JP6658073B2 - Method for producing antimicrobial polyamide or polyester resin composition - Google Patents

Description

  The present invention relates to an antibacterial resin composition in which metal fine particles coated with a specific polymer as a protective agent are supported on the surface of a polyamide or polyester resin having a specific particle size.

  Conventionally, metal particles are dispersed in a resin to produce a molded article using the same. Specifically, an inorganic antibacterial agent (activated carbon carrying silver or copper, apatite, zeolite, etc.) and a thermoplastic resin are used. Mixing, injection molding, and extrusion molding are used to produce fibers and film-like molded products. Generally, resins with antibacterial properties are prepared by melt kneading organic or inorganic antibacterial agents with thermoplastic resins or dispersing them in a solution, followed by post-processing such as casting, spinning, extrusion molding, and injection molding. As a result, resin films, fibers, and molded articles having antibacterial properties are obtained. However, organic antibacterial agents have problems in sustainability and stability of antibacterial effects such as easy recrystallization in resin and bleeding out.In addition, from the viewpoint of human safety, inorganic antibacterial agents have recently been used. Many blended resins have been used.

  The resin consisting of an inorganic antibacterial agent is processed into a masterbatch once by melting and kneading a thermoplastic resin with activated carbon, apatite, silica, zeolite, etc. carrying silver ions, copper ions, etc. You. Patent Literature 1 describes a method for producing a masterbatch by melt-kneading and extruding a soluble glass containing silver ions together with a resin together with a lubricant.

  A masterbatch can also be prepared by directly melting and kneading a silver compound with a resin to reduce it to silver nanoparticles. Patent Document 2 discloses a method for producing a masterbatch containing silver nanoparticles by melt-kneading silver lactate with a resin.

  On the other hand, in Patent Document 3, a nylon 6 pellet is immersed in a methanol solution containing silver trifluorobutyrate, and then dried to easily produce a master batch. A nylon fiber containing silver particles having a specific particle diameter by melt-spinning the master batch with nylon 66 pellets is described.

JP-A-5-255515 WO2010 / 098309 JP 06-287355 A

  In the conventional method of dispersing antibacterial silver fine particles and the like in a resin, when the mixing is insufficient, the inorganic antibacterial agent may be unevenly distributed and may not exert a sufficient effect. Therefore, as an improvement method, as in Patent Literature 1 and Patent Literature 2, it is necessary to form a master batch in which the antimicrobial component is once dispersed uniformly in the resin by melt-kneading, and in order to further commercialize it, it has been obtained. After kneading the masterbatch and the resin pellets again, it is necessary to perform post-processing such as injection molding or extrusion molding. For this reason, the melt-kneading step is required a plurality of times, and the antibacterial component causes agglomeration and the like, and there has been a problem that the antibacterial activity does not appear as much as the anticipated blending amount.

  In Patent Document 3, a masterbatch is formed without the need for a kneading step. However, at the stage of the masterbatch, silver ions or silver compounds are impregnated in the resin without a protective agent, so that Depending on the thermal processing conditions in processing, segregation, aggregation, and the like are generated in the generated silver nanoparticles, and there has been a problem in stably imparting antibacterial properties. For this reason, there has been a demand for an antibacterial resin in which the metal fine particles are coated with a protective agent or the like when the masterbatch is formed, and which is supported and stabilized by the resin.

  In order to solve the above, the inventor of the present invention has a technique in which metal fine particles protected by a nitrogen-containing polymer are supported on the surface of a thermoplastic resin having a particle size in the range of 100 μm to 50 mm, and a masterbatch process by melt-kneading is performed. Although a thermoplastic resin composition which is unnecessary and does not easily cause aggregation of the metal fine particles was studied, the maximum amount of the metal fine particles supported by the polyamide resin or the polyester resin under a predetermined experimental condition was 0.1. It is about 025% by mass, and from the viewpoint of cost, a master batch in which metal fine particles are further supported has been required.

