Molding resin composition and molded article

Abstract

To provide an urethane (urea) resin composition for molding which exhibits a high antiviral effect and is excellent in moldability.SOLUTION: A urethane (urea) resin composition for molding contains antiviral urethane (urea) resin particles (W) having an antiviral agent (Y) containing a phenyl ether derivative in at least a part of a surface of thermoplastic urethane (urea) resin particles (X), wherein a volume average particle diameter of the antiviral urethane (urea) resin particles (W) is 50 μm to 1,000 μm, and the weight of the antiviral agent (Y) is 0.25-3.0 wt.% with respect to 100 of a weight of the thermoplastic urethane (urea) resin particles (X).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition for molding and a molded article.

Background Art

[0002] As a method for imparting antiviral properties to a thermoplastic polyurethane resin (hereinafter referred to as TPU) molded article, there are a method of melt-mixing and containing an antiviral agent in the base resin of the TPU molded article and then molding, a method of containing an antiviral agent in a coating agent and applying it to the surface of a base material / product, and the like.

[0003] Only the antiviral agent dispersed and contained near the surface of the molded article during molding exhibits the efficacy as an antiviral agent. In order to impart sufficient antiviral properties to the molded article, a considerably large amount of antiviral agent must be blended. Most of the large amount of inorganic-based antiviral agents blended are wasted without exhibiting efficacy. Moreover, there are many problems such as the molded article being heavy, molding itself being difficult, or the physical properties of the obtained molded article deteriorating. In addition, the production cost is high because a large amount of expensive antiviral agent is added.

[0004] For example, in the method of containing an antiviral agent in a coating agent, there are problems such as the coating film lacking flexibility and being prone to cracking when applied to a soft molded article. Further, a method of forming an organic binder containing a copper compound as an antiviral component on the surface of a TPU molded article has been proposed (Patent Document 1). However, such a method requires a coating and curing process, resulting in high production costs and a high environmental load due to the use of a solvent.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] One aspect of the present invention aims to provide a urethane (urea) resin composition for molding that exhibits high antiviral effects and excellent moldability. [Means for solving the problem]

[0007] To solve the above problems, a molding urethane (urea) resin composition according to one aspect of the present invention contains antiviral urethane (urea) resin particles (W) having an antiviral agent (Y) containing a phenyl ether derivative on at least a portion of the surface of thermoplastic urethane (urea) resin particles (X), wherein the volume average particle diameter of the antiviral urethane (urea) resin particles (W) is 50 μm to 1000 μm, and the weight of the antiviral agent (Y) is 0.25 to 3.0% by weight per 100 units of the weight of thermoplastic urethane (urea) resin particles (X). [Effects of the Invention]

[0008] According to one aspect of the present invention, a urethane (urea) resin composition for molding that exhibits a high antiviral effect and excellent moldability can be provided. [Modes for carrying out the invention]

[0009] One embodiment of the present invention will be described in detail below. Unless otherwise specified in this specification, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B".

[0010] The molding urethane (urea) resin composition of the present invention contains antiviral urethane (urea) resin particles (W) having an antiviral agent (Y) containing a phenyl ether derivative on at least a portion of the surface of thermoplastic urethane (urea) resin particles (X).

[0011] In the present invention, "urethane (urea) resin" includes both urethane resin containing only urethane bonds and urethane-urea resin containing both urethane bonds and urea bonds.

[0012] In this invention, "particles" include pellets, granules, and powders.

[0013] In this invention, "antiviral activity" means the effect of inactivating a virus by reducing the number of viruses or reducing the infectious titer of the virus. Examples of viruses include enveloped viruses. Examples of enveloped viruses include influenza viruses and coronaviruses.

[0014] Examples of thermoplastic urethane (urea) resin particles (X) include resins obtained by reacting polymer diols (a), monools (c), and organic diisocyanates (e) having a number average molecular weight of 300 to 3000. The thermoplastic urethane (urea) resin particles (X) may also be resins obtained by reacting polymer diols (a), monools (c), and organic diisocyanates (e) with compounds selected from low molecular weight diols (b) and diamines (d) having a number average molecular weight of less than 300, if necessary.

[0015] The number-average molecular weight of polymer diol (a) (hereinafter abbreviated as Mn) can be calculated from the hydroxyl value of the diol, which is measured according to the method conforming to JIS K1557-1 (Plastics - Polyurethane raw material polyol test method - Part 1: Method for determining hydroxyl value).

[0016] Examples of polymeric diols (a) include polyester diols (a1), polycarbonate diols (a2), polyester diols synthesized from lactone monomers (a3), polyether diols (a4), polyether ester diols (a5), and polyalkanediene diols (a6).

[0017] Polyester diols (a1) to polyalkanediols (a6) may be used individually or in combination of two or more types.

[0018] Polyester diol (a1) can be obtained by the condensation of a difunctional alcohol (a11) and a difunctional carboxylic acid (a12). The difunctional carboxylic acid (a12) may be an esterifying derivative, such as an acid anhydride (e.g., phthalic anhydride), a lower alkyl ester (e.g., dimethyl terephthalate), or an acid halide (e.g., phthalic acid chloride).

