JP7836726B2 - Molding resin composition and molded article - Google Patents

Description

This invention relates to a resin composition for molding and a molded article.

Methods for imparting antiviral properties to thermoplastic polyurethane resin (hereinafter referred to as TPU) molded products include a method of melting and mixing an antiviral agent into the base resin of the TPU molded product before molding, and a method of incorporating an antiviral agent into a coating agent and applying it to the surface of the substrate or product.

Only antiviral agents dispersed and contained near the surface of the molded product during molding exhibit antiviral efficacy. To impart sufficient antiviral properties to the molded product, a considerably large amount of antiviral agent must be incorporated. Much of this large amount of inorganic antiviral agent is ineffective and wasted. Furthermore, there are many problems, such as the molded product being heavy, the molding process itself being difficult, or a decrease in the physical properties of the resulting molded product. Additionally, the production cost is high due to the addition of large amounts of expensive antiviral agent.

For example, methods that incorporate antiviral agents into coatings have problems such as the coating film lacking flexibility and being prone to cracking when applied to soft molded products. Furthermore, a method has been proposed (Patent Document 1) in which an organic binder containing a copper compound as an antiviral component is cured and formed on the surface of a TPU molded product. However, such methods have problems such as high production costs due to the need for a coating and curing process, and high environmental impact due to the use of solvents.

Japanese Patent Application No. 2018-215702

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

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 relative to 100 units of the weight of thermoplastic urethane (urea) resin particles (X).

According to one aspect of the present invention, a urethane (urea) resin composition for molding that exhibits high antiviral effects and excellent moldability can be provided.

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 "A or greater, B or less."

The present invention provides a urethane (urea) resin composition for molding containing 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).

In this invention, "urethane (urea) resin" includes both urethane resin containing only urethane bonds and urethane-urea resin containing both urethane bonds and urea bonds.

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

In this invention, "antiviral activity" refers to the effect of inactivating a virus by reducing the number of viruses or reducing the infectivity titer of the virus. Examples of viruses include enveloped viruses. Examples of enveloped viruses include influenza viruses and coronaviruses.

Examples of thermoplastic urethane (urea) resin particles (X) include resins obtained by reacting polymeric 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 polymeric 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.

The number-average molecular weight (hereinafter abbreviated as Mn) of polymeric diol (a) can be calculated from the hydroxyl value of the diol, measured according to the method specified in JIS K1557-1 (Plastics - Test methods for polyols used in polyurethane raw materials - Part 1: Method for determining hydroxyl value).

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).

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

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 ester-forming 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).

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.

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.

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

Examples of polycarbonate diols (a2) include polycarbonate polyols produced by condensing the aforementioned difunctional alcohol (a11) with a low molecular weight carbonate compound (for example, a dialkyl carbonate with an alkyl group having 1 to 6 carbon atoms, 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 undergoing a de-alcoholization reaction. Two or more types of difunctional alcohols (a11) and low molecular weight carbonate compounds may be used in combination.

Specific examples of polycarbonate polyols (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 with a dialkyl carbonate while undergoing a de-alcoholization reaction).

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

Examples of polyetherdiols (a4) include compounds in which an alkylene oxide is added to a compound containing two hydroxyl groups (e.g., a difunctional alcohol (a11), divalent phenols, etc.). Examples of the aforementioned divalent phenols include bisphenols [bisphenol A, bisphenol F, bisphenol S, etc.] and monocyclic phenols [catechol, hydroquinone, resorcinol, etc.].

Examples of compounds obtained by adding an alkylene oxide to a difunctional alcohol (a11) include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of compounds formed by the addition of alkylene oxides to divalent phenols include alkylene oxide adducts of hydroquinone (carbons 2-6), alkylene oxide adducts of catechol (carbons 2-6), alkylene oxide adducts of resorcinol (carbons 2-6), and alkylene oxide adducts of bisphenol A (carbons 2-6).

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

Examples of polyalkanedione diols (a6) include hydroxyl-terminated polyalkanedione diols such as 1,4-polyisoprendiol, 1,4-polybutadienediol, 1,2-polybutadienediol, and hydrogenated 1,4- or 1,2-polybutadienediol.