  Further, as a method for producing a polyamide fiber, after mixing a resin as a fiber raw material and an inorganic antibacterial agent comprising a silver ion-inorganic carrier (such as zeolite), fiberization can be performed by melt spinning. Since the particle size of the antibacterial agent is relatively large as 2 to 20 μm, the fiber cannot be thinned to a size smaller than the size of the inorganic antibacterial agent. Had been.

  In the present invention, a metal fine particle protected by a nitrogen-containing polymer is supported on a surface of a polyamide resin or a polyester resin having a particle size of 100 μm to 50 mm, and the content is 0.05% by mass to 1% by mass. A method for producing a polyamide resin composition or a polyester resin composition, which does not require a masterbatch step by melt-kneading and is less likely to cause aggregation of metal fine particles. It is.

  Further, according to the present invention, metal fine particles protected by a nitrogen-containing polymer are supported on the surface of a polyamide resin or a polyester resin having a particle size in the range of 100 μm to 50 mm, and the content is 0.05% by mass to 1% by mass. % Is a masterbatch made by using a method for producing a polyamide resin composition or a polyester resin composition, which is a masterbatch by a dipping method of a metal compound. An object of the present invention is to provide a polyamide resin or a polyester resin composition capable of exhibiting an antibacterial effect stably even after a post-processing step because it is carried with a polyester resin.

  Further, according to the present invention, metal fine particles protected by a nitrogen-containing polymer are supported on the surface of a polyamide resin or a polyester resin having a particle size in the range of 100 μm to 50 mm, and the content is 0.05% by mass to 1% by mass. % Of a fiber prepared using a masterbatch comprising a method for producing a polyamide resin composition or a polyester resin composition, the fiber having an antibacterial effect even in a dyeing step in an acidic solution after fiberization. To provide.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention. That is, the present invention is as follows.

1. Polyamide resin in which metal fine particles protected by a nitrogen-containing polymer are supported on the surface of a polyamide resin or a polyester resin having a particle size in the range of 100 μm to 50 mm, and the content is 0.05% by mass to 1% by mass A method for producing a composition or a polyester resin composition, wherein the mass ratio of the metal component to the resin at the time of compounding is 0.25 to 0.5. Manufacturing method.

2. 2. The production of the polyamide resin composition or the polyester resin composition according to the above item 1, wherein the mass mixing ratio of the metal component and the total solid components excluding the solvent at the time of compounding is 0.2 to 0.5. Method.

3. 3. The polyamide resin composition or the polyester resin composition according to the above item 1 or 2, wherein the molar compounding ratio of the metal component and the protective agent comprising the nitrogen-containing polymer at the time of compounding is 3.7 to 8. Method of manufacturing a product.

4. Item 4. The method for producing a polyamide resin composition or a polyester resin composition according to any one of Items 1 to 3, wherein the nitrogen-containing polymer is polyethyleneimine.

5. The method for producing a polyamide resin composition or a polyester resin composition according to any one of Items 1 to 4, wherein the nitrogen-containing polymer polyethyleneimine has a molecular weight of 250 to 400.

6. Item 5. The method for producing a polyamide resin composition or a polyester resin composition according to any one of Items 1 to 4, wherein the average particle diameter of the metal fine particles is 1 to 1000 nm.

7. 6. The method for producing a polyamide resin composition or a polyester resin composition according to any one of the above items 1 to 5, wherein the metal fine particles are made of gold, silver, copper, platinum or a composite thereof.

8. 7. The method for producing a polyamide resin composition or a polyester resin composition according to any one of the above items 1 to 6, wherein the metal fine particles have antibacterial properties.

9. Item 8. A polyamide resin composition or a polyester resin composition obtained by the production method according to any one of Items 1 to 7.

10. A fiber containing the polyamide resin composition or the polyester resin composition obtained by the production method according to any one of the above items 1 to 7.

