. On the other hand, when the average particle diameter of the polyethylene wax is 8 μm or less, it is possible to prevent the problem that the unevenness of the coating film surface becomes prominent and may cause poor appearance.

[0072] <Silicone (E)> The ultraviolet-curable varnish composition of the present invention contains silicone (polysiloxane). Examples of the silicone include various silicone oils such as methylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, tetradecamethylhexasiloxane, dimethylsiloxane·methyl(polyoxyethylene)siloxane·methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane·methyl(polyoxyethylene)siloxane copolymer, dimethylsiloxane·methyl(polyoxypropylene)siloxane copolymer, dimethylsiloxane·methylcetoxysiloxane copolymer, dimethylsiloxane·methylstearoxysiloxane copolymer. Among them, methylhydrogenpolysiloxane and methylpolysiloxane are preferred.

[0073] <Other components> In the ultraviolet-curable varnish composition of the present invention, it is necessary to add a photoinitiator for curing with ultraviolet rays. Also, in the present invention, it is important to contain a photopolymerization inhibitor.

[0074] Examples of the photoinitiator that can be used in the present invention include cleavage-type photoinitiators such as benzoin isobutyl ether, benzyl, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, phenylglyoxylic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and hydrogen abstraction-type photoinitiators such as benzophenone, 4-phenylbenzophenone, isophthalophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone. These can be used alone or in combination of two or more kinds.

[0075] The photopolymerization inhibitor is added for the purpose of preventing the polymerization reaction in the coating liquid during storage and storage of the paint or during the painting operation. As this component, for example, an appropriate amount of hydroquinone (HQ), methylhydroquinone (MEHQ), 3,5-dibutyl-4-hydroxytoluene (BHT), butylhydroxyanisole, etc. can be blended.

[0076] The ultraviolet-curable varnish composition of the present invention exhibits a low viscosity suitable for coating even without a solvent, but an organic solvent may be added if necessary. For example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran and dioxolane, esters such as methyl acetate, ethyl acetate, and butyl acetate, aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, toluene, isopropanol, butanol, and propylene glycol monomethyl ether can be mentioned. These may be used alone or in combination of two or more kinds. In addition, the ultraviolet-curable varnish composition of the present invention may contain various additives such as a leveling agent, a thixotropy-imparting agent, waxes other than those described above, a drying agent, a thickening agent, an anti-sagging agent, a plasticizer, a dispersant, an anti-settling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, a release agent, an inorganic pigment, an organic pigment, and a extender pigment, if necessary.

[0077] The ultraviolet-curable varnish composition of the present invention mixes the above-described components in appropriate desired ratios. The mixing ratios are not particularly limited. For example, with respect to the ultraviolet-curable varnish composition, urethane (meth)acrylate (A) is preferably contained in an amount of 50 to 90 parts by mass, more preferably 70 to 85 parts by mass. Also, with respect to the ultraviolet-curable varnish composition, epoxy resin (B) is preferably contained in an amount of 1 to 10 parts by mass, more preferably 5 to 7 parts by mass. Further, with respect to the ultraviolet-curable varnish composition, filler (C) containing resin beads and / or inorganic beads is preferably contained in an amount of 5 to 30 parts by mass, more preferably 9 to 12 parts by mass. Also, with respect to the ultraviolet-curable varnish composition, polyethylene wax (D) is preferably contained in an amount of 0.2 to 2 parts by mass, more preferably 0.4 to 1 part by mass. Moreover, with respect to the ultraviolet-curable varnish composition, silicone (E) is preferably contained in an amount of 0.1 to 1 part by mass, more preferably 0.1 to 0.5 part by mass. Furthermore, the ultraviolet-curable varnish composition of the present invention may contain a photoinitiator and a photopolymerization inhibitor. With respect to the ultraviolet-curable varnish composition, it is preferable to contain 1 to 5 parts by mass of the photoinitiator, and more preferably 1.5 to 3.5 parts by mass. Also, with respect to the ultraviolet-curable varnish composition, it is preferable to contain 0.1 to 1 part by mass of the photopolymerization inhibitor, and more preferably 0.1 to 0.5 part by mass.

