WO2003033596A1 - Particules composites antibacteriennes et composition de resine antibacterienne - Google Patents
Particules composites antibacteriennes et composition de resine antibacterienne Download PDFInfo
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- WO2003033596A1 WO2003033596A1 PCT/JP2002/010513 JP0210513W WO03033596A1 WO 2003033596 A1 WO2003033596 A1 WO 2003033596A1 JP 0210513 W JP0210513 W JP 0210513W WO 03033596 A1 WO03033596 A1 WO 03033596A1
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- antibacterial
- resin
- composite particles
- base material
- polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Definitions
- the present invention relates to an antibacterial composite particle having an antibacterial effect and an antibacterial resin composition.
- an antibacterial metal to synthetic resin materials.
- an antibacterial metal or metal compound is directly added to a synthetic resin material.
- the physical properties of the metal and the metal compound are significantly different from those of the synthetic resin material, so that the effect on the synthetic resin material is large, and the range of use is limited. May be released from the substance, affecting the persistence of the antibacterial action and causing unexpected side effects due to the released metal and metal compound.
- Japanese Patent Publication No. 63-54013 and Japanese Patent Application Laid-Open No. 63-175117 disclose an antibacterial metal supported on zeolite by ion exchange. It discloses the addition of antibacterial zeolite to fibers and fiber materials.
- an antibacterial composition in which an antibacterial metal and its metal ion are supported on hydroxyapatite, which is most frequently used as a calcium phosphate is disclosed in Japanese Patent Laid-Open Publication No. Hei. These are disclosed in, for example, Japanese Patent Application Laid-Open No. 187765/1995 and Japanese Patent Application Laid-Open No. 5-154 / 1994.
- the antibacterial zeolite supporting the antibacterial metal ion is If the apatite powder is mixed directly with the raw material polymer of the fiber for the purpose of preventing the growth of microorganisms, for example, the zeolite-hydroxyapatite powder is easily agglomerated between the particles and is difficult to disperse.
- the antimicrobial agent was hardly uniformly present on the surface, and it was difficult to obtain a good antibacterial effect. Therefore, using a small amount of antibacterial agent was likely to cause uneven quality in antibacterial properties.
- a master batch containing the antibacterial agent in a high concentration is manufactured as a first step, and as a second step, the masterbatch is formed.
- the masterbatch When implementing such a production method, it is necessary to simultaneously melt the master batch containing the antibacterial ceramic powder and the raw material polymer of the molded product. Therefore, it is desirable that the masterbatch has exactly the same melting point and physical properties as the raw material polymer of the synthetic resin composition constituting the molded product. To do so, it is necessary to use exactly the same base material for the masterbatch containing the antibacterial agent and to reduce the particle size of the masterbatch.
- the present invention therefore improves the uniformity of dispersion of the antibacterial agent when the inorganic antibacterial agent is added to various synthetic resin compositions such as fibers, and exhibits excellent antibacterial properties even with a small amount of the antibacterial agent.
- An object of the present invention is to provide an easy-to-use and useful manufacturing technique that can manufacture an antibacterial resin composition and an antibacterial resin product, and that is versatile.
- An object of the present invention is to provide an antibacterial resin composition and an antibacterial resin product having a sufficient antibacterial effect without impairing the intrinsic properties of the material by such a technique.
- an antibacterial composite particle composed of a polymer base material having a certain range of glass transition temperature, a melt viscosity at a certain temperature, and an inorganic fine particle carrying a metal having an antibacterial action. I found it.
- thermoplastic polymer substrate having a glass transition temperature of 10 to 85 ° C and a melt viscosity at 90 ° C within a certain range, and an inorganic material supporting a metal having an antibacterial action.
- the antibacterial composite particles composed of fine particles are melt-kneaded with the synthetic resin composition of the base material, and the inorganic antibacterial agent is further mixed with the synthetic resin composition by a known molding method such as extrusion molding, injection molding, or spinning. It is possible to obtain various synthetic resin molded products which are uniformly dispersed therein and have a good antibacterial effect.
- the glass transition temperature has an affinity with the fiber-forming polymer is 1 0 ⁇ 8 5 ° C
- the antibacterial composite particles obtained by containing and / or coating inorganic fine particles carrying a metal having an antibacterial effect on a base material are discharged into the fiber-forming polymer from the spinneret.
- the inorganic fine particles used for the antibacterial composite particles of the present invention will be described.
- the inorganic fine particles refer to an inorganic antibacterial agent obtained by supporting a metal element having antibacterial property and Z or metal ion (hereinafter sometimes referred to as antibacterial metal) on an inorganic ceramic support. There is no particular limitation as long as the particles are safe for the human body.
- the antibacterial metal contained in the inorganic antibacterial agent includes at least one selected from the group consisting of silver, copper, zinc, gold, platinum and nickel in consideration of human safety, but is high. In consideration of ensuring antibacterial properties, productivity, manufacturing costs, and the like, among the aforementioned antibacterial metals, silver, copper, and zinc are most preferably used. These antibacterial metals may be used alone or in combination of two or more.