  The polyamide resin composition or polyester in which metal fine particles protected by a nitrogen-containing polymer are supported at a high concentration of 0.05% by mass to 1% by mass by the method for producing a polyamide resin composition or a polyester resin composition of the present invention. A master batch of the resin composition is obtained. For this reason, in the post-process (molding) after blending the masterbatch, antibacterial properties can be imparted to the product with a smaller blending amount, so that the antibacterial resin composition can be provided at a lower cost.

  Further, since the size of the metal fine particles protected by the nitrogen-containing polymer is 1 to 1000 nm, it is possible to reduce the fiber to 10 μm or less when producing the fiber. In addition, there is an effect that fibers having antibacterial properties can be provided.

  Furthermore, in the present invention, since the metal fine particles are coated with the protective agent and supported by the resin, it is difficult for the metal fine particles to freely move in the resin, and aggregation does not easily occur even in a post-processing step or the like, As a result, a stable antibacterial effect can be exhibited.

  The present invention relates to a method for producing a resin composition having antibacterial properties by supporting metal fine particles protected by a nitrogen-containing polymer on a surface of a polyamide resin or a polyester resin, and a molded product using the resin composition.

  The polyamide resin in the present invention has an acid amide bond (—CONH—) in the main chain, and includes, for example, an aliphatic polyamide resin, an alicyclic polyamide resin, an aromatic polyamide resin, and a combination or combination thereof. Polyamide resins containing at least one resin selected from the corresponding (co) polymers are listed. The number of monomer units constituting the polyamide resin may be one or two or more.

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

Among these polyamide resins, an aliphatic polyamide resin or an aromatic polyamide resin is preferable from the viewpoints of economy and versatility, and an aliphatic polyamide resin is particularly preferable from the viewpoints of processability and obtained physical property balance.
As the polyamide resin, these polyamides can be used alone or in combination of two or more. Further, a copolymerized polyamide composed of a combination of two or more kinds 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, and nylon 6/66/12. Aliphatic polyamides used alone or in combination are preferred, and nylon 6 and nylon 66 are particularly preferred from the viewpoint of melting point and cost, and nylon 6 is most preferred.

  The polyester resin in the present invention is selected from the group consisting of (a) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, (b) hydroxycarboxylic acid or its ester-forming derivative, and (c) lactone. It is a polymer or copolymer having at least one residue as a main structural unit. Here, the main structural unit refers to a structural unit that accounts for 50 mol% or more of all the structural units.

  Examples of the dicarboxylic acid or its ester-forming derivative include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, and anthracenedicarboxylic acid Acids, aromatic dicarboxylic acids such as 4,4'-diphenylether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecandioic acid And aliphatic dicarboxylic acids such as malonic acid, glutaric acid and dimer acid; alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and ester-forming derivatives thereof. Two or more of these may be used.

  Examples of the diol or its ester-forming derivative include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, and cyclohexanediene. Long chain glycols having a molecular weight of 200 to 100,000, such as aliphatic glycols having 2 to 20 carbon atoms such as methanol, cyclohexanediol and dimer diol, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol; Aromatic dioxy compounds such as dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and ester-forming derivatives thereof; It is below. Two or more of these may be used.

Examples of the polymer or copolymer having a structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, and poly Xylene terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexane dimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene iso Phthalate / terephthalate, polybutylene isophthalate / terephthaleie , Polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate,
Polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexane dimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfoisophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / Polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, polypropylene terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate Tallates / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol,
Polybutylene terephthalate / isophthalate / polytetramethylene glycol, polyethylene terephthalate / succinate, polypropylene terephthalate / succinate,
Polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, polybutylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / iso Phthalate / adipate,
Aromatic polyester resins such as polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, Polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, Fats such as polybutylene succinate / adipate Such group polyester resins. Here, “/” represents a copolymer.

Further, as the hydroxycarboxylic acid or an ester-forming derivative thereof, for example,
Glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-
Examples include 2-naphthoic acid and ester-forming derivatives thereof. Two or more of these may be used. Examples of the polymer or copolymer having these as a structural unit include, for example, aliphatic acids such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, and polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyvaleric acid. A polyester resin is exemplified.

Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one, and the like. Two or more of these may be used. Further, as a polymer or copolymer having these as structural units,
For example, polycaprolactone, polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone and the like can be mentioned.

  Among these polyester resins, polyethylene terephthalate is particularly preferably used because it is more excellent in mechanical properties such as flame retardancy and strength, heat resistance and durability.

  The particle diameter of the polyamide resin or polyester resin in the present invention is preferably in the range of 100 μm to 50 mm, and more preferably 200 μm to 20 mm. If the particle diameter is less than 100 μm, the specific surface area is increased, so that the aggregation of the powder itself becomes strong and a further dispersant or the like is required, which is not preferable. On the other hand, when the particle diameter is 50 mm or more, the effect of supporting the metal compound is reduced, which is not preferable.

  The shape of the polyamide resin or polyester resin is not particularly limited, but powder, pellet, chip, sheet, fiber, etc. are industrially used because they are easily processed when used as a master batch after supporting metal fine particles. It is preferable because it is easily available as a material.

(2) Regarding metal fine particles As the metal fine particles in the present invention, any metal fine particles can be used as long as they exhibit antibacterial properties, and silver, copper, gold, platinum and the like are known to exhibit antibacterial properties. preferable. Among them, it is preferable to use silver fine particles from the viewpoints of easily obtaining a compound, being easily available at a low cost, and easily obtaining an antibacterial activity.

  The metal fine particles in the present invention have a primary particle diameter in the range of 1 nm to 1000 nm, and more preferably 2 nm to 500 nm. More preferably, it is 3 nm to 100 nm. The shape is not particularly limited, such as a sphere, an irregular shape, a lump, a needle, and a rod, but it is preferable that the particles have the same primary particle diameter and shape in order to obtain antibacterial activity and a molded product. Fine particles having a diameter of more than 1000 nm are not preferred because they cannot be thinned during fiberization.

  The content of the metal fine particles in the present invention is preferably in the range of 0.05 to 1% by mass. Further, the content is more preferably 0.08 to 0.5% by mass. If the amount is less than 0.05% by mass, the masterbatch content for the processed product to exhibit antibacterial properties increases, which is not preferable in terms of cost. 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.

  As the material for protecting the metal fine particles in the present invention, a nitrogen-containing polymer is desirable. In particular, those having —NH 2 in the molecular structure are particularly desirable. It has a high affinity for the terminal carboxylic acid (—COOH) or carbonyl group (> C ＝ O) present on the surface of the polyamide resin or polyester resin, and has a partial carboxylic acid (—COOH) nitrogen-containing polymer. It is considered that an amide bond is formed with NH2. Thus, it is considered that since the nitrogen-containing polymer coated with the metal fine particles is strongly bonded on the surface of the polyamide resin or the polyester resin, the metal fine particles are strongly supported on the resin surface and are not easily detached.

  Examples of the nitrogen-containing polymer in the present invention include polyethyleneimine, polyallylamine, polyvinylpyridine, polyvinylpyridine, polyaniline, polyaniline derivatives, polypyrrole, and polypyrrole derivatives.

  When the nitrogen-containing polymer in the present invention is polyethyleneimine, the number average molecular weight is preferably from 200 to 10,000. Further, from the viewpoint of increasing the carrying amount due to the protective effect of the metal fine particles, 220 to 1800 is more preferable, and 250 to 400 is most preferable. If the molecular weight of the polyethyleneimine is greater than 10,000, the protective effect of the metal fine particles is inferior and the amount of the metal particles is undesirably reduced. Further, if the molecular weight is 200 or less, it is not preferable in terms of handling from the viewpoint of flash point and the like.