[0078] As a preferred embodiment of the mixing ratio of each component of the ultraviolet-curable varnish composition, there is an ultraviolet-curable varnish composition mixed at a ratio of 50 to 90 parts by mass of urethane (meth) acrylate (A), 1 to 10 parts by mass of epoxy resin (B), and 5 to 30 parts by mass of a filler (C) containing resin beads and / or inorganic beads. Also, there is an ultraviolet-curable varnish composition mixed at a ratio of 50 to 90 parts by mass of urethane (meth) acrylate (A), 1 to 10 parts by mass of epoxy resin (B), 5 to 30 parts by mass of a filler (C) containing resin beads and / or inorganic beads, 0.2 to 2 parts by mass of polyethylene wax (D), and 0.1 to 1 part by mass of silicone (E). Furthermore, when the ultraviolet-curable varnish composition of the present invention contains a photoinitiator and a photopolymerization inhibitor, as a preferred embodiment of the mixing ratio of each component of the ultraviolet-curable varnish composition, there is an ultraviolet-curable varnish composition mixed at a ratio of 50 to 90 parts by mass of urethane (meth) acrylate (A), 1 to 10 parts by mass of epoxy resin (B), 5 to 30 parts by mass of a filler (C) containing resin beads and / or inorganic beads, 1 to 5 parts by mass of the photoinitiator, and 0.1 to 1 part by mass of the photopolymerization inhibitor. Also, there is an ultraviolet-curable varnish composition mixed at a ratio of 50 to 90 parts by mass of urethane (meth) acrylate (A), 1 to 10 parts by mass of epoxy resin (B), 5 to 30 parts by mass of a filler (C) containing resin beads and / or inorganic beads, 0.2 to 2 parts by mass of polyethylene wax (D), 0.1 to 1 part by mass of silicone (E), 1 to 5 parts by mass of the photoinitiator, and 0.1 to 1 part by mass of the photopolymerization inhibitor.

[0079] [Properties of Materials] When the reflectance specular component of the reflected light observed at multiple angles when light is incident on the surface of the material of this embodiment is fitted with the Phong model shown in the above formula (1), the value of n is 3 or more and 50 or less, and the coefficient of kinetic friction when the surface of the material is touched by a human hand is 0.40 or more and 1.00 or less.

[0080] <Phong model> The Phong model according to this embodiment is a model related to specular reflection of light used in computer graphics (for example, Non-Patent Document A below).

[0081] [Non-Patent Document A] Published by the Image Information Education Promotion Association, "Computer Graphics", Image Information Education Association, March 2015.

[0082] When the reflectance specular component of the reflected light observed at multiple angles when light is incident on the surface of the material of this embodiment is fitted with the Phong model shown in the following formula (1), the value of n is 3 or more and 50 or less. It is preferably 5 or more, and more preferably 7 or more. Also, it is preferably 40 or less, and more preferably 25 or less.

[0083]

Equation

[0084] (In the formula, I e is the intensity of the incident light, k s is the specular reflectance,

Equation

Equation

[0085] "Specular component of reflectance" Light is incident on an object from a certain angle and reflected at a certain angle. The gloss and matte feeling of a material can be expressed by the light reflection characteristics. The light reflection intensity can be expressed by the following formula (2) (reflection intensity = ambient light + diffuse reflection + specular reflection. Fig. 1).

[0086]

Number

[0087] (In formula (2), I a is the intensity of the ambient light, k a is the reflectivity of the ambient light, I e is the intensity of the incident light, k d is the diffuse reflectivity,

Number

Number

Number

Number

[0088] The Phong model shown in the above formula (1) is a reflection model representing the specular reflection.

[0089] In addition, the reflection characteristics of an object with respect to the incident light can be expressed by the bidirectional reflectance distribution function (BRDF). However, to accurately evaluate the BRDF, it is necessary to measure by varying the incident angle and the reflection angle, and a large device using a goniometer is required. A multi-angle reflectometer is a device with restricted light incident and reflection angles, and there are small commercially available products. It is a device that can evaluate the BRDF at limited incident and reflection angles, and many devices equipped with a spectroscopic function can obtain the reflection intensity for each wavelength. In this embodiment, it is only necessary to be able to calculate the reflectance characteristics at multiple angles for a plurality of wavelengths, and any of the above methods can be used. Regarding the angles, due to the fitting relationship of the Phong model, at least 5 points are required at intervals of 10° or more, and there is no upper limit on the number of points. Also, for the wavelengths, at least 3 points are required with a separation of 100 nm or more from each other, and there is no upper limit on this either. And the Phong model shown in the above formula (1) of this embodiment can be changed to the following formula (3).