- carriers for supporting antibacterial metal elements and metal ions include phosphate compounds such as calcium phosphate and zirconium phosphate, alumina, silica, zeolite, calcium carbonate, calcium silicate, bentonite. And at least one selected from the group consisting of titanium oxide and zinc oxide.
- the aforementioned compounds i.e., alumina, silica, zeolite, phosphate compounds, calcium carbonate, calcium silicate, bentonite, titanium oxide, and zinc oxide are safe for the human body, metal elements and / or metals It has excellent ability to fix ions.
- a single compound can be selected and used as a carrier, but a plurality of compounds can be selected and used as a carrier.
- the phosphate-based compound is tricalcium phosphate [C a 3 (P 0 4) 2 ], calcium hydrogen phosphate [C a HP 0 4], hydroxy Apatai 1 [C a 10 (P 0 4) 6 (OH) 2], pyrophosphate hydrogen Karushiu arm [C a H 2 P 2 0 7], calcium pyrophosphate [C a 2 ⁇ 2 ⁇ ⁇ ] calcium phosphate-based compound such as, T i (HP 0 4) 2 titanium phosphate based of compounds etc., Z r (HP 0 4) zirconium phosphate compound such as 2, Mg 3 (P 0 4 ) magnesium phosphate compounds such as 2, phosphorus such as a 1 P 0 4 acid Al Miyuumu compounds, Mil 3 (P 0 4) manganese phosphate compounds such as 2, and, F e 3 (P 0 4 ) at least one that is selected from the group consisting of iron phosphate-based compounds
- These carriers may be natural products or synthetic products, but synthetic products are preferable because uniform quality particles can be obtained.
- the phosphate is synthesized by a wet method based on a solution reaction, an amorphous product can be produced, and a highly crystalline product can be obtained by performing a firing step. Although any crystalline material can be obtained, any material may be used. Further, the phosphate may contain water of crystallization.
- the inorganic antibacterial agent used in the antibacterial composite particles of the present invention is selected from the above-mentioned compounds as a carrier, preferably a phosphate compound, particularly a calcium phosphate compound, as a carrier. It is preferable to carry at least one antibacterial metal selected from silver, copper, and zinc among the aforementioned antibacterial metals, and use this as the inorganic antibacterial agent.
- Examples of a method of supporting the antibacterial metal on the carrier include a method of supporting a metal element and a metal or a metal ion by adsorption, a method of supporting the metal element and a metal ion by an ion exchange reaction, and a method of supporting the metal element and a metal ion by a mechanochemical reaction.
- the mechanochemical reaction is a method for producing a slurry of an antibacterial agent having a uniform particle size while performing adsorption and / or ion exchange from a starting material by using a mixing device such as a ball mill.
- a starting material calcium compound such as calcium carbonate, phosphoric acid, etc.
- an antibacterial metal aqueous solution for manufacturing a carrier are charged into a pole mill, and the pole mill is operated for a certain period of time, so that a zircon air ball inside the ball mill comes out.
- the reaction product can be pulverized at the same time as the slurry of the kishi substance is stirred.
- the reaction of the starting material and the pulverization of the reaction product are simultaneously performed, so that an antibacterial agent having a uniform and uniform particle size can be obtained. Suitable for mass production.
- the inorganic antibacterial agent it is preferable that the aforementioned antibacterial metal is supported on the carrier in a range of 0.05% by weight to 30.0% by weight.
- the amount of the antibacterial metal carried is 0.05 weight. /. If the antibacterial performance is less than Low, may require the use of large quantities of the antimicrobial agent itself.
- the antibacterial metal is supported in a loading amount exceeding 30.0% by weight, the bond between the antibacterial metal and the carrier is weak, so that the antibacterial metal is easily detached. There is a tendency that the resin molded product is easily colored.
- the antibacterial composite particles of the present invention may contain, in addition to the inorganic compound as the carrier and the antibacterial metal, other than the inorganic compound and the antibacterial metal as long as the object of the present invention is not hindered. It may contain another inorganic compound such as zinc.
- silicon dioxide has the effect of improving the whiteness of the antibacterial agent
- zinc oxide has the effect of improving the antibacterial spectrum of the antibacterial agent. All inorganic compounds are safe for the human body. In this case, when silver is used as the antibacterial metal, in particular, the target of the antibacterial action is broadened, and copper has an antifungal effect.
- the inorganic antibacterial agent using a phosphate compound as a carrier is preferably further subjected to a calcination treatment at 500 to 1200 ° C. Since the inorganic antibacterial agent subjected to the calcination treatment has an extremely low rate of dissolution of the antibacterial metal and the durability (persistence) of the antibacterial effect is further excellent as compared with the non-calcined one. From the viewpoint of good storage stability of the product, it is more preferable to use a phosphate compound that has been subjected to a firing step.
- the addition amount of the inorganic antibacterial agent is preferably adjusted to be 0.1 to 10% by weight based on the weight of the base material resin, and is preferably 0.1 to 5.0% by weight. / 0 is more preferred.