  In the present invention, the resin composition is produced by reducing an ion containing a metal species in a solution in which a polyamide resin or a polyester resin is dispersed in the presence of a nitrogen-containing polymer. According to this method, the metal fine particles generated by the reduction are supported on the resin while being coated with the nitrogen-containing polymer, so that the nitrogen-containing polymer is strongly bonded on the resin surface, and thus the metal fine particles are made of polyamide or polyester. It is considered that they are strongly supported on the resin surface and do not easily detach. On the other hand, in the method in which the polyamide resin or the polyester resin is brought into contact with the reduced metal fine particle solution, the metal fine particles are hardly supported on the resin surface.

Examples of ions containing a metal species include metal chlorides, metal bromides, metal nitrates, metal sulfates, metal acetates, metal perchlorates, and the like. As a method for reducing metal species, hydrazine, a method of reducing at room temperature or low temperature using an inorganic reducing agent such as sodium borohydride, polyethyleneimine, by refluxing at 60 to 100 ℃ using amines such as 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, A method of irradiating with ultraviolet light at room temperature to reduce the temperature is exemplified, but the method is not limited thereto.
When the nitrogen-containing polymer itself has a reducing action such as polyethyleneimine, other reducing agents need not be used.

  The method for producing a polyamide resin or polyester resin composition of the present invention comprises suspending or immersing a resin in 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. In addition, metal fine particles can be supported on the resin surface in a solution via a protective agent.

  In the present invention, the mass compounding ratio of the metal component in the metal compound to be mixed at the time of production and the total solid components excluding the solvent is preferably 0.2 to 0.5, and more preferably 0.25 to 0.4. When the mass mixing ratio is 0.2 or less, the amount of the metal component carried on the resin decreases. On the other hand, if it is 0.5 or more, it is not preferable in terms of cost. Here, the all solid components excluding the solvent are all components other than the solvent to be mixed at the time of production.

  In the present invention, the mass compounding ratio of the metal component in the metal compound and the supported resin to be mixed at the time of production is preferably from 0.25 to 0.5, more preferably from 0.28 to 0.4. When the mass mixing ratio is 0.25 or less, the amount of the metal component supported on the resin decreases. On the other hand, if it is 0.5 or more, it is not preferable in terms of cost.

  In the present invention, the molar ratio of the metal component of the metal compound soluble in water or the organic solvent to the protective agent for the metal fine particles is preferably 3.7 to 8, and the metal component is preferably present in the system in excess. Further, 4.0 to 6.0 is more preferable. When the molar compounding ratio is 3.7 or less, the amount of the protective agent capturing the metal component is small, and the amount of the metal component supported on the resin is reduced. On the other hand, a value of 8 or more is not preferable in terms of cost.

  The polyamide resin or polyester resin composition in the present invention is produced by reducing ions containing a metal species in the presence of a nitrogen-containing polymer in a solution in which the resin is dispersed. According to this method, the metal fine particles generated by the reduction are supported on the resin while being covered with the nitrogen-containing polymer. It is considered that they are strongly supported and do not easily detach.

  As a process for producing a polyamide resin or a polyester resin composition, a solution in which a polyamide resin or a polyester resin is dispersed, a nitrogen-containing polymer, ions containing metal species and a reducing agent are all uniformly mixed before reducing the ions. If possible, the degree of coloring does not affect the order of their addition.

  In the method for producing a polyamide resin or polyester resin composition of the present invention, a higher solution temperature is preferred for the reduction of metal ions depending on the boiling point of the solvent used. In particular, when the solution is water, 70 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is more preferable. It is preferable that the temperature be higher because the amount of metal fine particles carried increases.

  In the method for producing a polyamide resin or polyester resin composition according to the present invention, the adjustment time at the time of reduction of metal ions is preferably from 180 to 300 minutes. If the time is shorter than 180 minutes, the reduction of metal ions is insufficient, and the amount of metal ions is undesirably reduced. There is no need for 300 minutes or more because there is no change in the supported amount.

  In the present invention, the produced polyamide resin or polyester resin composition can be subjected to solid-liquid separation by a method such as decantation, filtration or centrifugation. After that, drying can be performed using vacuum drying or constant temperature drying.

