JP6413667B2 - Thermoplastic resin composition, molded product containing the same, and method for producing thermoplastic resin composition - Google Patents

Description

  The present invention relates to a thermoplastic resin composition in which metal fine particles protected with a polyurethane resin are supported on the surface of a thermoplastic resin.

  Metal fine particles (particularly fine particles having a size on the order of nanometers) are often attracting attention because they often have different properties from the bulk. For example, many properties such as a significant decrease in melting temperature and firing temperature, fluorescence emission, surface plasmon absorption, high catalyst efficiency, and new reactions have been confirmed so far. These functions are thought to be due to an increase in atom migration / diffusion / solubility due to having a high surface area, a quantum size effect, or the influence of the surface or interface.

  As methods for producing such metal fine particles, there are a method using chemical metal ion reduction or thermal decomposition of a complex containing a metal (liquid phase method), and heating and evaporating the metal in a vacuum. The method of collecting and recovering (gas phase method) is widely known.

  In order to use the metal fine particles produced by these methods efficiently in the industry (for example, for improving the activity when used as a catalyst or for repeated use), a method for supporting the metal fine particles on a certain substrate has been developed. For example, as a method for supporting metal fine particles on a substrate, the following techniques can be cited. Here, the substrate is not particularly limited as long as it is an object capable of immobilizing metal fine particles, but refers to those having the shape of powder, short fiber, pellet, film, ingot, dango lump, or sheet.

  One of them is a method in which metal ions are reduced on the substrate surface and directly supported (for example, Patent Documents 1 and 2). In this method, the substrate is brought into contact with a solution containing a metal salt or a metal complex, and then the noble metal fine particles are directly deposited on the substrate surface while reducing the noble metal ions by adding a reducing agent. In addition to the addition of a reducing agent, there are a heat reduction with a reducing gas and a reduction method by ultraviolet light irradiation (for example, Reference Patent Document 3).

  Also known is a method in which fine metal particles are prepared in advance and then fixed to a substrate. Specifically, there is a method in which a colloidal solution containing metal fine particles as a colloid is brought into contact with a substrate to naturally adsorb noble metal fine particles on the surface of the substrate (for example, Patent Documents 4 and 5).

  In many cases, the surface of the metal fine particles produced in this way has a very high activity, and when the surface is exposed, the metal fine particles easily aggregate and become coarse, and various characteristics derived from the size can be expressed. Disappear. In order to prevent this, a method of protecting the surface of the metal fine particles with an organic compound (for example, a polymer such as polyvinylpyrrolidone) has been taken (for example, Reference Non-Patent Documents 1 to 3). However, depending on the type of the organic compound used for protecting the metal fine particles, there is a problem that the fixing to the substrate is not sufficient, and the organic compound drops off immediately or the expected function is not fully exhibited.

JP 9-47659 A JP 2003-320249 A JP 2000-157874 A JP 2004-100040 A JP 2002-305001 A

N. Toshima, M .; Harada, T .; Yonezawa, K .; Kushihashi, and K.K. Asakura, The Journal of Physical Chemistry, 1991, Vol. 95 p. 7448 H. Hirai, Y. et al. Nakao, and N.A. Toshima, J .; Macromol. Sci. Chem. 1979, Vol. A13 p. 727 N. Toshima, T .; Yonezawa, and K.K. K. Kushihashi, J. et al. Chem. Soc. , Faraday Trans. 1993, Vol. 89 p. 2537

  The present invention has been made in view of the background art described above, and the object thereof is to use a thermoplastic resin composition in which metal fine particles protected with a polyurethane resin are supported on the surface of a thermoplastic resin. An object of the present invention is to provide a thermoplastic resin composition in which fine particles are coated with a protective agent or the like and stabilized when supported on a resin, and the aggregation of metal fine particles hardly occurs.

  Further, the present invention uses a thermoplastic resin composition in which antibacterial metal fine particles protected by a polyurethane resin are supported on the surface of a thermoplastic resin, whereby the metal fine particles are protected with a protective agent, and Since it is carried, it is to provide a thermoplastic resin composition that can stably exhibit an antibacterial effect even after a post-processing step.

  As a result of intensive studies to solve the above problems, the present inventor has made the present invention. That is, the present invention is as follows.