- near connexion when using the inorganic antibacterial agent and the anti-fungal metal is 3 0.0 wt ° / 0 carrying the inorganic antibacterial agent
- the amount added is 0.01 weight. If the ratio is less than / Q, for example, it is difficult to impart sufficient antibacterial properties to the fiber, and particularly the antibacterial properties are poorly persistent.
- the antibacterial performance is sufficient, but for example, when the fiber is spun, the proportion of the inorganic antibacterial agent in the polymer stream becomes excessively large, which is not preferable because adverse effects such as a decrease in the strength and durability of the fiber itself are caused.
- the antibacterial agent is contained in a particulate polymer substrate described below, and its content is in the range of 0.1% by weight to 60% by weight based on the polymer substrate. If the content is too low, the antibacterial activity is poor, and if it is too high, the antibacterial property of the final product is not improved.
- the synthetic resin composition as a base material can be melted.
- the core base material is quickly melted and melt-mixed with the resin of the base material as a base, so that the inorganic antibacterial agent is uniformly dispersed in the synthetic resin composition in a molten state.
- the synthetic antibacterial agent is uniformly contained in the synthetic resin product of the present invention, a sufficient antibacterial effect can be exhibited without impairing the intrinsic properties of the material.
- the glass transition temperature of the core substrate is 10 ° C to 85 ° C, and the melt viscosity satisfies the following formula.
- the complex viscosity in the present invention is a dynamic viscoelastic property by a sinusoidal vibration method under a vibration frequency lrad / sec. For example, it is measured with an ARES measuring device manufactured by Rheometrics Scientific. Specific measurement conditions include the following conditions. After the powder to be measured is formed into tablets, it is set on a parallel plate, and the normal force is set to 0, and a sine wave vibration is applied at a vibration frequency of 1 rad / sec. After holding at the specified temperature for 20 minutes, the measurement was performed. It is preferable to set the temperature adjustment system after the start of measurement to ⁇ 1.0 ° C or less from the viewpoint of ensuring measurement accuracy. Also, during the measurement, Maintain the strain amount appropriately at each measurement temperature, and adjust appropriately to obtain the appropriate measurement value.
- the base material resin is mixed with various additives in a molten state at a high temperature, and is formed into molded articles, fibers, films, etc. through a cooling process.
- the melting temperature during kneading is generally about 150 to 400 ° C.
- a mold temperature of about 10 to 180 ° C is used. Therefore, additives such as antibacterial agents are required to be uniformly dispersed in the base material resin during melting, and to maintain a dispersed state without uneven distribution and aggregation even after the cooling process. Further, since the antibacterial effect is exhibited by the inorganic antibacterial agent present on the surface of the molded article, it is preferable that the antibacterial agent is present on the resin surface.
- the glass transition temperature of the polymer substrate is 1 ° C. or lower, the difference in viscoelasticity from the base resin at the melt-kneading temperature becomes too large, so that a uniform mixed state may not be obtained.
- the glass transition temperature exceeds 85 ° C, the viscosity at the time of melting is so high that the compatibility with the resin deteriorates and efficient mixing at the time of melting cannot be performed.
- the glass transition temperature is preferably between 30 ° C and 85 ° C, most preferably between 40 and 80 ° C.
- a polymer substrate having this viscosity range has a very good dispersion at the time of melting and also has a high antibacterial performance of a molded article. This is considered to be because when the base resin in the molten state is cooled, the antibacterial agent moves to the vicinity of the surface by having an appropriate viscosity at the above temperature.
- the complex viscosity at 90 ° C is 10 4 Pa'S or less, the viscosity of the polymer base material becomes too low, causing bleeding in the process from molding to cooling, causing the antibacterial agent to re-aggregate, or Is set on the resin surface This may lead to deterioration of the properties of the base material resin due to aggregation.
- the complex viscosity is 1Q S Pa'S or more, the antibacterial agent does not move to the surface due to the high viscosity, and effective antibacterial performance cannot be exhibited.
- the glass transition temperature can be lowered by selecting a monomer species or having a long-chain alkyl group. Generally, the glass transition temperature can be lowered by reducing the molecular weight of the polymer.
- the viscosity can be controlled in the above range by changing the kind of monomer, the molecular weight, and the degree of crosslinking, as in the control of the glass transition temperature.
- the low molecular weight component controls the viscosity in the low temperature range
- the high molecular weight component controls the viscosity in the high temperature range.
- melt viscosity satisfies the following expression.
- melt viscosity By controlling the melt viscosity at 100 ° C from 10 3 Pa'S to 10 5 Pa'S, a suitable viscosity can be obtained, the uniformity of dispersion is improved, and the exposure of the antibacterial agent to the surface is uniform.
- the melt-kneading with the base material resin can be performed more smoothly.
- the softening point of the polymer base material is preferably lower than the softening point of the base material resin by 20 ° C or more. Due to the appropriate difference in softening point, a more uniform antibacterial resin can be obtained by melting the base material resin after the softening of the polymer substrate has started.
- the softening point of the polymer substrate is preferably 50 to 150 ° C. More preferably, 70 to 150 ° C.
