EP3683341A1 - Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne - Google Patents
Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne Download PDFInfo
- Publication number
- EP3683341A1 EP3683341A1 EP19798520.3A EP19798520A EP3683341A1 EP 3683341 A1 EP3683341 A1 EP 3683341A1 EP 19798520 A EP19798520 A EP 19798520A EP 3683341 A1 EP3683341 A1 EP 3683341A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- antibacterial
- glass
- weight
- fiber
- preferable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Classifications
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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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
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
- D10B2101/06—Glass
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
- D10B2321/022—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polypropylene
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/13—Physical properties anti-allergenic or anti-bacterial
Definitions
- the present invention relates to an antibacterial fiber and a method for producing an antibacterial fiber.
- the invention relates particularly to an antibacterial fiber having a core portion and a sheath portion, in which the amount of incorporation of antibacterial glass is made sufficient with a small amount by reducing the content of the antibacterial glass in the core portion compared to the content of the antibacterial glass in the sheath portion, the antibacterial fiber exhibiting excellent antibacterial properties; and a method for producing an antibacterial fiber.
- antibacterial fiber products obtained by subjecting fiber products to antibacterial processing have been popularized.
- a method for producing such an antibacterial fiber available are a method of fixating an antibacterial glass composition (glass particles) on the surface of a textile substrate of a synthetic fiber or a natural fiber; and a method of dispersing an antibacterial glass composition into a textile substrate (Patent Document 1).
- antibacterial fibers are obtained by an example in which composite particles are fixated by (a) fixating glass particles in an adhered form by means of an adhesive polymer layer formed on the surface of the textile substrate; (b) further covering the surface side of the fixated glass particles with an overcoat based on a polymer or the like; and (c) having the surface of the glass particles covered in advance by a fixation resin layer, attaching the fixation resin layer to the surface of the textile substrate while softening the fixation resin layer by heating, and then curing the resin layer.
- an antibacterial fiber in a dispersed form is obtained by incorporating glass particles into a spinning dope that should become a textile substrate, and spinning this mixture.
- an antibacterial polyester fiber which is a core-sheath type composite fiber with a core portion containing an antibacterial agent, and in which the proportion of the sheath portion after alkali weight reduction processing is 2% to 20% by weight with respect to the fiber weight, the content of the antibacterial agent in the core portion is 0.1% to 10% by weight with respect to the fiber weight, and the color difference ( ⁇ E) before and after the alkali weight reduction processing is below 2.0.
- an antibacterial fiber obtainable by the method of dispersing antibacterial glass particles in a textile substrate as disclosed in Patent Document 1
- the component that exhibits an antibacterial effect is the antibacterial glass particles fixated to the fiber surface
- glass particles are also included in the core portion of the fiber. Therefore, there is a problem that antibacterial glass particles containing highly expensive silver and the like have to be added in large quantities.
- the antibacterial fiber disclosed in Patent Document 2 oxidation of silver as an antibacterial component occurs due to alkali weight reduction processing, and the antibacterial fiber is discolored (colored).
- the antibacterial fiber contains an antibacterial agent only in the core portion, in order to prevent deterioration of antibacterial properties. Therefore, since there is no antibacterial agent existing on the fiber surface, there is a problem that a sufficient antibacterial effect may not be obtained.
- the inventors of the invention conducted a thorough investigation, and as a result, the inventors found that when an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as mixing components is produced into an antibacterial fiber that has the average diameter adjusted to a value within the range of 1 to 50 ⁇ m and includes a core portion and a sheath portion, in which when a content of the antibacterial glass in the core portion is designated as Q1 (weight%) with respect to the total amount of the antibacterial fiber, and a content of the antibacterial glass in the sheath portion is designated as Q2 (weight%) with respect to the total amount of the antibacterial fiber, Q1 and Q2 satisfy a predetermined relational expression, the antibacterial fiber exhibits excellent antibacterial properties even when the amount of incorporation of the antibacterial glass is a small amount. Thus, the inventors completed the invention.
- an object of the invention is to provide an antibacterial fiber in which the amount of incorporation of antibacterial glass is made sufficient with a small amount by reducing the content of the antibacterial glass in the core portion compared to the content of the antibacterial glass in the sheath portion, and which exhibits excellent antibacterial properties; and an efficient method for producing such an antibacterial fiber.
- an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as mixing components, the antibacterial fiber having an average diameter adjusted to a value within the range of 1 to 50 ⁇ m, the antibacterial fiber including a core portion and a sheath portion, in which when a content of the antibacterial glass in the core portion is designated as Q1 (weight%) with respect to the total amount of the antibacterial fiber, and a content of the antibacterial glass in the sheath portion is designated as Q2 (weight%) with respect to the total amount of the antibacterial fiber, Q1 and Q2 satisfy the following relational expression (1), and thus the above-described problems could be solved.