1. A thermoplastic resin composition in which metal fine particles protected with a polyurethane resin are supported on the surface of a thermoplastic resin.

2. Item 2. The thermoplastic resin composition according to Item 1, wherein the shape of the thermoplastic resin is any one of powder, short fiber, pellet, film, ingot, dango lump, and sheet.

3. Item 3. The thermoplastic resin composition according to Item 1 or 2, wherein a size of the thermoplastic resin is in a range of 0.1 μm to 5 mm.

4). Item 4. The thermoplastic resin composition according to any one of Items 1 to 3, wherein the polyurethane resin is an aqueous polyurethane resin.

5. Item 5. The thermoplastic resin composition according to Item 4, wherein the aqueous polyurethane resin is an emulsion-type aqueous polyurethane resin.

6). Item 6. The thermoplastic resin composition according to any one of Items 1 to 5, wherein the metal fine particles have a particle diameter of 1 to 1000 nm.

7). Item 7. The thermoplastic resin composition according to any one of Items 1 to 6, wherein the metal fine particles are made of gold, silver, copper, platinum, or a composite thereof.

8). Item 8. The thermoplastic resin composition according to any one of Items 1 to 7, wherein the thermoplastic resin is at least one member selected from the group consisting of polyamide and rubber-reinforced styrene resin.

9. Item 9. The thermoplastic resin composition according to any one of Items 1 to 8, wherein the metal fine particles have antibacterial properties.

10. Suspending or immersing the thermoplastic resin in a solution containing a metal compound that dissolves in water or an organic solvent, a protective agent for the metal fine particles, and a reducing agent, and supporting the metal fine particles on the surface of the thermoplastic resin in the solution. A method for producing a thermoplastic resin composition.

11. Item 11. The method for producing a thermoplastic resin composition according to Item 10, wherein the protective agent for the metal fine particles is an aqueous polyurethane resin.

12 Item 12. The method for producing a thermoplastic resin composition according to Item 10 or 11, wherein the metal fine particles are composed of gold, silver, copper, platinum, or a composite thereof.

13. Item 10. A molded article using the thermoplastic resin composition according to any one of Items 1 to 8.

14 Item 10. An antibacterial molded article using the thermoplastic resin composition according to Item 9.

  The present invention can provide a thermoplastic resin composition or the like that hardly causes aggregation of particles by using a thermoplastic resin composition in which metal fine particles protected with a polyurethane resin are supported on the surface of a thermoplastic resin. effective.

  Furthermore, since the shape of the thermoplastic resin is any of powder, short fiber, pellet, film, ingot, dango lump, and sheet, metal fine particles can be stably supported on various shaped resins. The metal fine particles have an effect of imparting various functions (for example, antibacterial properties).

  Furthermore, when the size of the thermoplastic resin is in the range of 0.1 μm to 5 mm, the specific surface area of the thermoplastic resin is increased, which has the effect of increasing the loading efficiency of the metal fine particles.

  Further, when the size of the thermoplastic resin is in the range of 0.1 μm to 5 mm, the size becomes industrially easy to handle, and there is an effect that the molding process is facilitated in the subsequent process.

  Furthermore, since the size of the metal fine particles protected with the polyurethane resin is 1-1000 nm, it is possible to make a fine fiber when producing the fiber, and the antibacterial property is also obtained when the fiber is made fine. There is an effect that the provided fiber can be provided.

  Furthermore, since the present invention is such that the metal fine particles are coated with a protective agent and are supported with a resin, it is difficult to freely move the metal fine particles in the resin, and aggregation is unlikely to occur in post-processing steps, As a result, a stable antibacterial effect can be exhibited.

It is the result of having observed the cross section of the silver nanoparticle carrying | support pellet of Example 5 with the transmission electron microscope (TEM).

  The present invention relates to a thermoplastic resin composition in which metal fine particles protected with a polyurethane resin are supported on the surface of a thermoplastic resin, a method for producing the same, and a molded product using them.

(1) Thermoplastic resin Thermoplastic resins include polyamide resin, polyethylene, polypropylene, polystyrene, rubber-reinforced styrene resin (ABS resin, AS resin, etc.), acrylic resin and other general-purpose resin materials, polycarbonate, polyphenylene oxide, polyethylene Examples include terephthalate, polybutylene terephthalate, and polyphenylene sulfide. Among these, polyamide resin and / or ABS resin are preferable from the viewpoint of balance of heat resistance, toughness, and moldability. A resin having an amide bond or a carboxylic acid terminal is also preferred. Furthermore, maleic anhydride-modified resins that can be easily modified to carboxylic acids are also preferred.