- the softening point of the polymer determined by flow tester method, the temperature at which the apparent complex viscosity of 1 0 4 Pa ⁇ S and the softening point.
- the molecular weight of the polymer base resin is preferably from 100 to 100,000 in weight average molecular weight in view of viscosity control during melt-kneading. Preferably, it is not less than 200 ° and not more than 50,000.
- any of a crystalline polymer, an amorphous polymer, and a crystallized surface of an amorphous polymer can be used.
- the thermoplastic resin used for the polymer substrate is not particularly limited, and can be appropriately selected and used. Examples thereof include polyester, polyamide, styrene, vinyl, acrylic, epoxy, urethane, silicon, fluorine, cellulose, simple substance, and resins derived therefrom.
- polyesters, polyamides, polystyrenes, and polyolefins are preferred in consideration of the ease of blending, dispersibility, and versatility of the inorganic antibacterial particles.
- a polyester resin is most preferably used.
- polystyrene examples include styrene copolymers such as styrene, parachlorostyrene, methyl styrene, styrene / butadiene copolymer, styrene / diisoprene copolymer, and styrene / maleic acid copolymer. Can be.
- the polyester is not limited as long as it is a polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component.
- alcohol components include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butanediol, pentandiol, hexanediolone, cyclohexanedimethanol, xylylene glycolone, dipropylene.
- Gliconore, Polyp Divalent or higher alcohols such as propylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide, bisphenol A propylene oxide, sorbitol, and glycerin, and alcohol derivatives. it can.
- the carboxylic acid component includes maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, trimellitic acid, pyromellitic acid, cyclopentanedicarboxylic acid, succinic anhydride, trimellitic anhydride
- Examples thereof include divalent or higher carboxylic acids such as acid, maleic anhydride, and acid dodecenyl succinic anhydride, carboxylic acid derivatives and carboxylic anhydrides.
- Two or more alcohol components and two or more carboxylic acid components may be used in combination.
- polyethylene terephthalate polybutylene terephthalate, poly (ethylene terephthalate Z isophthalate), poly (ethylene glycol Z cyclohexane dimethanol / terephthalate), polycarbonate and polyarylate.
- polyamide examples include nylon 4, nylon 6, nylon 12, nylon 66, and nylon 610.
- polyolefin examples include polyethylene, polypropylene, polybutene, butadiene and the like.
- acrylate polymers such as polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, 2-ethylhexyl polyacrylate, lauryl polyacrylate, polymethyl methacrylate, polybutyl methacrylate, Polymers of methacrylates such as hexyl polymethacrylate, 2-ethylhexyl polymethacrylate, and radiryl polymethacrylate; copolymers of acrylate and methacrylate; styrene-based monomers and acrylate or Copolymer with methacrylic acid ester, poly (vinyl acetate), poly (vinyl propionate), poly (vinyl butyrate) Nylon, polyethylene and polypropylene and other ethylene-based polymers and their copolymers, polyvinyl ether, polyvinyl ketone, polyurethane, rubbers, epoxy resins, polybutyral, rosin, denatured rosin, terpene
- the base material resin in which the composite particles are blended there is no particular limitation on the base material resin in which the composite particles are blended.
- Polyamides such as nylon 6, nylon 66, etc.
- polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, polyethylene, polypropylene, poly Polyolefins such as methylpentene and polybutene, Atari mouth ethril 'butadiene styrene (ABS) resin, acrylonitrile' styrene (AS) resin, acrylic resins such as methacrylic resin, acrylonitrile, polyvier alcohol, polystyrene Resin, butadiene resin, polychlorinated biel resin, polyacetate resin, polyacetal resin, melamine resin, epoxy resin, urethane resin, phenol resin, fluororesin, and copolymers of these It can be mentioned synthetic resin and semi-synthetic resins such as. Among
- the effect can be particularly exhibited.
- These resins can take any form such as a homopolymer, a copolymer, and a mixture.
- the proportion of the antibacterial composite particles used may vary depending on the type of base material resin used as the base material and the type of core material, but in general, the amount of core material used is based on the mass of the base material resin. , 0.1 to 60 weight. / 0 , preferably about 0.5 to 20% by weight. If the amount of the core substrate used is less than 0.1% by weight, the dispersion of the antibacterial agent into the base resin becomes insufficient, and the antibacterial properties of the product and the antibacterial resin composition itself decrease. On the other hand, if the content is more than 60% by weight, in the case of fibrillation, the productivity is reduced and thread breakage is liable to occur, the strength of the obtained fiber is reduced, and the original characteristics of the fiber cannot be exhibited. There are cases.
- the antibacterial composite particles As a method of adding the antibacterial composite particles to the base material resin, it is preferable to add the antibacterial composite particles to the base material resin after the polymerization is completed, considering the effects of these components during the polymerization reaction.
- the antibacterial composite particles are mixed with the antibacterial fiber immediately after polymerization of the polymer constituting the base material resin, during melt-kneading for producing pellets, chips, and molded articles from the polymerized resin composition.
