JPH06287355A - Molding containing ultrafine particle dispersed therein - Google Patents

Abstract

PURPOSE:To provide a fiber or resin molding contg. ultrafine particles homogeneously dispersed therein. CONSTITUTION:A fiber or resin molding is provided wherein ultrafine particles having uniform particle sizes in the range of 1-200nm are dispersed almost without agglomerating. Typically, the fiber or resin molding is produced by mixing a raw material polymer with a metal salt, thermally treating the mixture to reduce the metal salt to produce uniform ultrafine particles in the polymer, and forming the mixture contg. the particles into a fiber or resin molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber and a resin molded product in which ultrafine particles are uniformly dispersed. By adding ultrafine particles to fibers and resin molded products, various functions such as
Antibacterial / mold / deodorant properties, flame retardancy, UV protection, heat storage properties, surface property improvement, and refreshing feeling are provided.

[0002]

2. Description of the Related Art It has been conventionally practiced to add various functions by adding inorganic fine particles having a particle size on the order of micron to a fiber or a resin molded product. For example, antibacterial / mold / deodorant properties, flame retardancy, UV protection, heat storage, surface property improvement, and refreshing sensation.

However, when ultrafine particles having an average particle size of less than 200 nm are used, the ultrafine particles aggregate during the production of the fiber or molded product when added to the fiber or resin molded product, and can be dispersed uniformly. It was difficult.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide ultrafine particle-dispersed fibers and resin molded products having excellent uniformity.

[0005]

[Means for Solving the Problems] When ultrafine particle powder is directly added in a step such as a melt-kneading step in producing a fiber or a resin molded product, the ultrafine particles are agglomerated and the ultrafine particles are uniform. Not dispersed in. However, they have found that a uniform dispersion state can be realized by directly producing ultrafine particles in a polymer, which is a raw material for a molded product, and have completed the present invention.

That is, the present invention has an average particle size of 200 nm.
In a molded product in which ultrafine particles having a size of less than 1 nm are dispersed, the particle size distribution and dispersed state of the ultrafine particles are maintained uniformly. In the present invention, the molded product is a fiber or resin molded product. The fibers include natural fibers such as cotton, wool, silk and hemp, recycled fibers such as rayon fibers and cupra fibers, acetate fibers, vinylon fibers, nylon fibers, vinylidene fibers, polyvinyl chloride fibers, polyester fibers, polyethylene fibers, acrylic fibers. , Synthetic fibers such as polypropylene fibers, and inorganic fibers such as glass fibers.

As the resin, a thermoplastic resin, a thermosetting resin or the like can be used. Specific examples of the thermoplastic resin include AAS resin, AES resin, AS resin, isophthalene-maleic anhydride copolymer resin, ABS resin, and AC resin.
S resin, ethylene-vinyl chloride copolymer resin, vinylidene chloride resin, vinyl chloride resin, coumarone resin, ketone resin, vinyl acetate resin, phenoxy resin, butadiene resin, fluororesin, polyacetal, polyamide, polyamideimide, polyarylate, polyetherimide, Polyether ether ketone, polyethylene, polyethylene terephthalate, polycarbonate, polystyrene, polysulfone, polyparamethylstyrene, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl formal, polyphenylene ether, polyphenylene sulfide, polypropylene, polymethylene pentene, methacrylic resin, liquid crystal polymer And so on.

Examples of the thermosetting resin include DFK resin, epoxy resin, xylene resin, phenol resin, polyimide, polyurethane, melanin resin, urea resin, vinyl ester resin and unsaturated polyester resin. Further, natural polymers such as methyl cellulose, ethyl cellulose, acetate plastic, cellulose acetate and the like can be mentioned.

The resin molded product of the present invention is a resin molded product obtained by molding the above resin into various shapes using a molding method such as injection molding, extrusion molding or compression molding. The material of the ultrafine particles of the present invention is not particularly limited, and examples thereof include metals, semiconductors, oxides, sulfides and organic substances. Preferably silver,
Metals such as gold, copper, palladium, rhodium and platinum, oxides such as silver oxide, copper oxide, titanium oxide and zinc oxide, semiconductors such as cadmium sulfide, cadmium selenide, zinc sulfide, zinc selenide, silicon and germanium. Can be mentioned. More preferably silver, gold, copper, palladium,
Metals such as rhodium and platinum and oxides such as silver oxide and copper oxide.

The average particle size was measured as follows. Using an ultramicrotome for the produced fibers and resin molded products,
An ultrathin section was prepared, and this section was placed on a copper grid to which a collodion support film was attached, and carbon vapor deposition treatment was performed to obtain a sample for transmission electron microscope observation. The thickness of the ultrathin section is 50 nm or more and 100 nm or less. Using a transmission electron microscope (JEM-4000FX, manufactured by JEOL Ltd.), an observation magnification of 50,000 times or 1 at an acceleration voltage of 200 kV.
Photographs were taken at a magnification of 200,000 and a magnification of 200,000 or 400,000 was used. Next, using this photograph, the diameters of 100 adjacent ultrafine particles within a certain range in the photograph of the image analyzer were measured, and the arithmetic average thereof was taken as the average particle diameter. However, when the number of ultrafine particles in the photograph was less than 100, the required number of transmission electron micrographs at different locations were used to obtain 100 particles, and the average particle diameter was obtained.