[0019] Examples of difunctional alcohols (a11) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, spiroglycol, dioxane glycol, adamantanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4- Examples include cyclohexanedimethanol, 2-methylpropanediol, 1,3,3-methylpentanediol, 1,5-hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, 1,4-polyisoprendiol, 1,4-polybutadienediol, 1,2-polybutadienediol, and hydroxyl-terminated polyalkanediols such as hydrogenated 1,4- or 1,2-polybutadienediol.

[0020] Examples of difunctional carboxylic acids (a12) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, orthophthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid.

[0021] Specific examples of the polyester diol (a1) include polyethylene adipate, polyethylene isophthalate, polyethylene terephthalate, polybutylene adipate, polybutylene terephthalate, polybutylene isophthalate, hexamethylene adipate, 1-hexamethylene terephthalate, hexamethylene isophthalate, and the like.

[0022] Examples of the polycarbonate diol (a2) include polycarbonate polyols produced by condensing the bifunctional alcohol (a11) and a low molecular weight carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms in the alkyl group, an alkylene carbonate having an alkylene group with 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group with 6 to 9 carbon atoms) while performing a dealcoholization reaction. The bifunctional alcohol (a11) and the low molecular weight carbonate compound may be used in combination of two or more kinds each.

[0023] Specific examples of the polycarbonate diol (a2) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly(pentamethylene / hexamethylene) carbonate diol (for example, a diol obtained by condensing 1,5-pentanediol and 1,6-hexanediol while performing a dealcoholization reaction with a dialkyl carbonate), and the like.

[0024] In the polyester diol (a3) synthesized from a lactone monomer, examples of the lactone monomer include lactones having 4 to 12 carbon atoms, such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, and polyester diols obtained by polymerizing a mixture of two or more of these.

[0025] Examples of the polyether diol (a4) include compounds obtained by adding an alkylene oxide to a hydroxyl group-containing compound having two hydroxyl groups (e.g., a difunctional alcohol (a11), a divalent phenol, etc.). Examples of the divalent phenols include bisphenols [bisphenol A, bisphenol F, bisphenol S, etc.] and monocyclic phenols [catechol, hydroquinone, resorcinol, etc.].

[0026] Examples of the compound obtained by adding an alkylene oxide to the difunctional alcohol (a11) include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0027] Examples of the compound obtained by adding an alkylene oxide to the divalent phenols include an adduct of hydroquinone with an alkylene oxide having 2 to 6 carbon atoms, an adduct of catechol with an alkylene oxide having 2 to 6 carbon atoms, an adduct of resorcinol with an alkylene oxide having 2 to 6 carbon atoms, and an adduct of bisphenol A with an alkylene oxide having 2 to 6 carbon atoms.

[0028] Examples of the polyether ester diol (a5) include those obtained by using the above polyether diol (a4) in place of the difunctional alcohol (a11) as a raw material in the above polyester diol (a1), for example, those obtained by polycondensing one or more of the above polyether diols (a4) and one or more of the dicarboxylic acids exemplified as raw materials of the above polyester diol (a4). Specific examples of the above polyether diol (a4) include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0029] Examples of the polyalkadiene diol (a6) include hydroxyl-terminated polyalkadiene diols such as 1,4-polyisoprene diol, 1,4-polybutadiene diol, 1,2-polybutadiene diol, and a hydrogenated product of 1,4- or 1,2-polybutadiene diol.

[0030] Of these, polyester diol (a1) and polycarbonate diol (a2) are preferred as polymer diols (a) from the viewpoint of heat resistance.

[0031] From the viewpoint of tensile strength and elongation at break of the molded article, the number average molecular weight (Mn) of polymer diol (a) is preferably 500 to 3,000, and particularly preferably 800 to 2,300.

[0032] As the low molecular weight diol (b), a diol with a number average molecular weight of less than 300 can be used. Examples of low molecular weight diols (b) include the alcohols exemplified in the difunctional alcohol (a11). Preferably, the low molecular weight diol (b) is 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, with 1,4-butanediol and 1,6-hexanediol being preferred from the viewpoint of the strength of the molded article. One type of low molecular weight diol (b) may be used alone, or two or more types may be used in combination.

[0033] Examples of monools (c) include aliphatic monools having 1 to 8 carbon atoms [linear monools (methanol, ethanol, propanol, butanol, pentanol, hexanol, and octanol, etc.) and branched monools (isopropyl alcohol, neopentyl alcohol, 3-methyl-pentanol, and 2-ethylhexanol, etc.)]; monools having cyclic groups with 6 to 10 carbon atoms [alicyclic monools (cyclohexanol, etc.) and aromatic monools having 7 to 12 carbon atoms (benzyl alcohol and naphthylethanol, etc.)]; and mixtures of two or more of these. Polymeric monools such as polyester monools, polyether monools, and polyether ester monools can also be used as monools (c). Among these, aliphatic monools having 6 to 10 carbon atoms and aromatic monools having 7 to 12 carbon atoms are preferred.