- the object of the present invention is achieved by using the antibacterial composite particles as an essential component.
- the antibacterial composite particles contain and / or cover the inorganic fine particles on the core substrate. It can be obtained by:
- a method for obtaining the antibacterial composite particles of the present invention a method of coating inorganic fine particles on a core substrate by a mechanical method can be adopted.
- the mechanical method described above means that the inorganic fine particles and the core substrate are mixed in a high-speed air-flow mixer or pulverizer such as a Henschel mixer-1, a high pretizer, an ng mill, a mechanofusion, a coatmizer, a disperser coat, and a jetmizer.
- a rotational speed of 500 to 100,000 O rpm for 1 to 120 minutes under a temperature condition such that the temperature inside the device is lower than the softening temperature of the core substrate.
- the volume average particle size of the antibacterial composite particles obtained as described above is arbitrarily selected and is not particularly limited, but usually 1 ⁇ to 200 ⁇ is practical. And preferably 100 ⁇ m to 100 ⁇ m. Production of polymer particles having a particle size of less than 1 ⁇ m is disadvantageous in terms of cost, and it is not preferable because remarkable improvement in effect cannot be expected.
- the particle size of the antibacterial composite particles can be selected from the above range according to the application.However, when the particle size is relatively small, in addition to being able to be uniformly dispersed in the resin composition, The content of the antibacterial metal component can be increased, and a high antibacterial effect can be obtained with a small addition amount.
- the state of the antibacterial metal component carried on the polymer constituting the core substrate eg, a polymer having a functional group having a different coordination property with respect to the antibacterial metal component is used for the core substrate
- the antibacterial metal component The release of antibacterial metal components can be controlled by controlling the surrounding environment (hydrophilicity and hydrophobicity of the polymer), and a fast-acting or persistent antibacterial agent can be obtained.
- the volume average particle size is ⁇ !
- a core substrate of ⁇ 2000 / zm is used.
- the shape of the core substrate is not particularly limited, and may be any shape such as a spherical shape, a needle shape, a spindle shape, a rod shape, a column shape, a polyhedral shape, and a polyneedle shape.
- the larger the particle size of the core substrate the lower the speed in the airflow of the mixer, and the more unevenly the coating of the inorganic fine particles becomes.
- the volume average particle diameter of the inorganic fine particles coated on the surface of the core is preferably not more than 10 ⁇ m, more preferably not more than 1 ⁇ m.
- the particle diameter of the inorganic fine particles exceeds the particle diameter of the core substrate, a part of the inorganic fine particles is crushed, but it becomes difficult to produce the antibacterial composite particles of the present invention. Further, when the volume average particle diameter of the inorganic fine particles exceeds 10 m, for example, in the case of producing antibacterial fibers, thread breakage occurs during spinning, and the processability during spinning deteriorates.
- an ultraviolet absorber in addition to the above-mentioned inorganic antibacterial agent, if necessary, an ultraviolet absorber, an antistatic agent, an antioxidant, a lubricant, a hardener, which is usually used in a resin composition as a raw material of various resin products, Other additives such as flammables, pigments, plasticizers and the like may be used.
- thermoplastic resin used as a raw material of the core base material is mixed with inorganic fine particles, and then melt-kneaded to produce a kneaded product, and pulverized to a predetermined particle size by a mechanical method or the like. Can also produce the antibacterial composite particles of the present invention.
- thermoplastic resin and the inorganic fine particles it is considered appropriate to mix the thermoplastic resin and the inorganic fine particles using a known blender such as a V-type blender, a Henschel Miki-I, a super mixer, and a ribbon blender before melt-kneading.
- a known blender such as a V-type blender, a Henschel Miki-I, a super mixer, and a ribbon blender before melt-kneading.
- an ultraviolet absorber, an antistatic agent, an antioxidant, a lubricant, a hardener which is usually used in a resin composition as a raw material of various resin products.
- Other additives such as flammables, pigments, plasticizers and the like may be used.
- the stirrer capacity, the rotation speed of the stirrer blades, the stirring time, and the like are appropriately selected to sufficiently blend.
- the mixture is melt-kneaded using a single-screw or multi-screw extruder.
- the screw number of the extruder, the number of kneading screw zones, the cylinder temperature, the kneading speed, etc. are adjusted so that the resin temperature becomes appropriate in accordance with the physical properties of the thermoplastic resin.
- various parameters such as the number of screws and the kneading speed must be comprehensively determined.
- the mixture is pulverized by a known method such as a ball mill, a sand miner, a hammer mill, or a pneumatic pulverization method. If cooling by conventional methods is not sufficient, cooling or freeze-pulverization methods can be selected.
- the antibacterial composite particles of the present invention are obtained by adding a calcium phosphate-based antibacterial agent to a monomer component of a polymer of a core substrate, for example, by emulsion polymerization, suspension polymerization, or the like. It can be manufactured by using the method described above.
- the antibacterial property of the present invention is obtained by polymerizing a monomer mixture consisting of an inorganic antibacterial agent component and a polymerizable monomer in an aqueous medium in the presence of an emulsifier and a water-soluble polymerization initiator.