[0090]

Equation

[0091] (In the formula, I e is the intensity of the incident light, k s is the specular reflectance, θ is the angle formed by the vector between the highlight and the observation point, and n is a parameter that controls the characteristics of the highlight.) According to the above formula (3), the specular reflection component decreases in intensity as θ increases. The larger the value of n, the sharper the highlight, and one can feel the shine when the angle is changed. The smaller the value of n, the less the highlight is felt, and the stronger the matte feeling becomes. That is, the texture of the material can be controlled by the value of n.

[0092] Also, when the sample in this embodiment is a laminate, the laminated film is transparent. And when the sample in this embodiment is a veneer, the veneer was black and monotone, but depending on the sample, it exhibits various colors such as red and blue. However, in the present invention, since the value of n is fixed even when fitting by changing RGB or the wavelength, it is not affected by the color tone of the material.

[0093] "n of the Phong model" As an apparatus capable of measuring reflectance from multiple angles, as shown in the embodiment, an apparatus can be used in which an industrial camera and a lens are attached to a goniometer, and a self-made point light source is attached to the lens side (Fig. 2). Install this apparatus in a dark room, and irradiate light from the position of the angle θ formed with the normal of the surface onto the sample, and take a photo of the sample with the camera at the same angle. By using a computer and image analysis software, the RGB luminance values of the sample can be obtained from the center position of the photographed sample image. By changing the angle θ formed on the goniometer from 0 to 90°, RGB luminance values at various angles θ can be obtained. Here, a method using an industrial camera was used, but any method that can obtain reflectance from multiple angles may be used. For example, a system in which a spectro-radiance meter is installed on the goniometer may be used, or commercially available multi-angle reflectometers and BRDF measuring instruments can be mentioned.

[0094] The θ-dependence of the RGB luminance values is fitted with the Phong model of the above formula (1) for each RGB. In the measurement system of the present invention, using the angle θ formed between the viewing point and the highlight, the specular reflection represented by the Phong model, the ambient light, and the diffuse reflection are included in the light reflection intensity I r can be transformed into the simple form of the following formula (4).

[0095]

Equation

[0096] (In formula (4), I d is the reflection intensity of the ambient light and the diffuse reflection light, I s is the intensity of the specular reflection light, θ is the angle formed by the vector between the highlight and the observation point, and n is a parameter for controlling the characteristics of the highlight.)

[0097] The fitting variables are three points of I d , I s , and n, but I d and I sAlthough it may vary for each RGB, the value of n is made the same for RGB for fitting. Note that since the RGB values captured by the camera are affected by ambient light, it is desirable to perform fitting after color correction using a color chart. Examples of color charts include the Macbeth ColorChecker by X-Rite. Let the obtained value of n be the n according to the phone model.

[0098] There is no particular limitation on the fitting using Equation (4) as long as it is non-linear regression. As the regression method, mainly least-squares type non-linear regression is used. To utilize function fitting, there is a method of using the solver of Microsoft's spreadsheet software Excel, and there is also a method of using the regression fitting function provided in graph software such as KaleidaGraph by SynergySofrware. In addition, data analysis programming languages such as R and Python are equipped with libraries and functions capable of non-linear regression.

[0099] Convergence conditions are important in function fitting, and in particular, the initial value and the range of possible values are important. If this deviates significantly from the convergence value, the data cannot be fitted. In Equation (4), it is necessary to determine the initial values of the three points of the fitting variables I d , I s , and n. For example, as the initial value of I d , the average value of the measured RGB luminance at the highest θ can be used, and as the initial value of I s , the value obtained by subtracting I d from the average value of the measured RGB luminance at the lowest θ can be used.

[0100] Figure 3 plots the θ-dependence of the RGB values of the sample of Example 5 as points. The lines in Figure 3 are the results of fitting each RGB with Equation (4). In this embodiment, a method using an industrial camera is employed. However, when using a system in which a spectro-radiance meter is installed on a goniometer, a commercially available multi-angle reflectometer, or a BRDF measuring instrument, unlike an industrial camera that can only obtain RGB luminance values, reflectances at various visible light wavelengths can be obtained. Even in such cases, Equation (1) can be modified according to each measurement system, and the θ-dependence fitting of the luminance values can be performed at all the measured wavelengths. Then, the value of n obtained there can be used as n in the Phong model.