  The polyamide resin or polyester resin composition includes pellets and particles, and the molded article containing the polyamide resin or polyester resin composition includes injection molded articles and extrusion molded articles formed using the pellets and particles. , Films, fibers and the like.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present 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 using a laser diffraction type particle size distribution analyzer. The volume average particle diameter (Dv) is represented by the following equation 1.

Xi；個々の粒子径
n；測定数

Xi: Individual particle size
n; number of measurements

  Regarding the particle diameter of the pellets exceeding 1 mm, 100 particles were actually measured with calipers or the like, and the average value of the longest one was taken as the particle diameter.

  The metal content in the polyamide resin or polyester resin composition was determined by wet decomposing 5 mg of the dried polyamide resin or polyester resin composition sample with nitric acid, and then performing ICP emission analysis to determine the metal component in the resin composition sample. The mass fraction was determined from the emission intensity of

  The presence of the metal fine particles in the polyamide resin or polyester resin composition was confirmed by a TEM photograph of the color and cross section of the polyamide resin or polyester resin composition.

  The test method of the antibacterial property of a molded sheet pressed using a polyamide resin or a polyester resin composition was measured in accordance with JIS Z2801 (film adhesion method), and the test strain used was Klebsiella pneumoniae or Escherichia coli NBRC3982. .

  On the other hand, the test method of the antibacterial property (bacteriostasis and sterilization) of the multifilament fiber produced using the melt spinning apparatus was measured in accordance with JIS standard L1902, and Klebsiella pneumoniae or Escherichia coli NBRC3301 was used as the test strain.

(Example 1)
40 g of polyamide 6 pellets (average particle size: 3 mm: 1011FB manufactured by Ube Industries, Ltd.) are dispersed in 60 g of water, 1.86 g of a 10% by weight aqueous solution of silver nitrate and 0.8 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight 300). Was added and mixed by stirring at 80 ° C. for 180 minutes. Polyamide 6 pellets carrying silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 6 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 6 pellet was colored yellow, and the carried amount of silver was 0.059% by mass. Table 1 shows the results. Observation of the cross section of the pellet by a transmission electron microscope (TEM) confirmed the presence of silver nanoparticles on the surface of the pellet, and the average particle diameter of the silver nanoparticles was 10 nm. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS Z2801 was 6.0 or more.

(Example 2)
40 g of polyamide 6 pellets (average particle size: 3 mm: 1011FB manufactured by Ube Industries, Ltd.) are dispersed in 60 g of water, 2.13 g of a 10% by weight aqueous solution of silver nitrate and 0.8 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 300). Was added and stirred and mixed at 100 ° C. for 180 minutes. Polyamide 6 pellets carrying silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 6 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 6 pellet was colored yellow, and the supported amount of silver was 0.1% by mass. Observation of the cross section of the pellet by a transmission electron microscope (TEM) confirmed the presence of silver nanoparticles on the surface of the pellet, and the average particle diameter of the silver nanoparticles was 10 nm. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS Z2801 was 6.0 or more.

(Example 3)
16 kg of polyamide 6 pellets (average particle size: 3 mm: 1011FB manufactured by Ube Industries, Ltd.) are dispersed in 24 kg of water, 852 g of a 10% by weight aqueous solution of silver nitrate and 320 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 300) are added, The mixture was stirred and mixed at 100 ° C. for 210 minutes. Polyamide 6 pellets carrying antimicrobial silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 6 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 6 pellet was colored yellow, and the carried amount of silver was 0.11% by mass. Observation of the cross section of the pellet by a transmission electron microscope (TEM) confirmed the presence of silver nanoparticles on the surface of the pellet, and the average particle diameter of the silver nanoparticles was 10 nm. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS standard Z2801 was 6.0 or more.