- Composite particles can be produced.
- the antimicrobial composite particles of the present invention can also be produced by soap free emulsion polymerization without using an emulsifier.
- a polymerization initiator When polymerizing the monomer component, a polymerization initiator can be used.
- a conventionally known polymerization initiator can be used. That is, for example, hydrogen peroxide; persulfates such as sodium persulfate, ammonium persulfate, persulfate and the like; benzoyl peroxide, lauryloyl peroxide, capryloyl peroxide, peracetic acid, t-butyl hydroxy peroxide, Radical polymerization initiators such as organic peroxides such as methyl ethyl ketone peroxide and t-butyl perphthalate; and azo compounds such as azobisisobutyronitrile and azobisisobutyramide.
- These polymerization initiators may be used alone, or two or more of them may be used as an appropriate mixture.
- ultraviolet absorbers and antistatic agents commonly used in resin compositions as raw materials for various resin products are used.
- Other additives such as agents, antioxidants, lubricants, flame retardants, pigments, plasticizers and the like may be used.
- the molding method for obtaining the antibacterial resin composition and the antibacterial resin product of the present invention can employ conventionally known techniques and is not particularly limited.
- the antibacterial composite particles are melt-kneaded with the synthetic resin composition of the base material, and the inorganic antibacterial agent is uniformly dispersed in the synthetic resin composition by a known molding method such as extrusion molding or injection molding.
- a known molding method such as extrusion molding or injection molding.
- the antibacterial composite particles of the present invention are added to the fiber-forming polymer at any stage until the fiber-forming polymer is discharged from the spinneret. By mixing and spinning the particles, a fiber having a sufficient antibacterial effect can be obtained without impairing the intrinsic properties of the material.
- the antibacterial composite particles are melted and atomized again to be used for molded articles, or melted and kneaded with a base material resin at an appropriate concentration and atomized to prepare a compound or a masterbatch.
- the antibacterial resin composition, the antibacterial resin product, the antibacterial fiber and the like may be produced.
- the antibacterial resin composition of the present invention include various packaging materials such as packaging films, air conditioner filters, filters for water purifiers, cutting boards, interiors of refrigerators, medical instruments, various tubes, packing, and foodstuffs. It can be used for various products such as containers, and can impart durable and good antibacterial properties to those products.
- the antimicrobial fiber of the present invention provides Men's yarns, spun yarns, woven and knitted fabrics, non-woven fabrics, etc. can be manufactured, such as clothing such as outerwear, underwear, work clothes, insoles, socks, rags, socks, toys, paints, futons, and beds. Used for carpets, white coats, sick coats, bandages, gauze, tooth brushes, etc. BEST MODE FOR CARRYING OUT THE INVENTION
- Antibacterial composite particles of the present invention (Production Examples 1 and 2)
- Polyester shown in Table 1 composition: polycondensate of terephthalic acid / bisphenol A polyoxyethylene 2 mol adduct Z number average molecular weight 5.2 X10 3 ) is pulverized to obtain a volume average particle diameter of 100 m. Was prepared.
- polyester particles and the antibacterial tricalcium phosphate inorganic fine particles are charged into a Henschel mixer at a predetermined ratio (Table 1) and stirred at a high speed to obtain the antibacterial composite particles of the present invention (Production Example 1, 2) was obtained.
- Polyesters listed in Table 1 Composition: terephthalic acid / bisphenol A Poly O carboxymethyl ethylene 2 mol adduct polycondensates / number average molecular weight 5.2 XI 0 3 of), so that the amount of the antibacterial tricalcium phosphate inorganic fine particles of the is 30 wt% of the polymer, the antimicrobial of the present invention
- Composite particles (Production Example 3) were produced by a kneading and pulverizing method. That is, the antimicrobial tricalcium phosphate inorganic fine particles and the polyester were put into a Henschel mixer and preliminarily dispersed. Next, the mixture is melt-kneaded using an extruder, the obtained kneaded material is cooled, and pulverized so that the volume average particle diameter becomes 100 xm. 3) was obtained.
- the antimicrobial composite particles (Production Example 4) were produced by a kneading and pulverization method using the above-mentioned inorganic particles of the antimicrobial tricalcium phosphate. That is, the antimicrobial tricalcium phosphate inorganic fine particles and the polymer were charged into a Henschel mixer and preliminarily dispersed.
- the amount of the antibacterial agent was 20% by weight of the polymer.
- Antibacterial composite particles (Production Example 5) were produced by a kneading and pulverization method using the styrene resin (number average molecular weight 2.5 ⁇ 10 4 ) shown in Table 1 and the above-mentioned inorganic microparticles of antibacterial tricalcium phosphate. That is, the antimicrobial tricalcium phosphate inorganic fine particles and the polymer were put into a Henschel mixer and preliminarily dispersed. Next, the mixture was melted and kneaded using an Etas truder, and the obtained kneaded product was cooled and pulverized so that the volume average particle diameter became 100 / zm. Thus, Production Example 5 was obtained. The amount of the antibacterial agent was 10% by weight of the polymer.