  The polyamide resin has an acid amide bond (—CONH—) in the main chain, and corresponds to, for example, an aliphatic polyamide resin, an alicyclic polyamide resin, an aromatic polyamide resin, and a combination or combination thereof ( Examples thereof include polyamide resins containing at least one resin selected from (co) polymers. The monomer unit constituting the polyamide resin may be one type or two or more types.

  Examples of the aliphatic polyamide resin, alicyclic polyamide resin and / or aromatic polyamide resin include polyamide resins derived from lactam, aminocarboxylic acid, or a combination of diamine and dicarboxylic acid.

Among these polyamide resins, an aliphatic polyamide resin or an aromatic polyamide resin is preferable from the viewpoint of economy and versatility, and an aliphatic polyamide resin is particularly preferable from the viewpoint of workability and the balance of physical properties obtained.
As the polyamide resin, these polyamides can be used alone, or two or more kinds can be mixed and used. Furthermore, a copolyamide composed of a combination of two or more types can be used.

  Among the above aliphatic polyamide resins, selected from nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 612, nylon 6/66, nylon 6/11, nylon 6/12, nylon 6/66/12 Aliphatic polyamides used alone or in combination are preferred, and from the viewpoints of melting point and cost, nylon 6 and nylon 66 are particularly preferred, and nylon 6 is most preferred.

  The rubber-reinforced styrene resin used in the present invention is a copolymer comprising an aromatic vinyl monomer (a) component, a vinyl cyanide monomer (b) component and a rubbery polymer (c), Or it is resin characterized by being comprised from this and the copolymer of said (a) and (b). Examples of preferable rubber-reinforced styrene-based resins include those containing a graft copolymer in which the components (a) and (b) are graft-copolymerized in the presence of the rubbery polymer (c), and more preferably a bulk An ABS resin made by polymerization may be mentioned.

  Examples of the aromatic vinyl monomer (a) component include styrene, α-methyl styrene, o-, m-, p-methyl styrene, vinyl xylene, ethyl styrene, vinyl naphthalene, and the like. More than seeds can be used. Styrene is preferably used.

  Examples of the vinyl cyanide monomer (b) component include acrylonitrile, methacrylonitrile, and the like, and one or more of these can be used. Preferably, acrylonitrile is used.

  Examples of the rubber polymer (c) include polybutadiene, styrene-butadiene random copolymer or block copolymer, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, isoprene-butadiene copolymer, and the like. Diene rubber, ethylene-propylene random copolymer or block copolymer, polyisoprene, ethylene and α-olefin copolymer, ethylene-unsaturated such as ethylene-methacrylate, ethylene-butyl acrylate Copolymer with carboxylic acid ester, acrylic elastic polymer such as acrylic ester-butadiene copolymer, butyl acrylate-butadiene copolymer, copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, Ethylene such as ethylene-propylene-hexadiene copolymer - propylene nonconjugated Jienta - polymer -, butylene - Isoburen copolymers, chlorinated polyethylene and the like, may be to use them in one or two or more thereof. Preferred rubbery polymers are diene rubbers, ethylene-propylene non-conjugated diene polymers, and acrylic elastic polymers, and particularly preferred are polybutadiene and styrene-butadiene copolymers.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), (c), It can adjust according to a use.

  The shape of the thermoplastic resin is not particularly limited as long as it is a known shape, but since it can be easily produced industrially, it can be any shape of powder, short fiber, pellet, film, ingot, dango lump, and sheet. Preferably there is.

  The size of the thermoplastic resin is preferably in the range of 0.1 μm to 5 mm, and more preferably 1 μm to 3 mm. When the particle diameter is 0.1 μm or less, the specific surface area is increased, so that the powder itself is strongly aggregated and further dispersing agents are required, which is not preferable. On the other hand, when the particle diameter is 5 mm or more, the specific surface area becomes small and the effect of supporting the metal compound becomes low, which is not preferable. In particular, in a small size range (1 μm to 100 μm), the specific surface area is large, and therefore, it is suitably used for applications where the supporting efficiency of metal fine particles must be increased. On the other hand, in a large size range (500 μm to 3 mm), the size is industrially easy to handle, and it is suitably used for applications that require molding in a subsequent process.