[0034] Examples of diamine (d) include alicyclic diamines having 6 to 10 carbon atoms (such as 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, diaminocyclohexane, and isophorone diamine); aliphatic diamines having 2 to 10 carbon atoms (such as ethylenediamine, butylenediamine, and hexamethylenediamine); aromatic aliphatic diamines having 8 to 10 carbon atoms (such as xylylenediamine); and mixtures of two or more of these. Of these, alicyclic diamines having 6 to 10 carbon atoms and aliphatic diamines having 2 to 10 carbon atoms are preferred, and isophorone diamine and hexamethylenediamine are particularly preferred.

[0035] Examples of organic diisocyanates (e) include the following:

[0036] (i) Aliphatic diisocyanates with 2 to 18 carbon atoms (excluding carbon atoms in the NCO group; the same applies hereinafter) [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.].

[0037] (ii) Alicyclic diisocyanates having 4 to 15 carbon atoms [isophorone diisocyanate (hereinafter abbreviated as IPDI), dicyclohexylmethane-4,4'-diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis(2-isocyanatoethyl)-4-cyclohexene, etc.].

[0038] (iii) Aromatic aliphatic diisocyanates having 8 to 15 carbon atoms [such as m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate].

[0039] (iv) Aromatic diisocyanates [1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylenediisocyanate (hereinafter abbreviated as TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, and 1,5-naphthylenediisocyanate, etc.].

[0040] (v) Modified diisocyanates (diisocyanate modified products having a carbodiimide group, uretodione group, uretoimine group, or urea group, etc.).

[0041] Of these, aliphatic diisocyanates and alicyclic diisocyanates are preferred from the viewpoint of weather resistance, and HDI, IPDI, and hydrogenated MDI are even more preferred.

[0042] Organic diisocyanate (e) may be used alone or in combination of two or more types.

[0043] In the present invention, the thermoplastic urethane (urea) resin particles (X) may be perfectly spherical or non-spherical.

[0044] The volume-average particle size of the thermoplastic urethane (urea) resin particles (X) is preferably 50 to 1000 μm, particularly preferably 100 to 500 μm, and most preferably 150 to 300 μm.

[0045] In the present invention, the volume-average particle diameter of thermoplastic urethane (urea) resin particles (X) is the particle diameter (d50) when the cumulative amount is 50%, as measured using a laser diffraction particle diameter distribution analyzer and relative cumulative particle diameter distribution curve (volume-based).

[0046] The Mn of the thermoplastic urethane (urea) resin particles (X) is preferably 10,000 to 40,000, and more preferably 13,000 to 30,000. The Mn of the thermoplastic urethane (urea) resin particles (X) is measured, for example, by the method described in the examples.

[0047] The following are some examples of methods for producing thermoplastic urethane (urea) resin particles (X). The following describes a method using low molecular weight diols (b) and diamines (d), but the method for producing thermoplastic urethane (urea) resin particles (X) is not limited to these methods.

[0048] (1) A method of reacting a mixture of a high molecular weight diol (a), a low molecular weight diol (b), and a monool (c) with an organic diisocyanate (e) in the presence or absence of an organic solvent, such that the molar ratio of hydroxyl groups in the mixture to isocyanate groups of the organic diisocyanate (e) is 1:1.2 to 1:4.0, and then extending the resulting urethane prepolymer (Up) having isocyanate groups at the ends with a diamine (d) in the presence of water and a dispersion stabilizer. Note that a blocked linear aliphatic diamine (e.g., a ketimine compound) can be used as the diamine.

[0049] (2) A method for extending the above-mentioned urethane prepolymer (Up) with diamine (d) in the presence of a nonpolar organic solvent and a dispersion stabilizer.

[0050] (3) A method for reacting a high molecular weight diol (a), a low molecular weight diol (b), a monool (c), a diamine (d), and an organic diisocyanate (e) in a single reaction.

[0051] If thermoplastic urethane (urea) resin particles (X) are obtained as a dispersion, the dispersion medium may be removed and the particles may be further pulverized.

[0052] Organic solvents used in the production of thermoplastic urethane (urea) resin particles (X) include ketones with 3 to 9 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone, etc.), ethers with 4 to 8 carbon atoms (tetrahydrofuran, etc.), and esters with 3 to 6 carbon atoms (methyl acetate and ethyl acetate, etc.).

[0053] Organic solvents may be used individually or in combination of two or more.

[0054] Examples of dispersion stabilizers used in the production of thermoplastic urethane (urea) resin particles (X) include water-soluble polymers (methylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylates, polyvinylpyrrolidone, and sodium salts of copolymers of diisobutylene and maleic acid, etc.), inorganic powders (calcium carbonate powder, calcium phosphate powder, hydroxyapatite powder, silica powder, etc.), and surfactants (sodium dodecylbenzenesulfonate and sodium lauryl sulfate, etc.).

[0055] Dispersion stabilizers may be used individually or in combination of two or more types.

[0056] Examples of nonpolar organic solvents used in the production of thermoplastic urethane (urea) resin particles (X) include pentane, hexane, heptane, toluene, and xylene.

[0057] Organic solvents may be used individually or in combination of two or more.