- the oxidized polyethylene wax (number average molecular weight 1.8 ⁇ 10 3 ) described in Table 1 was pulverized to prepare resin particles having a volume average particle diameter of 100 / zm, and then the antibacterial tricalcium phosphate inorganic fine particles described above were prepared.
- Production Example 6 was obtained.
- the amount of the antibacterial agent was 10% by weight of the polymer.
- the polystyrene resin (number average molecular weight 1.8 ⁇ 10 5 ) shown in Table 1 was pulverized to prepare resin particles having a volume average particle diameter of 100 ⁇ , and then the antibacterial tricalcium phosphate inorganic fine particles were used.
- Antibacterial composite particles (Production Example 7) were produced. That is, the antimicrobial tricalcium phosphate inorganic fine particles and the polymer were put into a Henschel mixer and stirred at high speed to obtain Production Example 7. The amount of the antibacterial agent was 10% by weight of the polymer.
- the glass transition temperature was measured at a heating rate of 10 ° CZmin using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50).
- the melt viscosity at 90 ° C * (9Q ° C), the melt viscosity at 100 ° C 77 * (100 ° C) and the melt viscosity at 180 ° C ⁇ * (180 ° C) of Production Examples 1 to 7 are As described above, the measurement was performed using an ARES measuring device manufactured by Rheometric Scientific.
- the softening point was measured using a flow tester CFT-500F type (manufactured by Shimadzu Corporation) using a die with a diameter of 1. Omm and an Imra length under the conditions of a load of 10 kgf and a sample amount of 1.0 g.
- the temperature at which the melt viscosity was 1 ⁇ 10 4 Pa'S was defined as the softening point.
- the weight-average molecular weight was measured using a molecular weight measuring device (manufactured by Tosoichi Co., Ltd., HLC-8120) using polystyrene as a standard polymer.
- the antibacterial resin plate was prepared using a melt-kneading extruder (Table 2).
- Acrylic - tolyl 9 6 wt 0/0 consists acetate Biel 4 wt 0/0 monomer mixed compound persulfate ammonium - with aqueous suspension polymerization ⁇ beam as the initiator, the weight average molecular weight 20 X 1 0 created the 4 polyacrylonitrile-based polymer.
- the obtained polymer was dissolved in dimethylformamide, and 5% by weight of each of the antibacterial composite particles of Production Examples 1 to 7 was added to such a polymer stock solution to prepare a spinning stock solution having a polymer concentration of 20%. .
- the spinning solution was discharged from a nozzle by a wet spinning method, solidified in an aqueous solution of dimethylformamide, and washed with ion-exchanged water to remove dimethylformamide. Then, it was stretched twice under the moist heat of 100 ° C and dried at 120 ° C with a heater roller. The dried fiber is further heated through a heating roller with a surface temperature set at 170 ° C, stretched by a factor of 2 and applied with an oil agent, and then wound up with a heating roller to provide an antibacterial agent. Twisted fibers were prepared (Table 4).
- the softening point difference is defined as a value obtained by subtracting the composite resin softening temperature from the base material resin softening temperature.
- the antibacterial test was performed on the antibacterial resin plate prepared as described above and the antibacterial false twisted fiber as follows. 1. Antibacterial resin plate
- Antibacterial test method for antibacterial products The antibacterial test was performed in accordance with JIS Z2801.
- the test bacteria used was Escherichia coli (IF03972).
- an ordinary broth medium was prepared by dissolving 5 mg of meat extract, 1 Omg of peptone, and 5 nig of sodium chloride in 1 liter of distilled water.
- a solution was prepared by further diluting the above-mentioned broth medium with distilled water by 500 times, and Escherichia coli was suspended in such a solution so that the number of bacteria per 1 ml was 10 s .
- Table 5 shows the results of the antibacterial test. Table 5.
- Antibacterial test method for textile products ⁇ Antibacterial effect An antibacterial test was conducted in accordance with JIS L 1902.
- 1.3 ⁇ 10 5 bacterial cells ( ⁇ ⁇ ⁇ ) of the following test bacteria were prepared with sterilized 1/20 concentration -eutrient broth, and 0.2 ml of the prepared bacterial solution was used in Examples 1-4 and Comparative Example 1. Inoculate 0.4 g of each of the samples 3 to 3 uniformly, and incubate at 37 ° C for 18 hours. After the culture is completed, the test bacteria are washed out, and the liquid is cultured at 37 ° C for 24-48 hours by a pour plate agar culture method, and the number of viable bacteria is measured. In addition, Staphylococcus aureus ATCC 6538P was used as a test bacterium. Tables 6 and 7 show the results of the antibacterial test. Table 6. PE fiber softening point 240 ° C
- the antibacterial resin molded articles and the antibacterial fibers of the examples have sufficiently high antibacterial performance even when the amount of the inorganic antibacterial agent is the same.
- the antibacterial composite particles manufactured using the antibacterial composite particles of the comparative example contained the same amount or more antibacterial agents as compared with those using the antibacterial composite particles of the present invention. It was found that the antibacterial performance was significantly reduced.