Uniform particle size distribution means that when the average particle size is R, 50% or more of the measured ultrafine particles are in the range of 0.5R or more and 1.5R or less. It means that it exists. When the particle size distribution is more uniform, 75% or more is present. The uniform dispersion state means a state in which, in the electron micrograph for measuring the average particle diameter, out of 100 particles used for measuring the average particle diameter, 30 or less overlapped particles. When the dispersed state is more uniform, the number of overlapping particles is 10 or less.

The portion where the dispersion state is uniform may be localized. Of course, it does not matter if the entire dispersion state is uniform. Localized means that, for example, ultrafine particles exist only near the surface or only near the center,
This means that the dispersed state is uniform in that portion. The amount of ultrafine particles in the material naturally depends on what is dispersed and what performance is given. For example, when dispersed in a polymer such as fiber or resin, the content is 5 wt% or less and 0.1 ppm or more.

In the present invention, the average particle size of the ultrafine particles is 2
It is necessary to be less than 00 nm and 1 nm or more. Ultrafine particles having an average particle size of less than 1 nm cannot be currently produced in the dispersed state as described above. The means for achieving the above-mentioned dispersed state and particle size distribution is not particularly limited as long as the above conditions can be achieved, but a preferable method is in a polymer solid phase which is a raw material for producing fibers and resin molded products. And a method for producing ultrafine particles. For example, a method of producing ultrafine particles in a polymer raw material by heating a polymer raw material such as a polymer pellet in which a metal salt and a reducing agent are dissolved or impregnated to reduce the polymer raw material be able to. Also, after dissolving a polymer soluble in a solvent in a solvent, ultrafine particles are prepared by a reduction reaction by adding a metal salt and a reducing agent, and then the solvent is removed to prepare a polymer raw material in which the ultrafine particles are dispersed. It is possible to use a method of producing, in which the metal salt alone is dissolved or impregnated in the polymer raw material, and then heat treatment is performed to reduce the metal salt to produce ultrafine particles in the polymer raw material.

The polymer raw material can be used to process into fibers. Further, various resin molded products can be produced by performing injection molding, extrusion molding, blow molding and the like using this polymer raw material.
When ultrafine particles are dispersed on the surface of fibers or resin molded products, the fibers or resin molded products are directly impregnated with a metal salt or the like, and subjected to heat treatment or reduction treatment,
It is also possible to disperse in high concentration on the surface.

[0015]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0016]

Example 1 A masterbatch was prepared as follows. A coating liquid having the composition shown below was prepared. Polystyrene 10 g Silver heptafluorobutyrate 0.01 g 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 0.02 g Methyl ethyl ketone 60 g Toluene 30 g After filtering through a filter with an average pore size of 0.2 μm, the film thickness after drying was 6 using a blade coater.
Polyethylene terephthalate (PE
T) A film was evenly applied and naturally dried. After that, heat treatment was performed for 30 minutes at 150 ° C. in an oven, and then the styrene film was peeled off from the PET film, and this styrene film was used as a masterbatch. Using this masterbatch, it was mixed with polystyrene so that the amount of silver was 0.05 wt%, and injection molding was performed to prepare an antibacterial property evaluation sample.

When the particle size was measured using an electron micrograph, the average particle size was 9 nm. Also, measured 10
All 0 silver particles were dispersed independently. Regarding the particle size distribution, 85% of particles were present in the range of 4.5 nm to 13.5 nm.

[0018]

Example 2 A masterbatch was prepared as follows. A liquid having the composition shown below was prepared. Silver trifluoroacetate 0.1 g Methanol 15 g After immersing the nylon 6 pellets in this solution overnight, the pellets were taken out from the solution, the solvent was removed, and then heat treatment was performed at 150 ° C. for 30 minutes using an oven. Using this masterbatch, nylon 66 chips were mixed so that the amount of silver was about 0.01 wt%, to prepare a 10 denier yarn. Then, a cloth was produced using this thread. When the particle size was measured using an electron micrograph, the average particle size was 19 nm. All 100 fine silver particles measured were independently dispersed. Regarding the particle size distribution, 75% of ultrafine particles were present in the range of particle size 9.5 nm or more and 28.5 nm or less.

[0019]

Example 3 A coating solution containing the following components was prepared. Sodium chloroaurate 0.1 g Polyurethane 100 g Isopropyl alcohol 700 g Methyl alcohol 100 g Toluene 400 g After filtering this coating solution through a filter having an average pore size of 0.2 μm, it was dried with a blade coater to give a film thickness of 6 μm.
Asahi Kasei nylon 6 (Part No. 116
2) It was evenly applied onto a cloth and dried under the conditions of a temperature of 30 ° C. and a humidity of 45% RH. The sample was heated at 150 ° C. for 20 minutes. A section for a transmission electron microscope was prepared from this sample using a microtome and observed using an electron microscope. As an electron microscope, H-500 manufactured by Hitachi, Ltd. was used. When the diameter of 100 fine gold particles was measured from the photograph, the arithmetic average particle diameter was 28 nm. 95 of 100 gold particles were dispersed independently. Regarding the particle size distribution, 90% of ultrafine particles were present in the range of 14 nm to 42 nm.

[0020]

EFFECT OF THE INVENTION The particle size distribution of ultrafine particles is sharp,
In addition, it is possible to provide a highly uniform new fiber or resin molded product in which ultrafine particles have little aggregation and exist independently.

Claims (1)

[Claims] 1. A molded article in which ultrafine particles having an average particle size of less than 200 nm and 1 nm or more are dispersed, wherein the particle size distribution and dispersed state of the ultrafine particles are maintained uniformly.