[0058] The reaction temperature for producing the urethane prepolymer (Up) may be the same as the temperature used for urethane formation. When an organic solvent is used, the temperature is preferably 20°C to 100°C, and when an organic solvent is not used, the temperature is preferably 20°C to 140°C, more preferably 80°C to 130°C.

[0059] In the above urethane formation reaction, catalysts used for polyurethanes may be used as needed to accelerate the reaction. Examples of catalysts include amine-based catalysts (triethylamine, N-ethylmorpholine, and triethylenediamine, etc.) and tin-based catalysts (trimethyl thyn laurate, dibutyl thyn dilaurate, and dibutyl thyn maleate, etc.).

[0060] The antiviral agent (Y) used in the present invention can be any antiviral agent used for antiviral purposes without particular limitations, but examples include antiviral agents that are insoluble in water at 25°C.

[0061] Using an antiviral agent that is insoluble in 25°C water makes it less likely for the antiviral agent to peel off or detach from the molded product, resulting in a high antiviral effect that lasts for a long period even with a small amount of use.

[0062] In this invention, insolubility means that the solubility in 100g of deionized water at 25°C is 0.1g or less.

[0063] The aforementioned solubility can be measured by the following method: Add the thoroughly dried target (antiviral agent) to 100g of ion-exchanged water at 25°C in a 200mL beaker, insert a stirrer tip measuring 20mm in length and 7mm in width, and stir with a magnetic stirrer. If the antiviral agent does not dissolve after 1 hour of stirring, the amount of antiviral agent added immediately before that point is taken as the solubility of the antiviral agent in 25°C water. A magnetic stirrer such as the HPS-100 manufactured by AS ONE Corporation can be used.

[0064] Examples of antiviral agents include phenyl ether derivative type antiviral agents. Specifically, an example of a phenyl ether derivative type antiviral agent is Willtaker IV [manufactured by Sekisui Material Solutions Co., Ltd.].

[0065] The form of the antiviral agent used in this invention is not particularly limited and may be a liquid, powder, etc., but particles are preferred. The shape of the antiviral agent particles is not particularly limited and may be spherical, cylindrical, irregularly shaped, etc.

[0066] The volume-average particle diameter of the antiviral agent particles used in this invention is preferably 0.01 to 29 μm, more preferably 0.05 to 5 μm, and most preferably 0.1 to 4 μm. By setting the volume-average particle diameter of the antiviral agent particles to 0.01 to 29 μm, the antiviral agent (Y) can be incorporated into at least a portion of the surface of the thermoplastic urethane (urea) resin particles (X).

[0067] In the present invention, the volume-average particle diameter of the antiviral agent (Y) is the particle diameter (d50) when the cumulative amount reaches 50%, as measured using a laser diffraction particle diameter distribution analyzer and relative cumulative particle diameter distribution curve (volume-based).

[0068] The content of the antiviral agent (Y) is 0.25 to 3.0% by weight, based on the weight of the thermoplastic urethane (urea) resin particles (X). By having an antiviral agent (Y) content of 0.25% by weight or more in the antiviral urethane (urea) resin particles (W), antiviral properties can be imparted to the thermoplastic urethane (urea) resin particles (W) without any special treatment. Furthermore, by having an antiviral agent content of 3.0% by weight or less, a urethane (urea) resin composition for molding with excellent moldability can be provided.

[0069] The antiviral urethane (urea) resin particles (W) of the present invention have an antiviral agent (Y) on at least a portion of the surface of thermoplastic urethane (urea) resin particles (X). Specifically, the antiviral agent (Y) coats at least a portion of the surface of the thermoplastic urethane (urea) resin particles (X). By coating at least a portion of the surface of the thermoplastic urethane (urea) resin particles (X) with the antiviral agent (Y), antiviral properties can be imparted to the antiviral urethane (urea) resin particles (W), and by using a molding urethane (urea) resin composition containing the antiviral urethane (urea) resin particles (W), it is possible to create a molded article having a desired shape.

[0070] The volume-average particle size of the antiviral urethane (urea) resin particles (W) is 50 μm to 1000 μm, preferably 100 to 500 μm, and most preferably 150 to 300 μm. Because the volume-average particle size of the antiviral urethane (urea) resin particles (W) is 50 μm to 1000 μm, the antiviral agent (Y) is less likely to detach from the surface of the resin particles (W).

[0071] The following conditions (1) and (2) can be cited as conditions under which the antiviral agent (Y) is less likely to detach from the surface of the resin particles (W): (1) The volume-average particle size of the antiviral agent (Y) is smaller than the particle size of the thermoplastic urethane (urea) resin particles (X). (2) The surface of the thermoplastic urethane (urea) resin particles (X) is uneven.

[0072] In the present invention, the volume-average particle diameter of the antiviral urethane (urea) resin particles (W) is the particle diameter (d50) when the cumulative amount is 50%, as measured using a laser diffraction particle size distribution analyzer in the relative cumulative particle size distribution curve (volume-based).

[0073] In the antiviral urethane (urea) resin particles (W), having the antiviral agent (Y) on at least a part of the surface of the thermoplastic urethane (urea) resin particles (X) can be confirmed, for example, by that in the elemental mass concentration of SEM-EDX on the antiviral urethane (urea) resin particles (W), the mass concentration of the constituent elements of the antiviral agent (Y) is 0.05% or more.