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

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

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. The low molecular weight diol (b) may be used alone or in combination of two or more types.

Examples of monools (c) include aliphatic monools with 1 to 8 carbon atoms [linear monools (methanol, ethanol, propanol, butanol, pentanol, hexanol, and octanol, etc.) and branched monools (isopropyl alcohol, neopentyl alcohol, 3-methylpentanol, and 2-ethylhexanol, etc.)]; monools with cyclic groups with 6 to 10 carbon atoms [alicyclic monools (cyclohexanol, etc.) and aromatic monools with 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 with 6 to 10 carbon atoms and aromatic monools with 7 to 12 carbon atoms are preferred.

Examples of diamine (d) include alicyclic diamines having 6 to 10 carbon atoms (e.g., 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, diaminocyclohexane, and isophorone diamine); aliphatic diamines having 2 to 10 carbon atoms (e.g., ethylenediamine, butylenediamine, hexamethylenediamine); aromatic aliphatic diamines having 8 to 10 carbon atoms (e.g., 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, with isophorone diamine and hexamethylenediamine being particularly preferred.

Examples of organic diisocyanates (e) include the following:

(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.].

(ii) Alicyclic diisocyanates with 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.].

(iii) Aromatic aliphatic diisocyanates with 8 to 15 carbon atoms [e.g., m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate].

(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.].

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

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.

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

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

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.

In this invention, the volume-average particle diameter of the thermoplastic urethane (urea) resin particles (X) is the particle diameter (d50) at which the cumulative amount reaches 50%, as measured using a laser diffraction particle size distribution analyzer in the relative cumulative particle size distribution curve (volume-based).

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.

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

(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.

(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.

(3) A method for reacting high molecular weight diols (a), low molecular weight diols (b), monools (c), diamines (d), and organic diisocyanates (e) in a single reaction.

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.

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.).

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

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, and silica powder, etc.), and surfactants (sodium dodecylbenzenesulfonate and sodium lauryl sulfate, etc.).

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

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

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

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

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.).

The antiviral agent (Y) used in this 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.

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 agent used.

In this invention, insolubility refers to a solubility of 0.1 g or less per 100 g of deionized water at 25°C.

The aforementioned solubility can be measured by the following method: Add 100 g of deionized water at 25°C to a 200 mL beaker, add the thoroughly dried substance to be measured (antiviral agent), insert a stirrer tip measuring 20 mm in length and 7 mm 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 this point is considered 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.

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

The form of the antiviral agent used in this invention is not particularly limited; it may be a liquid, powder, etc., but particles are preferred. The shape of the antiviral agent particles is not particularly limited; for example, they may be spherical, cylindrical, or irregularly shaped.

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).

In this invention, the volume-average particle diameter of the antiviral agent (Y) is the particle diameter (d50) at which the cumulative amount reaches 50%, as measured using a laser diffraction particle size distribution analyzer in the relative cumulative particle size distribution curve (volume-based).

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 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.

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 with a desired shape.

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).

The following conditions (1) and (2) are considered to be 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) has irregularities.

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

In antiviral urethane (urea) resin particles (W), the presence of an antiviral agent (Y) on at least a portion of the surface of the thermoplastic urethane (urea) resin particles (X) can be confirmed, for example, by observing that the mass concentration of the constituent elements of the antiviral agent (Y) is 0.05% or higher in the SEM-EDX elemental mass concentration on the antiviral urethane (urea) resin particles (W).

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 higher, a large amount of the antiviral agent (Y) adheres to the thermoplastic urethane (urea) resin particles (X), and a sufficient antiviral effect can be achieved. 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%.

The following are the desirable SEM-EDX measurement conditions.
<SEM-EDX measurement conditions>
<Carbon vapor deposition processing equipment>
Sanyu 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 level: 1 × 10⁻⁴ Pa or less. Acceleration voltage: 25 kV
Current mode: Medium.

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

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

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.

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).

The inorganic filler (Z1) must not have antiviral properties and must not serve as a carrier for antiviral agents. Examples include talc, calcium carbonate, sericite, graphite, magnesium hydroxide, aluminum hydroxide, and zinc borate. Of these, talc is preferred.