[0101] <Coefficient of kinetic friction when touched by hand (Coefficient of kinetic friction of hand)> The coefficient of kinetic friction of the hand measured by a human touching the surface (coated surface) of the material of this embodiment is 0.4 or more. It is preferably 0.55 or more, and more preferably 0.70 or more. Also, the coefficient of kinetic friction of the human hand is 1.0 or less. The higher the coefficient of friction felt by rubbing against a human hand, the more moist feeling is felt by feeling the resistance and weight when touched. If the coefficient of kinetic friction is 1.0 or more, a sticky feeling is felt and it is felt unpleasant.

[0102] In this embodiment, the coefficient of kinetic friction is obtained not by measuring using a device having a friction element, but by directly measuring by touching with a human hand. Thereby, since the tactile sensation received from the measurement sample can be quantified and evaluated in consideration of the tactile sensation due to the movement of a human finger, friction data having a better correlation with the human tactile sensation can be obtained.

[0103] As a method of directly measuring by touching with a human hand, there is a method of using a force plate type friction meter as described in JP-A-2019-144213. This can evaluate the friction when a human hand touches a material. When targeting a thick material or a three-dimensional object, there is a method of evaluating the friction by a human hand using a Wearable type tactile sensor or a force sensor as described in Patent No. 5809452. Any method may be used in the present invention.

[0104] As long as the measurement is done by human touch, there may be fluctuations in the measurement results. Therefore, it is preferable to average the results of multiple experimenters of a wide range of ages and genders. There is no upper limit to the number of experimenters, but it is preferable to average the data of five or more experimenters. Also, it is preferable to standardize the way of touching, such as the vertical load applied, the speed of touching, and which finger to trace with. For example, it is desirable to give prior instructions such as tracing with the palm at a speed of 50 mm / s and a vertical load of 200 g, and to sufficiently practice touching the material before this measurement.

[0105] From the coordinates when the material is touched by hand, or the displacement when touched, the speed when touching can be obtained excluding the unit time. Also, the friction coefficient when touching can be obtained by dividing the horizontal load when touched by the vertical load. Even with prior instructions, since it is touched by a human hand, friction values at various speeds and vertical loads can be obtained. Therefore, it is preferable to focus on the friction coefficient at a specific speed and vertical load. For example, it is preferable to obtain the value obtained by aggregating and averaging the friction coefficient values at a speed of 50 mm / s and a vertical load of 200 g for all subjects.

Example

[0106] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. Also, "%" in the compositions of the following examples means "mass%".

[0107] (Raw materials for manufacturing a laminate) ·Urethane acrylate (A): Lucidya manufactured by DIC Corporation (Tg: 50°C) ·Bifunctional epoxy resin (B): Epiklon manufactured by DIC Corporation ·Filler (C) ·Urethane resin beads: Art Pearl manufactured by Negami Kogyo Co., Ltd., particle diameter: 15 μm ·Soft urethane resin beads: Art Pearl manufactured by Negami Kogyo Co., Ltd., particle diameter: 15 μm ·Acrylic resin beads: Art Pearl manufactured by Negami Kogyo Co., Ltd., particle diameters: 10, 15 μm ·Nylon resin beads: Orgazol manufactured by Arkema, particle diameter: 6 μm · Polyethylene wax: Clariant, Ceridust, particle size: 8 μm · Silicone: KF series, manufactured by Shin-Etsu Chemical Co., Ltd. · Photo radical polymerization initiator: Adeka Arcles, manufactured by ADEKA Corporation · Photopolymerization inhibitor: Photopolymerization inhibitor, manufactured by Tokyo Chemical Industry Co., Ltd.