[0074] If the mass concentration of the constituent elements of the antiviral agent (Y) on the antiviral urethane (urea) resin particles (W) is 0.03% or more, the amount of the antiviral agent (Y) attached to the thermoplastic urethane (urea) resin particles (X) is large and a sufficient antiviral effect can be exhibited. The mass concentration of the constituent elements of the antiviral agent (Y) is more preferably 0.04 to 0.40%, and most preferably 0.05 to 0.15%.

[0075] The desirable SEM-EDX measurement conditions are shown below. <SEM-EDX Measurement Conditions> <Carbon Deposition Processing Apparatus> Sunyu Electronics QUICK CARBON MODEL SC-701C Thickness Count: 3 times, Vacuum Degree: 10^-2 Torr <Measuring Device> ·SEM: JEOL JSM-7000 ·EDX: OXFORD INCA X-sight Vacuum Degree: 1×10^-4 Pa or less Accelerating Voltage: 25 kV Current Mode: Medium.

[0076] The urethane (urea) resin composition for molding of the present invention may contain components other than the thermoplastic urethane (urea) resin particles (X) and the antiviral agent (Y) [hereinafter also referred to as "additive (Z)"].

[0077] The additive (Z) may be mixed in the production of the urethane prepolymer (Up) which is a raw material for thermoplastic urethane (urea) resin particles (X), or it may be mixed in the thermoplastic urethane (urea) resin particles (X), or it may be mixed in with antiviral urethane (urea) resin particles (W).

[0078] Examples of additives (Z) include inorganic fillers (Z1), pigments (Z2), plasticizers (Z3), mold release agents (Z4), stabilizers (Z5), and anti-blocking agents (powder flow improvers) (Z6). Additives may be used individually or in combination of two or more.

[0079] Of these, it is preferable to use the plasticizer (Z3), mold release agent (Z4), stabilizer (Z5), and anti-blocking agent (Z6) mixed with thermoplastic urethane (urea) resin particles (X) or antiviral urethane (urea) resin particles (W).

[0080] Examples of inorganic fillers (Z1) include those that do not have antiviral properties and do not serve as carriers for antiviral agents, such as talc, calcium carbonate, sericite, graphite, magnesium hydroxide, aluminum hydroxide, and zinc borate. Of these, talc is preferred.

[0081] The volume-average particle size of the inorganic filler (Z1) is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 2 to 10 μm, from the viewpoint of dispersibility in the urethane (urea) resin composition for molding.

[0082] The amount of inorganic filler (Z1) added is preferably 0 to 40 parts by weight, and more preferably 1 to 20 parts by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0083] The pigment (Z2) is not particularly limited, and known organic and inorganic pigments can be used. Examples of organic pigments include azo pigments, copper phthalocyanine pigments, and quinacridone pigments, while examples of inorganic pigments include those that do not have antiviral properties and do not serve as carriers for antiviral agents, such as chromates, ferrocyanine compounds, carbonates (calcium carbonate and magnesium carbonate, etc.) and phosphates (calcium phosphate and magnesium phosphate, etc.), metal powders (aluminum powder, iron powder, nickel powder and copper powder, etc.) and carbon black.

[0084] There are no particular limitations on the average particle size of the pigment, but it is preferably 0.2 to 5.0 μm, and more preferably 0.5 to 1.0 μm.

[0085] The amount of pigment (Z2) added is preferably 10 parts by weight or less, more preferably 0.01 to 5 parts by weight, and even more preferably 1 to 3 parts by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0086] Plasticizers (Z3) include phthalate esters (dibutyl phthalate, dioctyl phthalate, dibutylbenzyl phthalate and diisodecyl phthalate, etc.); benzoate esters (polyethylene glycol dibenzoate, etc.); aliphatic dibasic acid esters (di-2-ethylhexyl adipate and 2-ethylhexyl sebacate, etc.); trimellitic acid esters ( Examples include tri-2-ethylhexyl rimellitic acid and trioctyl trimellitic acid; fatty acid esters (butyl oleate, etc.); aliphatic phosphate esters (trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, and tributoxy phosphate, etc.); aromatic phosphate esters [triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and tris(2,6-dimethylphenyl) phosphate, etc.]; halogenated aliphatic phosphate esters [tris(chloroethyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, and tris(tribromoneopentyl) phosphate, etc.]; and mixtures of two or more of these.

[0087] The amount of plasticizer (Z3) added is preferably 0 to 50 parts by weight, and more preferably 5 to 20 parts by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0088] As the release agent (Z4), known release agents can be used, including fluorine compound type release agents [triperfluoroalkyl (8-20 carbon atoms) esters (triperfluorooctyl phosphate and triperfluorododecyl phosphate, etc.)]; silicone compound type release agents (dimethylpolysiloxane, amino-modified dimethylpolysiloxane and carboxyl-modified dimethylpolysiloxane, etc.); fatty acid ester type release agents [mono or polyhydric alcohol esters of fatty acids with 10-24 carbon atoms (butyl stearate, hydrogenated castor oil and ethylene glycol monostearate, etc.)]; aliphatic acid amide type release agents [mono or bisamides of fatty acids with 8-24 carbon atoms (oleamide, palmitamide, stearamide and distearate amides such as ethylenediamine, etc.)]; metal soaps (magnesium stearate and zinc stearate, etc.); natural or synthetic waxes (paraffin wax, microcrystalline wax, polyethylene wax and polypropylene wax, etc.); and mixtures of two or more of these.