(2) Metal fine particles The metal fine particles in the present invention may be any metal fine particles, preferably metal fine particles that exhibit antibacterial properties, and silver, copper, gold, platinum, etc. are known to exhibit antibacterial properties. Therefore, it is preferable. Among them, it is preferable to use silver fine particles from the viewpoints of easy availability of the compound, easy availability at low cost, and easy antibacterial activity.

  The metal fine particles in the present invention have a primary particle diameter in the range of 1 nm to 1000 nm, for example, which is observed using a transmission electron microscope (TEM), and preferably 2 nm to 500 nm. The shape is not particularly limited to a spherical shape, an indefinite shape, a lump shape, a needle shape, a rod shape, or the like, but in order to obtain antibacterial activity and a molded product, it is preferable that the primary particle diameter and shape of the particles are uniform. Fine particles larger than 1000 nm may be inconvenient in the resin molding process after supporting metal fine particles (for example, they cannot be thinned during fiberization), which is not preferable.

  The metal fine particle content in the present invention is preferably in the range of 0.0005 to 1% by mass. Furthermore, 0.001-0.05 mass% is preferable. If it is less than 0.0005% by mass, the antibacterial activity cannot be obtained, which is not preferable. When the amount is more than 1% by mass, aggregation of metal fine particles may occur, and a uniform particle size and dispersion cannot be obtained, so that antibacterial properties may be lowered, which is not preferable.

(3) Polyurethane resin The polyurethane resin in the present invention is not particularly limited, and examples thereof include a polyether polyurethane resin, a polyester polyurethane resin, and a polycarbonate polyurethane resin. These can be used alone or in combination of two or more. In addition, the form of the polyurethane resin can be used regardless of whether it is a solventless system, a hot melt system, a solvent system, an aqueous system, etc. It can be selected appropriately. Among these, water-based aqueous polyurethane resins are particularly preferably used from the viewpoint of safety and processability in which dispersions and solutions can be adjusted.

As the aqueous polyurethane resin in the present invention, any of an emulsion type dispersed in a solvent and a solution type existing in a dissolved state in the solvent may be used. The emulsion type can be classified into a forced emulsification type and a self-emulsification type depending on the emulsification method, but any type can be used in this embodiment.
The aqueous polyurethane resin in the present invention may be polymerized from, for example, a polyol, a diisocyanate compound, a diamine compound and a diol compound, but is not particularly limited in the present invention. Also, the synthesis method is not particularly limited. The aqueous polyurethane resin may be polymerized from, for example, a polymer diol, diisocyanate, and a low molecular weight diamine, or may be polymerized from a polymer diol, diisocyanate, a low molecular weight diol, or the like.

When the thermoplastic resin in the present invention is a polyamide resin and / or an ABS resin, a polyurethane resin is desirable as a material for protecting the metal fine particles. In particular, those having —NH ₂ in the molecular structure are particularly desirable. This has a high affinity with the carboxylic acid (—COOH) or carbonyl group (> C═O) at the end of the polyamide present on the surface of the polyamide resin, and part of the carboxylic acid (—COOH) and —NH _{2 of the} polyurethane resin It is considered that an amide bond is formed between these. Accordingly, since the polyurethane resin coated with the metal fine particles is strongly bonded on the surface of the polyamide resin, the metal fine particles are strongly supported in the polyamide resin and are not easily detached.

  The thermoplastic resin in the present invention is not limited to polyamide as long as it has an amide bond or a carboxylic acid terminal in the molecule from the viewpoint of affinity with the protective agent comprising the polyurethane resin. For example, polyamic acid, which is a precursor of polyimide, a protein having a peptide bond, maleic anhydride-modified resin, such as maleic anhydride-modified polypropylene, and the like.

  In the case where the thermoplastic resin in the present invention is a polyamide resin and / or an ABS resin, the polyamide resin and / or the ABS resin may be used in a solution in which the polyamide resin and / or the ABS resin are dispersed in the presence of the polyurethane resin. It is produced by reducing the ions it contains. According to this method, since the metal fine particles generated by reduction are supported on the polyamide resin and / or ABS resin in a state of being covered with the polyurethane resin, the polyurethane resin is strongly bonded on the surface of the polyamide resin and / or ABS resin. Therefore, it is considered that the metal fine particles are strongly supported in the polyamide and / or ABS resin particles and are not easily detached. In contrast, in the method in which the polyamide resin and / or ABS resin is brought into contact with the reduced metal fine particle solution, the metal fine particles are hardly supported on the polyamide and / or ABS resin.