- the antibacterial resin plate of Example 5, the antibacterial PET fiber of Example 4, and the antibacterial acryl resin fiber of Example 4 are compared with each other in the antibacterial test results (Tables 5 to 7). It is manufactured using the antibacterial composite particles (Production Example 4) and has a certain antibacterial activity, but the difference between the softening point of the resin particles constituting the antibacterial composite particles and the softening point is less than 20 ° C. It can be seen that the antibacterial effect is reduced when the base material resin is used.
- the antibacterial composite particles of the present invention are composed of a polymer base material having a specific glass transition point and a melt viscosity and fine particles of an inorganic antibacterial agent, the basic material constituting the synthetic resin product It is possible to obtain various synthetic resin molded products having a good dispersibility with respect to water and a good antibacterial effect. Further, when an antibacterial fiber is produced using the antibacterial composite particles of the present invention, a fiber having a sufficient antibacterial effect can be obtained without impairing the intrinsic properties of the material.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2003536328A JP4031759B2 (ja) | 2001-10-17 | 2002-10-10 | 抗菌性複合粒子及び抗菌性樹脂組成物 |
US10/492,352 US7250453B2 (en) | 2001-10-17 | 2002-10-10 | Anti-bacterial composite particles and anti-bacterial resin composition |
EP02801524A EP1449889B1 (en) | 2001-10-17 | 2002-10-10 | Antibacterial composite particles and antibacterial resin composition |
KR1020047005582A KR100636403B1 (ko) | 2001-10-17 | 2002-10-10 | 항균성 복합입자 및 항균성 수지조성물 |
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JP2001319574 | 2001-10-17 | ||
JP2001-319574 | 2001-10-17 |
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WO2003033596A1 true WO2003033596A1 (fr) | 2003-04-24 |
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PCT/JP2002/010513 WO2003033596A1 (fr) | 2001-10-17 | 2002-10-10 | Particules composites antibacteriennes et composition de resine antibacterienne |
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Country | Link |
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US (1) | US7250453B2 (ja) |
EP (1) | EP1449889B1 (ja) |
JP (1) | JP4031759B2 (ja) |
KR (1) | KR100636403B1 (ja) |
CN (1) | CN1320063C (ja) |
WO (1) | WO2003033596A1 (ja) |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1721939A1 (en) * | 2004-02-18 | 2006-11-15 | Nippon Wishborn Corporation | Resin composition and utilizing the same, furniture, electrical household appliance and molding |
CN100417695C (zh) * | 2004-02-18 | 2008-09-10 | 日本望兴株式会社 | 树脂组合物,使用树脂组合物的家具、家庭电气化产品、成型制品 |
EP1721939A4 (en) * | 2004-02-18 | 2009-11-18 | Nippon Wishborn Corp | RESIN COMPOSITION AND USING THE SAME, FURNITURE, HOUSEHOLD APPLIANCE AND MOLDING |
JP2010525091A (ja) * | 2007-04-18 | 2010-07-22 | ビーエーエスエフ ソシエタス・ヨーロピア | 抗微生物プラスチック及びコーティング |
JP2011037982A (ja) * | 2009-08-10 | 2011-02-24 | Ceramics Craft Co Ltd | 樹脂成型部材 |
JP2013508513A (ja) * | 2009-10-26 | 2013-03-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 抗菌組成物、抗菌ブラシフィラメントおよびその製造方法 |
JP2011094828A (ja) * | 2009-10-27 | 2011-05-12 | Mitsubishi Electric Corp | エアフィルタ及びこのエアフィルタを備えた空気調和機 |
JP2013049944A (ja) * | 2011-07-29 | 2013-03-14 | Nbc Meshtec Inc | 抗ウイルス性を有する繊維およびその製造方法 |
JP2013056833A (ja) * | 2011-09-07 | 2013-03-28 | Toagosei Co Ltd | 水処理用抗菌処理材および水処理方法 |
JP2015025038A (ja) * | 2013-07-25 | 2015-02-05 | 富士ケミカル株式会社 | 抗菌剤含有熱可塑性樹脂組成物及びこれを用いた抗菌剤含有熱可塑性樹脂製品の製造方法 |
CN112409724A (zh) * | 2020-11-19 | 2021-02-26 | 长虹美菱股份有限公司 | 一种冰箱用抗菌pvc门封条及其制备方法 |
Also Published As
Publication number | Publication date |
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EP1449889A1 (en) | 2004-08-25 |
EP1449889B1 (en) | 2013-03-06 |
KR20040054723A (ko) | 2004-06-25 |
EP1449889A4 (en) | 2006-06-14 |
JPWO2003033596A1 (ja) | 2005-02-03 |
CN1320063C (zh) | 2007-06-06 |
JP4031759B2 (ja) | 2008-01-09 |
US7250453B2 (en) | 2007-07-31 |
CN1604941A (zh) | 2005-04-06 |
KR100636403B1 (ko) | 2006-10-19 |
US20040259973A1 (en) | 2004-12-23 |
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