[0089] The amount of release agent (Z4) added is preferably 0 to 1 part by weight, and more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0090] As stabilizers (Z5), in addition to ultraviolet absorbers (Z51), antioxidants (Z52), and hydrolysis inhibitors (Z53), compounds having a carbon-carbon double bond (such as an ethylene bond which may have substituents) (excluding double bonds in aromatic rings) or a carbon-carbon triple bond (such as an acetylene bond which may have substituents) in the molecule can be used.

[0091] Examples of UV absorbers (Z51) include benzophenone-based [2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, etc.]; benzotriazole-based [2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.]; salicylic acid-based [phenyl salicylate, etc.]; and hindered amine-based [bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, etc.].

[0092] Examples of antioxidants (Z52) include phenolic compounds [such as 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole]; bisphenolic compounds [such as 2,2'-methylenebis(4-methyl-6-t-butylphenol)]; and phosphorus compounds [such as triphenyl phosphite and diphenyl isodecyl phosphite].

[0093] Examples of hydrolysis inhibitors (Z53) include those having a functional group that reacts with a carboxyl group within the molecule. Examples of functional groups that react with a carboxyl group include carbodiimide groups, oxazoline groups, epoxy groups, cyclocarbonate groups, and aziridine groups.

[0094] Examples of compounds having a carbon-carbon double bond or carbon-carbon triple bond in the molecule include esters of (meth)acrylic acid with 2-10 valent polyhydric alcohols (2-10 valent polyhydric alcohols, the same applies hereinafter) [ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc.]; esters of (meth)allyl alcohol with 2-6 valent polycarboxylic acids [diallyl phthalate and trimellitic acid trialyl ester, etc.]; poly(meth)allyl ethers of polyhydric alcohols [pentaerythritol(meth)allyl ether, etc.]; polyvinyl ethers of polyhydric alcohols (ethylene glycol divinyl ether, etc.); polypropenyl ethers of polyhydric alcohols (ethylene glycol dipropenyl ether, etc.); polyvinylbenzene (divinylbenzene, etc.) and mixtures of two or more of these.

[0095] Of these, from the viewpoint of stability (radical polymerization rate), esters of (meth)acrylic acid and polyhydric alcohols are preferred, and more preferably trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0096] The amount of stabilizer (Z5) added is preferably 0 to 20 parts by weight, and more preferably 1 to 15 parts by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0097] Examples of blocking inhibitors (powder flow improvers) (Z6) include thermosetting resins with a particle size of 10 μm or less (thermosetting polyurethane resins, guanamine-based resins, epoxy-based resins, etc.) and thermoplastic resins with a particle size of 10 μm or less [thermoplastic polyurethane urea resins, poly(meth)acrylate resins, etc.].

[0098] The amount of blocking inhibitor (fluidity improver) (Z6) added is preferably 0 to 5 parts by weight, and more preferably 0.5 to 1 part by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0099] The total amount of additive (Z) is preferably 0.01 to 50 parts by weight, and more preferably 1 to 30 parts by weight, per 100 parts by weight of thermoplastic urethane (urea) resin particles (X).

[0100] [Method for producing urethane (urea) resin composition for molding] The present invention provides a method for producing a urethane (urea) resin composition for molding, comprising a step of mixing thermoplastic urethane (urea) resin particles (X) with an antiviral agent (Y) in an amount of 0.25 to 3.0% by weight per 100 units of thermoplastic urethane (urea) resin particles (hereinafter also referred to as the "mixing step"). This method makes it possible to easily impart antiviral properties to thermoplastic urethane (urea) resin particles (X).

[0101] As mixing equipment used in the mixing process, known powder mixing equipment can be used, and any of the following can be used: rotary container mixers, stationary container mixers, and fluid-motion mixers. For example, stationary container mixers include high-speed fluid mixers, double-shaft paddle mixers, high-speed shear mixers [Hensiel Mixer (registered trademark), etc.], low-speed mixers (planetary mixers, etc.), and conical screw mixers [Nauta Mixer (registered trademark, hereinafter omitted), etc.]. Among these, the double-shaft paddle mixers, low-speed mixers (planetary mixers, etc.), and conical screw mixers (Nauta Mixer, etc.) are preferred.

[0102] [Molded body] The molded article of the present invention is obtained by molding the urethane (urea) resin composition for molding of the present invention.

[0103] By having an antiviral agent (Y) on at least a portion of the surface of thermoplastic urethane (urea) resin particles (X), a molded article formed from the urethane (urea) resin composition for molding of the present invention is less susceptible to a decrease in antiviral properties due to peeling and detachment of the antiviral agent, and a desired shape can be obtained.

[0104] Methods for forming molded articles include injection molding, compression molding, calendering, slush molding, rotational molding, extrusion molding, blow molding, and film molding (casting method, tenter method, and inflation method, etc.).