[0108] (Visual evaluation: n of the von model) A self-made goniometer was equipped with an industrial camera DFK27BUP006 (The Imaging Source) and a lens H0514-MP2 (CBC), and a self-made point light source was attached to the lens side (Figure 2). The device was installed in a dark room, and light was incident from the position of the angle θ formed from the normal of the surface on the sample, and a photograph of the sample was taken at the same angle with the camera. By using a computer and the OpenCV library of the Python program, the RGB luminance values of the sample can be obtained from the center position of the photographed sample image. By changing the angle θ formed on the goniometer from 0 to 90°, the RGB luminance values at various angles θ can be obtained (Figure 3). The θ-dependence of the RGB luminance values was fitted using Equation (4) for each RGB, and n according to the von model was obtained (Figure 3). In the present invention, the fitting of Equation (4) was performed using the nls function of the R programming language, and for the initial values of the three points of the fitting variables I d 、I s 、n, the average value of the actually measured RGB luminance values at the highest θ was used as the initial value of I d , and the value obtained by subtracting I s from the average value of the actually measured RGB luminance values at the lowest θ was used as the initial value of I d , and n = 20 was used. Also, as the range of possible values of the fitting variables, I d and I s were from 0 to 255. n was from 1 to 100. I d and I sThe reason why the upper limit is 255 is that the industrial camera DFK27BUP006 used is an 8-bit camera. Of course, other than 8-bit cameras can also be used. In this case, set the upper limit value according to the number of bits. Also, n does not take a value of 1 or less. Although there is no clear specification for the upper limit of n, ordinary materials do not take a value of 100 or more, so this value is set. Also, the fitting variable I d , I s , among the three points of I, I d and I s may change for each RGB, but the value of n is made the same for RGB for fitting. Note that since the RGB values captured by the camera are affected by ambient light, in the present invention, fitting is performed after color correction using a Macbeth color chart of X-Rite. For example, FIG. 3 plots the angular θ dependence of the RGB values of the sample of Example 5 as points respectively. The solid line in FIG. 3 is the result of fitting each of RGB with the formula (4). As a result of fitting, the I of R d is 56, I s is 87, n is 16.1, the I of G d is 34, I s is 92, n is 16.1, the I of B d is 41, I s is 83, n was 16.1. I d and I s change for each RGB, but fitting is performed so that the value of n is the same for RGB, and n = 16.1 is recovered as the n of the von model.

[0109] (Measurement of the coefficient of kinetic friction of the hand) Using the tactile force plate TF-2020-GVS of Techno Gihan Co., Ltd., the coefficient of kinetic friction when measured by human touch was determined. Eight healthy men and women aged 20 to 50 served as subjects. They placed their hands on the sample fixed on the tactile force plate and repeated the action of tracing from left to right across the sample with the palm for 30 seconds. Before the experiment, sufficient practice was carried out to trace with the palm at a speed of 50 mm / s and a vertical load of 200 g. From the coordinates and load when the hand touched the material, the speed and coefficient of friction at each time were calculated, and the coefficients of friction at a speed of 50 mm / s and a vertical load of 200 g were aggregated to obtain the average value. The value further averaged across all subjects was taken as the coefficient of kinetic friction of the hand.

[0110] (Evaluation of moist feeling) As an evaluation of the moist feeling of the sample, a questionnaire survey was conducted among the subjects. Eight healthy men and women aged 20 to 50 served as subjects. The subjects "touched the material with the palm after observing the material", and evaluated the moist feeling of the material on a scale of 1 to 5, where 1 means no moist feeling at all and 5 means a very strong moist feeling. The scores of all subjects were tabulated as percentages and rounded to the first decimal place, which was used as the evaluation criterion. Materials with a moist feeling score of 4 or more were considered to have a sufficient moist feeling.

[0111] (Examples 1 to 3, Comparative Examples 1 to 3) "Manufacture of synthetic leather" <Urethane resin composition for the epidermal layer> A compound solution obtained by diluting the urethane resin "Chrisbon NY-214L" or "Chrisbon NY-328FTR" manufactured by DIC Corporation with DMF was prepared as the urethane resin composition for the epidermal layer.

[0112] <Urethane resin composition for the adhesive layer> A compound solution consisting of 100 parts by mass of the urethane resin "Chrisbon TA-205FT" manufactured by DIC Corporation, 60 parts by mass of DMF, 12 parts by mass of the polyisocyanate crosslinking agent "Burnock DN-950" manufactured by DIC Corporation, and 1 part by mass of the tin catalyst "Accel T-81E" manufactured by DIC Corporation was prepared as the urethane resin composition for the adhesive layer.

[0113] <Release paper> The following release paper was used. 155T Flat: Manufactured by Ajinomoto Trading ARX-134: Manufactured by Asahi Roll R-261: Manufactured by Lintec R-295: Manufactured by Lintec

[0114] In accordance with the types of the epidermis and release paper of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1 below, the compounded liquid of the urethane resin composition for the epidermis layer obtained above was applied onto the above release paper so that the film thickness after drying would be 30 microns, and dried at 70°C for 2 minutes and further at 120°C for 2 minutes to form films of each example / comparative example on the release paper. Next, the compounded liquid of the urethane resin composition for the adhesive layer obtained above was applied onto this film so that the film thickness after drying would be 60 microns, and dried at 100°C for 1 minute. Next, a polyester base fabric was placed thereon, and after being pressure-bonded with a laminator at 120°C, it was aged at 50°C for 3 days. Thereafter, the release paper was peeled off to obtain the synthetic leathers (synthetic leather) of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1.