(Comparative Example 1)
20 g of polyamide 6 pellets (average particle size: 3 mm: 1013B, manufactured by Ube Industries, Ltd.) are dispersed in 80 g of water, 0.33 g of a 10% by weight aqueous solution of silver nitrate, and 1.00 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 1800). Was added and stirred and mixed at 100 ° C. for 150 minutes. Polyamide 6 pellets carrying silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 6 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 6 pellet was colored yellow, and the carried amount of silver was 0.002% by mass. Observation of the cross section of the pellet by a transmission electron microscope (TEM) confirmed the presence of silver nanoparticles on the surface of the pellet, and the average particle diameter of the silver nanoparticles was 10 nm. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS standard Z2801 was 3.1.

(Comparative Example 2)
2000 g of polyamide 6 pellets (average particle size: 3 mm: 1013B manufactured by Ube Industries, Ltd.) are dispersed in 6000 g of water, 33 g of a 10% by weight aqueous solution of silver nitrate and 100 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 1800) are added. The mixture was stirred and mixed at 95 ° C. for 150 minutes. Polyamide 6 pellets carrying silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 6 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 6 pellet was colored yellow, and the carried amount of silver was 0.006% by mass.
The thus obtained silver-carrying polyamide 6 pellets were molded into a fiber shape using a monofilament melt spinning apparatus. The fiber diameter measured by an optical microscope was 180 μm. The obtained silver-carrying polyamide 6 fiber has a bacteriostatic activity value against Escherichia coli and a bactericidal activity value of 6.1 or more and 3.1 or more based on JIS standard L1902, and has sufficient antibacterial activity. Was confirmed.

(Comparative Example 3)
200 g of polyamide 6 pellets (average particle size: 3 mm: 1013B manufactured by Ube Industries, Ltd.) are dispersed in 800 g of water, 3.3 g of a 10% by weight aqueous solution of silver nitrate, 10.0 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 600). Was added and stirred and mixed at 100 ° C. for 150 minutes. Polyamide 6 pellets carrying silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 6 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 6 pellet was colored yellow, and the carried amount of silver was 0.025% by mass. Observation of the cross section of the pellet by a transmission electron microscope (TEM) confirmed the presence of silver nanoparticles on the surface of the pellet, and the average particle diameter of the silver nanoparticles was 10 nm. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS Z2801 was 5.1.

(Comparative Example 4)
20 g of polyamide 12 pellets (average particle size: 3 mm; 3012U, manufactured by Ube Industries, Ltd.) are dispersed in 80 g of water, 0.3 g of a 10% by weight aqueous solution of silver nitrate, 0.2 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 600) are used. Was added and stirred and mixed at 70 ° C. for 120 minutes. Polyamide 12 pellets carrying silver nanoparticles protected by polyethyleneimine (antibacterial polyamide 12 pellets) were collected by filtration, washed repeatedly with water, and vacuum dried.
The obtained antibacterial polyamide 12 pellets were colored yellow, and the supported amount of silver was 0.008% by mass. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS Z2801 was 4.8.

(Example 4)
40 g of polyethylene terephthalate pellets (average particle size: 2 mm; TRN-8550FF manufactured by Teijin) are dispersed in 60 g of water, and 1.86 g of a 10% by weight aqueous solution of silver nitrate and 0.8 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 300) are added. Then, the mixture was stirred and mixed at 100 ° C. for 180 minutes. Polyethylene terephthalate pellets (antimicrobial polyethylene terephthalate pellets) carrying silver nanoparticles protected by polyethylene imine were collected by filtration, washed repeatedly with water, and dried in vacuo.
The obtained antibacterial polyethylene terephthalate pellets were colored yellow, and the supported amount of silver was 0.1% by mass. The pellets were kneaded with a Labo Plastomill, and a molded sheet was produced by pressing. The antibacterial activity value of the obtained molded sheet against Escherichia coli according to JIS standard Z2801 was 6.0 or more.