Examples of ions containing metal species include metal chlorides, metal bromides, metal nitrates, metal sulfates, metal acetates, and metal perchlorates. As a method for reducing metal species, a method of reducing at room temperature or low temperature using an inorganic reducing agent such as hydrazine or sodium borohydride, or refluxing at 60 to 100 ° C. using amines such as polyethyleneimine or triethylamine. A method of reducing, a method of reducing by refluxing at 60 to 80 ° C. in an alcohol such as methanol and ethanol, a method of reducing by refluxing at 60 to 80 ° C. using an organic reducing agent such as ascorbic acid and formaldehyde, Although the method etc. which reduce | restore by irradiating an ultraviolet light at normal temperature are mentioned, It is not limited to this.
Moreover, when the polyurethane resin to be used itself has a reducing action, it is not necessary to use another reducing agent.

(4) Thermoplastic Resin Composition As a method for producing a thermoplastic resin composition, a thermoplastic resin is added to a solution containing a metal compound dissolved in water or an organic solvent, and a protective agent for metal fine particles generated from the metal compound. Can be suspended or immersed, and metal fine particles can be supported on the surface of the thermoplastic resin in the solution via a protective agent.

  The thermoplastic resin composition in the present invention is produced by reducing ions containing metal species in the presence of a polyurethane resin in a solution in which a thermoplastic resin is dispersed. According to this method, since the metal fine particles generated by reduction are supported on the thermoplastic resin in a state of being covered with the polyurethane resin, the polyurethane fine resin is strongly bonded on the surface of the thermoplastic resin. It is considered that it is strongly supported in the inside and is not easily detached.

  As a manufacturing process of a thermoplastic resin composition, a solution in which a thermoplastic resin is dispersed, a polyurethane resin, an ion containing a metal species, and a reducing agent can be colored if they can be mixed uniformly before reducing the ions. The degree does not affect their order of addition.

  In the present invention, the produced thermoplastic resin composition can be solid-liquid separated by a method such as decantation, filtration or centrifugation. Moreover, it can be made to dry later using vacuum drying or constant temperature drying.

  The thermoplastic resin composition includes pellets and particles, and may be a thermoplastic resin composition in which metal fine particles are also supported on a thermoplastic resin such as pellets. A thermoplastic resin composition may be used. The molded product containing the thermoplastic resin composition includes an injection molded product, an extrusion molded product and the like molded using pellets and particles.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. The particle size, ICP, TEM, antibacterial activity value, and the like were measured as follows.

(Average particle size)
The average particle size and particle size distribution of the powder were measured in accordance with ISO 13319 using a Coulter counter. Further, particles outside the measurable range of the Coulter counter were measured by a laser diffraction scattering method (based on ISO13320). The number average particle size, volume average particle size, and particle size distribution index (PDI) are expressed by the following equations.

Xi；個々の粒子径
n；測定数

Xi: Individual particle size
n: Number of measurements

  About the particle diameter of the pellet exceeding 1 mm, it measured with calipers etc. and made the longest thing the particle diameter.

  Quantification of the metal content in the thermoplastic resin compound is obtained by wet decomposition of 5 mg of the dried thermoplastic resin compound sample with nitric acid, and then by mass from the emission intensity of the metal component in the thermoplastic resin compound sample by ICP emission analysis. The fraction was determined.

  The presence of metal fine particles in the thermoplastic resin compound was confirmed by a TEM photograph of the color and cross section of the thermoplastic resin compound.

  For the antibacterial activity value, a molded sheet pressed with a thermoplastic resin compound was used. The antibacterial test method was measured according to JIS Z2801 (film adhesion method), and Escherichia coli NBRC3982 was used as the test strain.

(Specific surface area)
The specific surface area was measured at 3 points (based on ISO 9277) by the BET method using nitrogen adsorption.