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 molding urethane (urea) resin composition.

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).

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. 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.

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.

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).

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.); trimellitate esters (tri-2-ethylhexyl trimellitate and trioctyl trimellitate, etc.); fatty acid esters (butyl oleate, etc.); aliphatic phosphate esters (trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, etc.); Examples include phosphates and tributoxyphosphates; 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.]; halogen 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.

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).

As the release agent (Z4), known release agents can be used, including fluorine compound type release agents [triperfluoroalkyl phosphate (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.

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).

As stabilizers (Z5), in addition to ultraviolet absorbers (Z51), antioxidants (Z52), and hydrolysis inhibitors (Z53), compounds containing carbon-carbon double bonds (such as ethylene bonds, which may have substituents) (excluding double bonds in aromatic rings) or carbon-carbon triple bonds (such as acetylene bonds, which may have substituents) in their molecules can be used.

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.].

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].

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.

Examples of compounds having a carbon-carbon double bond or carbon-carbon triple bond in their molecule include esters of (meth)acrylic acid with 2-10 valent polyhydric alcohols (2-10 valent polyhydric alcohols, hereinafter the same) [ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 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.

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.

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).

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

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).

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).

[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 the 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 the 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).

In the mixing process, any known powder mixing device can be used, including rotary container mixers, stationary container mixers, and fluid-motion mixers. For example, stationary container mixers include high-speed fluid mixers, double-screw paddle mixers, high-speed shear mixers [e.g., Henschel Mixer®], low-speed mixers (e.g., planetary mixers), and conical screw mixers [e.g., Nauta Mixer®]. Among these, preferred are the double-screw paddle mixer, low-speed mixers (e.g., planetary mixers), and conical screw mixers (e.g., Nauta Mixer).

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

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.

Methods for molding 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.).

The urethane (urea) resin composition for molding of the present invention contains a high concentration of antiviral agent on the surface of the particles. Therefore, by molding the particles directly, 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.).

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.

[Manufacturing Example 1: Manufacturing of Thermoplastic Urethane Urea Resin Particles (X-1)]
In a reaction vessel equipped with a thermometer, a stirrer, and a 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%.

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 uniformly stirred at 20°C. Then, using an Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.], 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). Subsequently, 103.3 parts of a solution of prepolymer (Up-1) warmed 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).

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.

[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 to 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 stirred for 1 minute at a rotation speed of 700 ^min⁻¹ .

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: Chinuvin 765, manufactured by BASF Japan Ltd.] (Z51-1) were added as an ultraviolet absorber (Z51). The mixture was mixed at 70°C under stirring for 4 hours to impregnate the thermoplastic urethane urea resin particles (X-1) with the plasticizer (Z3-1) and ultraviolet absorber (Z51-1).

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.

(1-2) Manufacturing of molded articles The molding resin composition manufactured 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.

Furthermore, a Ni electroformed mold with a textured surface, preheated to 250°C, was filled with a urethane (urea) resin composition for molding. After holding for 60 seconds, 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.

[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.

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 underwent antiviral and moldability tests. The results are shown in Table 1.

<Evaluation Method>
[Method for measuring Mn in thermoplastic urethane urea resin particles]
The manganese (Mn) of thermoplastic urethane urea resin particles (X) was measured using gel permeation chromatography under the following conditions.
• Equipment: "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: 100 μL
• Detection device: Refractive index detector • Reference material: 12 samples of standard polystyrene (TSK standard POLYSTYRENE) (molecular weights 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.

[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.

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

<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 markings were drawn at 40 mm intervals in the center of each specimen. The minimum thickness between the five markings 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.

<Moldability>
The molded skins with a thickness of 1.0 mm obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were cut into 100 mm x 100 mm sections. 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 has a smooth surface.
4: There are some parts that are uneven in a particulate manner, derived from 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.

<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.

Claims (3)

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). The molding urethane (urea) resin composition according to claim 1, wherein the antiviral agent (Y) is insoluble in water at 25°C. A molded article obtained by molding the urethane (urea) resin composition for molding described in claim 1 or 2.