[0105] The urethane (urea) resin composition for molding of the present invention contains a high concentration of antiviral agent on the surface of the particles, so by molding the particles as they are, a molded body with a high concentration of antiviral agent on the surface can be obtained. For this reason, among the molding methods described above, a molding method that obtains a molded body without pouring the heated and molten resin composition into a mold, such as a molding method in which resin particles are directly filled into a mold and molded integrally by applying heat or pressure (slush molding, rotational molding, compression molding, and calendering molding, etc.), is preferred. Examples of molded body forms include plates, sheets, films, and fibers (including nonwoven fabrics, etc.). [Examples]

[0106] The present invention will be further described by the following examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight, and % represents weight percent.

[0107] [Manufacturing Example 1: Manufacturing of Thermoplastic Urethane Urea Resin Particles (X-1)] In a reaction vessel equipped with a thermometer, stirrer, and nitrogen inlet, 282.9 parts of polyethylene isophthalate with a manganese content of 2300 as polyester diol (a1), 424.4 parts of polybutylene adipate with a manganese content of 1000 as polyester diol (a1), 9.34 parts of benzyl alcohol as monool (c), and 5.88 parts of 1,4-butanediol as low molecular weight diol (b) were charged. After purging the reaction vessel with nitrogen, the mixture was heated to 110°C with stirring to melt the substances, and then cooled to 50°C. Subsequently, 150.0 parts of methyl ethyl ketone as an organic solvent and 132.0 parts of hexamethylene diisocyanate as organic diisocyanate (e) were added, and the mixture was reacted at 90°C for 6 hours. Next, after cooling to 70°C, 1.4 parts of Irganox 1010 [manufactured by Ciba Specialty Chemicals Co., Ltd.] as a stabilizer were added and mixed uniformly to obtain a urethane prepolymer (Up-1) solution. The isocyanate group content of the obtained prepolymer solution was 1.63%.

[0108] Next, 157.9 parts of an aqueous solution prepared by dissolving 5.9 parts of Sanspar PS-8 [manufactured by Sanyo Chemical Industries, Ltd.] as a dispersion stabilizer in 152 parts of water, and 37.1 parts of methyl ethyl ketone as an organic solvent were added to the reaction vessel and the mixture was uniformly stirred at 20°C. Then, 1.7 parts of hexamethylenediamine as diamine (d) were added and mixed for 1 minute under stirring at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm) using an Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.]. Subsequently, 103.3 parts of a solution of prepolymer (Up-1) heated to 75°C were added and mixed for 2 minutes at a peripheral speed of 23 m / s. After that, the mixture was transferred to a reaction vessel equipped with a thermometer, stirrer, and nitrogen injection tube, the reaction vessel was purged with nitrogen, and the mixture was reacted at 50°C for 10 hours while stirring. After the reaction was complete, the mixture was filtered and dried to obtain thermoplastic urethane urea resin particles (X-1).

[0109] The obtained thermoplastic urethane urea resin particles (X-1) were in powder form, with a volume-average particle size of 205 μm and a manganese content of 25,000.

[0110] [Example 1] (1-1) Production of molding resin composition 6.1 parts of a pigment dispersion, prepared by dispersing 5.8 parts of polyethylene glycol (degree of polymerization 2-10) dibenzoic acid ester (Z3-1) [product name: Sunsoft EB300, manufactured by Sanyo Chemical Industries, Ltd.] as a plasticizer (Z3) with 1.3 parts of carbon black (Z2-1) as a pigment (Z2), and 100 parts of granular thermoplastic urethane urea resin particles (X-1) obtained in Production Example 1, were placed in a mixer [CRUSH MILLSER, manufactured by Iwatani] and turned at a rotation speed of 700 min⁻¹. -1 Stirred for 1 minute.

[0111] Next, the mixture was transferred to a Nauter mixer [LABOMIXER LV-1, manufactured by Hosokawa Micron], and 0.3 parts of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture) [product name: Tinuvin 765, manufactured by BASF Japan Ltd.] (Z51-1) as an ultraviolet absorber (Z51) were added. The mixture was stirred at 70°C for 4 hours to impregnate the thermoplastic urethane urea resin particles (X-1) with the plasticizer (Z3-1) and ultraviolet absorber (Z51-1).

[0112] Next, 0.06 parts of (Z4-1) dimethylpolysiloxane [product name: Kei L45-10000, manufactured by Nippon Unicar Co., Ltd.] as a mold release agent (Z4) were added and mixed for 30 minutes, then cooled to room temperature. Finally, 0.5 parts of cross-linked polymethyl methacrylate (Z6-1) [product name: Gantzpearl PM-030S, manufactured by Gantz Chemicals Co., Ltd.] as an anti-blocking agent (Z6) and 1.0 part of a phenyl ether derivative type antiviral agent [product name: Willtaker IV, manufactured by Sekisui Material Solutions Co., Ltd.] were mixed at room temperature for 30 minutes to obtain a molding resin composition.