(Production Example 1)
A nylon solution consisting of 200 g of polyamide 6 (molecular weight 8000) and 800 g of phenol was prepared. To this polyamide 6 solution, 4000 g of isopropanol, which is a non-solvent of polyamide, and 500 g of water were stirred and mixed with a magnetic stirrer and stirred for 1 minute, and the solution became uniform. Polymer was precipitated after 2 minutes of stirring. The mixed solution was allowed to stand for 24 hours to complete the precipitation of the polymer. The obtained precipitated polymer was washed with warm methanol and acetone, and then the polymer was isolated by centrifugation.
Observation of the obtained particles with a scanning electron microscope revealed porous polyamide spherical particles having a number average particle size of 6.8 μm and a volume average particle size of 10.6 μm. The PDI was 1.56 and the specific surface area was 19.4 m ² / g.

Example 1
1.25 g of porous polyamide spherical particles (number average particle size 6.8 μm) produced by the method described in Production Example 1 are dispersed in 119 g of ethanol, and 2.00 g of a 1% by weight aqueous solution of chloroauric acid tetrahydrate, 18.64 g of “ETARNACOLL UW-1005-E” (emulsion-type aqueous polyurethane resin, solid content 30% by weight) manufactured by Ube Industries, Ltd. was added and mixed with stirring at 70 ° C. for 1 hour. Porous polyamide spherical particles carrying gold nanoparticles protected with a polyurethane resin were collected by filtration, repeatedly washed with methanol, and then vacuum dried. The obtained powder was colored pink and the amount of gold supported was 0.19% by mass.

(Example 2)
1.25 g of porous polyamide spherical particles (number average particle size 6.8 μm) produced by the method described in Production Example 1 are dispersed in 119 g of ethanol, and 2.00 g of a 1% by weight aqueous solution of chloroauric acid tetrahydrate, 20.12 g of “ETARNACOLL UW-5002” (emulsion-type aqueous polyurethane resin, solid content 30% by weight) manufactured by Ube Industries, Ltd. was added and mixed with stirring at 70 ° C. for 1 hour. Porous polyamide spherical particles carrying gold nanoparticles protected with a polyurethane resin were collected by filtration, repeatedly washed with methanol, and then vacuum dried. The obtained powder was colored pink and the amount of gold supported was 0.20% by mass.

(Example 3)
1.25 g of porous polyamide spherical particles (number average particle size: 6.8 μm) prepared by the method described in Production Example 1 are dispersed in 119 g of ethanol, 1.00 g of a 10 wt% silver nitrate aqueous solution, “ETARNACOLL” manufactured by Ube Industries, Ltd. 18.82 g of “UW-1005-E” (emulsion type aqueous polyurethane resin, solid content 30% by weight) was added, and the mixture was stirred and mixed at 70 ° C. for 1 hour. Porous polyamide spherical particles carrying silver nanoparticles protected with a polyurethane resin were collected by filtration, washed repeatedly with methanol, and then vacuum dried. The obtained powder was colored yellow and the supported amount of silver was 0.29% by mass.

Example 4
1.25 g of porous polyamide spherical particles (number average particle size: 6.8 μm) prepared by the method described in Production Example 1 are dispersed in 119 g of ethanol, 1.00 g of a 10 wt% silver nitrate aqueous solution, “ETARNACOLL” manufactured by Ube Industries, Ltd. UW-5002 ”(emulsion-type aqueous polyurethane resin, solid content 30% by weight) was added and mixed with stirring at 70 ° C. for 1 hour. Porous polyamide spherical particles carrying silver nanoparticles protected with a polyurethane resin were collected by filtration, washed repeatedly with methanol, and then vacuum dried. The obtained powder was colored yellow and the supported amount of silver was 0.21% by mass.

(Example 5)
20.04 g of polyamide 6 pellets (average particle size 3 mm) manufactured by Ube Industries, Ltd. are dispersed in 252 g of ethanol, 8.02 g of a 10% by weight aqueous solution of silver nitrate, “ETARNACOLL UW-1005-E” (emulsion type) manufactured by Ube Industries, Ltd. 5.75 g of an aqueous polyurethane resin (solid content 30 wt%) was added, and the mixture was stirred and mixed at 70 ° C. for 2 hours. Polyamide 6 pellets carrying silver nanoparticles protected with polyurethane resin were collected by filtration, washed repeatedly with methanol, and then vacuum dried. The obtained pellets were colored yellow-brown, and the supported amount of silver was 0.074% by mass. The result of having observed the cross section of the silver nanoparticle carrying | support pellet obtained with the transmission electron microscope (TEM) is shown in FIG. It was confirmed that silver nanoparticles having a particle diameter of 30 nm or less were uniformly fixed on the surface of the nylon pellet.
The pellets were kneaded with polyamide pellets using a lab plast mill, and a molded sheet was prepared by pressing. As a result, the silver content in the obtained molded sheet was 0.021% by mass. The obtained molded sheet had an antibacterial activity value against Escherichia coli based on JIS standard Z2801 of 4.9.