[0115]

Table 1

[0116] For the synthetic leathers (synthetic leather) manufactured in Examples 1 to 3 and Comparative Examples 1 to 3 above, the surface was visually evaluated (n of the von model), the evaluation of the moist feeling, and the measurement of the dynamic friction coefficient were performed by the method shown above. The results are shown in Tables 2 and 3.

[0117]

Table 2

[0118]

Table 3

[0119] (Examples 4 to 6, Comparative Examples 4 to 7) "Manufacture of Laminated Body Containing Coating Film (Laminated Film)" <Varnish Composition> The following raw materials were blended at the ratios of Examples 4 to 6 and Comparative Examples 4 to 7 shown in Table 4 below (the numbers in the table indicate the solid content mass ratio), and stirred with a dispersion stirrer at a rotation speed of 3000 rpm for 3 minutes to prepare varnish composition samples of Examples 4 to 6 and Comparative Examples 4 to 7.

Table 4

[0120] The varnish compositions having the mixing ratios shown in Table 4 were applied to a 50-μm-thick PET film E-5102 manufactured by Toyobo Co., Ltd. with a dry coating amount of 4 to 6 g / m 2 using a bar coater, dried and heated at 100 °C for 5 seconds to volatilize the solvent (methyl ethyl ketone) component, and then treated with a UV irradiation device manufactured by Fusion UV Systems at an integrated light amount of 300 mJ / cm 2 Thereby, the coating films of Examples 4 to 6 and Comparative Examples 4 to 7 were obtained.

[0121] For the coating films of Examples 4 to 6 and Comparative Examples 4 to 7, visual evaluation (n of the von model), evaluation of moist feeling, and measurement of kinetic friction coefficient were performed on the surface by the method shown above. The results are shown in Table 2 and Table 3.

[0122] (Discussion) From Table 2 and Table 3, for those with a moist feeling of 4 or more given as examples, regardless of the material, the kinetic friction coefficient when touching the material surface with a human hand is 0.40 or more and 1.00, and the value of n when fitting the specular component of the reflectance of the material surface with the von model of Equation (1) is 3 or more and 50 or less. That is, a moist feeling with a consistent feeling when seeing and touching can be felt by a tactile sensation with a frictional response and an appearance with moderately suppressed gloss, satisfying the sense of satisfaction and the desire for possession.

Industrial Applicability

[0123] When the material of this embodiment is applied to articles such as durable consumer goods like backs, packaging materials and containers for food and cosmetics, building materials like desks, and electrical appliances like personal computers and refrigerators, there is an effect that the visual (appearance) and the tactile (feel) sensations of smoothness on its surface match, satisfying the sense of satisfaction and desire for possession.

Explanation of Signs

[0124] 1 ··· Tactile Sensing Device 2 ··· Plate 3 ··· Load Detection Sensor 4 ··· Measurement Specimen 41 ··· Fixture

Claims

1. A material in which, when the specular component of the reflectance obtained by observing the reflected light at multiple angles when light is incident on the material surface is fitted with the Phong model represented by the following formula (1), the value of n is 3 or more and 50 or less, and the coefficient of kinetic friction when the material surface is touched by a human hand is 0.40 or more and 1.00 or less. 【Number 1】 (where I ｅ is the intensity of the incident light, k ｓ is the specular reflectance, 【Number 2】 is a vector in the highlight direction, 【Number 3】 is a vector representing the direction of the observation point.)

2. The material according to claim 1, wherein the Phong model is represented by the following formula (3). 【Number 4】 (where I ｅ is the intensity of the incident light, k ｓ is the specular reflectance, θ is the angle between the vector of the highlight and the observation point, and n is a parameter that controls the characteristics of the highlight.)

3. The material according to claim 1 or 2, wherein the specular component of the reflectance observed at multiple angles is obtained using a camera, a multi-angle reflectometer, or a BRDF measuring instrument.

4. The material according to claim 1 or 2, wherein the material is a leatherette or a laminate.

5. The material according to claim 4, wherein the leatherette has a base material and a layer formed of a urethane resin composition.

6. The material according to claim 4, wherein the laminate has a surface layer (laminated film) formed using an ultraviolet curable varnish composition.

7. The material according to claim 6, wherein the ultraviolet curable varnish composition contains urethane (meth)acrylate (A), epoxy resin (B), and a filler (C) containing resin beads and / or inorganic beads.

Images