[0113] (1-2) Manufacturing of molded products The molding resin composition prepared in (1-1) was press-molded at 180°C for 60 seconds at 5 MPa to obtain a sheet with a thickness of 0.8 mm. The tensile strength and elongation of the obtained sheet were evaluated, and the results are shown in Table 1.

[0114] Furthermore, a textured Ni electroformed mold, preheated to 250°C, was filled with a urethane (urea) resin composition for molding and held for 60 seconds. After that, the excess urethane (urea) resin composition was discharged. The mold was then water-cooled for 60 seconds to produce a molded surface with a thickness of 1.0 mm. Antiviral and moldability tests were then conducted, and the results are shown in Table 1.

[0115] [Examples 2-8, Comparative Examples 1-3] In Example 1 (1-1), the same procedure as in Example 1 (1-1) and (1-2) was performed to produce a urethane urea resin composition for molding, except that the weight of the phenyl ether derivative type antiviral agent was set to the weight shown in Table 1.

[0116] Furthermore, sheets and molded skins were obtained using the composition. The obtained sheets were evaluated for tensile strength and elongation at break, and the obtained molded skins were subjected to antiviral and moldability tests. The results are shown in Table 1.

[0117] <Evaluation Method> [Method for measuring Mn in thermoplastic urethane urea resin particles] The manganese content (Mn) of thermoplastic urethane urea resin particles (X) was measured using gel permeation chromatography under the following conditions. • Device: "HLC-8320" [Manufactured by Tosoh Corporation] • Columns: "TSKgel Guardcolumn α", "TSKgel α-M" [Manufactured by Tosoh Corporation] ·Measurement temperature: 40℃ • Sample solution: 0.125% by weight of N,N-dimethylformamide solution ·Solution injection volume: 100μL • Detection device: Refractive index detector • Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE) 12 samples (molecular weight 589, 1,050, 2,630, 5,970, 9,100, 19,500, 37,900, 96,400, 190,000, 427,000, 1,090,000, 2,110,000) [Manufactured by Tosoh Corporation] For the measurement of Mn, the sample was dissolved in N,N-dimethylformamide, and the insoluble portion was filtered out using a glass filter to obtain the sample solution.

[0118] [Method for measuring volume-average particle diameter] The volume-average particle diameters of thermoplastic urethane urea resin particles (X), phenyl ether derivative-type antiviral agent, and antiviral urethane urea resin particles (W) were measured by the following method.

[0119] Measurements were performed using a laser diffraction particle size distribution analyzer [MicrotracMT3000II manufactured by Nikkiso Co., Ltd.], and the particle size (d50) at which the cumulative amount reached 50% in the obtained relative cumulative particle size distribution curve was defined as the volume-average particle size.

[0120] <Method for measuring tensile strength and elongation at break> Measurements were performed in accordance with JIS K 6251:2010. Specifically, three dumbbell-shaped tensile test specimens (Type 1) were punched out from the 0.8 mm thick sheets obtained in Examples 1-8 and Comparative Examples 1-3, and gauge marks were drawn at 40 mm intervals in the center of each specimen. The minimum thickness between the five gauge marks was used. These specimens were mounted on an autograph under a 25°C atmosphere and pulled at a speed of 200 mm / min to measure tensile strength and elongation at break.

[0121] <Moldability> The molded skins with a thickness of 1.0 mm obtained in Examples 1-8 and Comparative Examples 1-3 were cut into 100 mm x 100 mm sections, and the moldability was confirmed by visually observing the center of the back surface and evaluating the meltability according to the following criteria. 5. The resin composition melts uniformly and is smooth. 4: There are some parts with uneven surfaces due to the unmelted molding resin composition, but there are also some smooth parts. 3: The entire back surface has an uneven texture. There are no pinholes that penetrate from the back to the front. 2: The entire back surface is uneven, and there are pinholes that penetrate from the back surface to the front surface. 1: The molding resin composition does not melt, and a molded product is not formed.

[0122] <Antiviral Test> The test was conducted in accordance with ISO 21702 (excluding textiles) to calculate the antiviral activity value against influenza virus. The antiviral activity value is the difference in viral infectivity titer (common logarithm of the number of viruses that can infect cells) between the antiviral processed product and the unprocessed product after dropping a virus solution onto them and letting them stand for 24 hours. A higher antiviral activity value indicates higher antiviral activity. The antiviral activity value of the antiviral urethane urea resin particles is preferably 2.0 or higher, and more preferably 2.5 or higher.

[0123] [Table 1]

Claims

1. The antiviral urethane (urea) resin particles (W) have an antiviral agent (Y) containing a phenyl ether derivative on at least a portion of the surface of thermoplastic urethane (urea) resin particles (X), The volume-average particle size of the aforementioned antiviral urethane (urea) resin particles (W) is 50 μm to 1000 μm. A urethane (urea) resin composition for molding, wherein the weight of the antiviral agent (Y) is 0.25 to 3.0% by weight relative to 100 units of thermoplastic urethane (urea) resin particles (X).

2. The molding urethane (urea) resin composition according to claim 1, wherein the antiviral agent (Y) is insoluble in water at 25°C.

3. A molded article obtained by molding a urethane (urea) resin composition for molding according to claim 1 or 2.

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