(Example 6)
32.30 g of ABS resin pellet EX120 (average particle size 2 mm) manufactured by UMG-ABS Co., Ltd. was dispersed in a mixed solvent of 150 g of ethanol and 151 g of water, 3.38 g of a 10 wt% aqueous solution of silver nitrate, “ETARNACOLL” manufactured by Ube Industries, Ltd. 2.39 g of “UW-1005-E” (emulsion type aqueous polyurethane resin, solid content 30% by weight) was added, and the mixture was stirred and mixed at 70 ° C. for 1 hour. ABS resin pellets carrying silver nanoparticles protected with polyurethane resin were collected by filtration, washed repeatedly with methanol, and then vacuum dried. The obtained pellets were colored brown and the supported amount of silver was 0.098% by mass.
The pellets were kneaded with polyamide pellets using a lab plast mill, and a molded sheet was prepared by pressing. The obtained molded sheet had an antibacterial activity value against Escherichia coli according to JIS standard Z2801 of 4.4.

(Example 7)
ABS resin pellet EX120 (average particle size 2 mm) manufactured by UMG-ABS Co., Ltd. 1.25 g was dispersed in 116 g of ethanol, 0.51 g of a 10% by weight silver nitrate aqueous solution, “ETARNACOLL UW-5002” manufactured by Ube Industries, Ltd. (emulsion) Type aqueous polyurethane resin, solid content 30 wt%) 0.41 g was added and stirred and mixed at 70 ° C. for 1 hour. ABS resin pellets carrying silver nanoparticles protected with polyurethane resin were collected by filtration, washed repeatedly with methanol, and then vacuum dried. The obtained pellet was colored brown and the supported amount of silver was 0.078% by mass.

Claims (13)

A thermoplastic resin composition in which metal fine particles protected with a polyurethane resin are supported on the surface of a thermoplastic resin having an amide bond, a carboxylic acid terminal or a carbonyl group, and / or a rubber-reinforced styrene thermoplastic resin , A thermoplastic resin composition in which the size of the thermoplastic resin is in the range of 0.1 μm to 5 mm . The thermoplastic resin composition according to claim 1, wherein the shape of the thermoplastic resin is any one of powder, short fiber, pellet, film, ingot, dango lump, and sheet. The thermoplastic resin composition according to claim 1, wherein the polyurethane resin is an aqueous polyurethane resin. The thermoplastic resin composition according to claim 3, wherein the aqueous polyurethane resin is an emulsion-type aqueous polyurethane resin. The thermoplastic resin composition according to any one of claims 1 to 4, wherein a particle diameter of the metal fine particles is 1-1000 nm. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the metal fine particles are made of gold, silver, copper, platinum, or a composite thereof. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin is a polyamide resin and / or an ABS resin . The thermoplastic resin composition according to claim 1, wherein the metal fine particles have antibacterial properties. Suspending or immersing a thermoplastic resin having an amide bond, a carboxylic acid terminal or a carbonyl group and / or a rubber-reinforced styrene-based thermoplastic resin in a solution containing a metal compound, a polyurethane resin , and a reducing agent dissolved in water or an organic solvent And a method for producing a thermoplastic resin composition, comprising supporting metal fine particles on the surface of the thermoplastic resin in a solution. The method for producing a thermoplastic resin composition according to claim 9, wherein the polyurethane resin is an aqueous polyurethane resin. The method for producing a thermoplastic resin composition according to claim 10, wherein the metal fine particles are made of gold, silver, copper, platinum, or a composite thereof. The molded article using the thermoplastic resin composition in any one of Claims 1-7. A molded article having antibacterial properties using the thermoplastic resin composition according to claim 8.

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