(Comparative Example 5)
20 g of polyethylene terephthalate pellets (average particle size: 2 mm; TRN-8550FF manufactured by Teijin) are dispersed in 80 g of water, and 0.63 g of a 10% by weight aqueous solution of silver nitrate and 0.22 g of a 10% by weight aqueous solution of polyethyleneimine (number average molecular weight: 300) are added. Then, the mixture was stirred and mixed at 70 ° C. for 60 minutes. Polyethylene terephthalate pellets (antimicrobial polyethylene terephthalate pellets) carrying silver nanoparticles protected by polyethylene imine were collected by filtration, washed repeatedly with water, and dried in vacuo.
The obtained antibacterial polyethylene terephthalate pellets were colored yellow, and the supported amount of silver was 0.010% by mass.

(Example 5)
Using 2% by mass of the antibacterial polyamide 6 pellets obtained in Example 3 as a master batch and 98% by mass of polyamide 6 pellets (average particle size: 3 mm: 1011FB manufactured by Ube Industries, Ltd.), and then a melt spinning device was used. Was used to make a multifilament. The diameter of the obtained fiber was 10 μm. The bacteriostatic activity value against Klebsiella pneumoniae and the bactericidal activity value based on JIS L1902 were 6.1 or more and 3.1 or more, and it was confirmed that they had sufficient antibacterial properties. In addition, the bacteriostatic activity value after performing the washing test 10 times is 5.3 in accordance with JEC 326 “Washing method for SEK mark textile products” determined by the Japan Textile Evaluation Technology Council, and after washing 10 times. It turned out that it has sufficient antimicrobial durability.

(Comparative Example 6)
Using 2% by mass of the antibacterial polyamide 6 pellets obtained in Comparative Example 3 as a master batch, 98% by mass of polyamide 6 pellets (average particle size: 3 mm: 1011FK manufactured by Ube Industries, Ltd.) were dry blended, and then melt-spun. A multifilament was prepared using UM2002-R manufactured by Uniplus. About the obtained fiber, the bacteriostatic activity value with respect to Klebsiella pneumoniae and the bactericidal activity value based on JIS L1902 were 0.3 or less, and 0.0 or less, and it was confirmed that it did not have antibacterial property. .

  Table 1 shows the experimental results of Examples 1 to 4 and Comparative Examples 1 to 5.

Claims (6)

Metal fine particles protected by a nitrogen-containing polymer are supported on the surface of a polyamide resin or polyester resin having a particle size in the range of 100 μm to 50 mm, and the content of the metal fine particles is 0.05% by mass to 1% by mass. a manufacturing method of a polyamide resin composition or polyester resin composition, the mass mixing ratio of the metal components and the resin during compounding, 0.25 to 0.5 der is, the nitrogen-containing polymer with polyethyleneimine There, the number average molecular weight of the polyethyleneimine is from 250 to 400, wherein the fine metal particles consist of gold, silver, copper, platinum or their conjugates, mean particle diameter 1~1000nm der Rukoto of the metal fine particles A method for producing a polyamide resin composition or a polyester resin composition, comprising:   2. The polyamide resin composition or the polyester resin composition according to claim 1, wherein a mass mixing ratio of the metal component and the total solid components excluding the solvent at the time of compounding is 0.2 to 0.5. Method.   The polyamide resin composition or the polyester resin composition according to claim 1 or 2, wherein a molar mixing ratio of the metal component and the protective agent composed of the nitrogen-containing polymer at the time of compounding is 3.7 to 8. Method of manufacturing a product. The method for producing a polyamide resin composition or a polyester resin composition according to any one of claims 1 to 3 , wherein the metal fine particles have antibacterial properties. Metal fine particles protected by a nitrogen-containing polymer are supported on the surface of a polyamide resin or polyester resin having a particle size in the range of 100 μm to 50 mm, and the content of the metal fine particles is 0.05% by mass to 1% by mass. A polyamide resin composition or a polyester resin composition, wherein the nitrogen-containing polymer is polyethyleneimine, the polyethyleneimine has a number average molecular weight of 250 to 400, and the metal fine particles are gold, silver, copper, and platinum. Alternatively, a polyamide resin composition or a polyester resin composition comprising a composite thereof, wherein the metal fine particles have an average particle diameter of 1 to 1000 nm. Fibers containing polyamides resin composition or a polyester resin composition according to claim 5.