- the content of the antibacterial glass in the core portion could be regulated to be smaller than the content of the antibacterial glass in the sheath portion, and furthermore, even when the amount of incorporation of the antibacterial glass is relatively a small amount with respect to the total amount of the antibacterial fiber, excellent antibacterial properties could be exhibited from an early stage over a long period of time.
- Q1 is adjusted to 0 or 0% to below 1% by weight (provided that excluding 0% by weight) .
- the content of the antibacterial glass in the core portion which may not easily participate in the exhibition of an antibacterial effect, could be reduced.
- Q2 is adjusted to a value within the range of 1% to 10% by weight.
- antibacterial glass could be incorporated in an amount within a more suitable range with respect to the total amount of the antibacterial fiber.
- the antibacterial fiber of the invention further contains aggregated silica particles as a mixing component.
- the antibacterial fiber is configured as such, as silica particles that are richly hydrophilic attach to the periphery of antibacterial glass, the rate of dissolution of the antibacterial glass becomes uniform, and the antibacterial fiber acquires an excellent anti-color-ability.
- the volume average particle size of antibacterial glass is adjusted to a value within the range of 0.1 to 5 ⁇ m.
- antibacterial glass could be uniformly dispersed in the resin component, and also, antibacterial glass could be stably processed into the antibacterial fiber.
- thermoplastic resin is selected to be any one or more of a polyester resin, a polyamide resin, and a polyolefin resin.
- the antibacterial fiber is configured as such, since antibacterial glass could be dispersed more uniformly in the resin component, an excellent antibacterial effect could be obtained.
- the antibacterial fiber is in the form of any one of a woven fabric, a nonwoven fabric, and felt.
- the antibacterial fiber of the invention is an antibacterial fiber having a predetermined shape, even when the amount of incorporation of antibacterial is reduced, a woven fabric, a nonwoven fabric, and felt, all of which exhibit excellent antibacterial properties, could be obtained.
- another embodiment of the invention is a method for producing an antibacterial fiber including a core portion and a sheath portion and containing a thermoplastic resin and an antibacterial glass as mixing components, the method including the following steps (1) to (3) :
- the content of the antibacterial glass in the core portion could be reduced compared to the content of the antibacterial glass in the sheath portion.
- the amount of incorporation of the antibacterial glass is made sufficient with a relatively small amount with respect to the total amount of the antibacterial fiber, and furthermore, excellent antibacterial properties could be exhibited.
- a first embodiment is an antibacterial fiber containing a thermoplastic resin and an antibacterial glass as mixing components, the antibacterial fiber having the average diameter adjusted to a value within the range of 1 to 50 ⁇ m, the antibacterial fiber including a core portion and a sheath portion, in which when a content of the antibacterial glass in the core portion is designated as Q1 (weight%) with respect to the total amount of the antibacterial fiber, and a content of the antibacterial glass in the sheath portion is designated as Q2 (weight%) with respect to the total amount of the antibacterial fiber, Q1 and Q2 satisfy the following relational expression (1): Q 1 ⁇ Q 2
- thermoplastic resin As a main component of a resin that constitutes the antibacterial fiber of the present embodiment, a thermoplastic resin is used.
- thermoplastic resin is not particularly limited; however, it is preferable that the thermoplastic resin is at least one of a polyester resin, a polyamide resin, a polyurethane resin, a polyolefin resin (including a polyacrylic resin), a rayon-based resin, a polyvinyl acetate-based resin, a cellulose-based resin, a polyvinyl chloride-based resin, and a polyacetal resin.
- the thermoplastic resin is at least one of a polyester resin, a polyamide resin, a polyurethane resin, a polyolefin resin (including a polyacrylic resin), a rayon-based resin, a polyvinyl acetate-based resin, a cellulose-based resin, a polyvinyl chloride-based resin, and a polyacetal resin.
- thermoplastic resins more preferred is a polyester resin or a polyolefin resin.
- a suitable polyester resin may be at least one of a polyethylene terephthalate resin, a polypropylene terephthalate resin, a polybutylene terephthalate resin, a polycyclohexanedimethylene terephthalate resin, a polylactic acid resin, a polybutylene succinate resin, a polyglycolic acid resin, and the like, and above all, preferred is a polyethylene terephthalate resin.
- a suitable polyolefin resin may be at least one of a polypropylene resin, polyethylene resins (a high-density polyethylene resin, a linear polyethylene resin, a low-density polyethylene resin, and the like), a polymethylpentene resin, a vinyl acetate copolymer resin, a propylene copolymer resin, and the like, and above all, preferred is a polypropylene resin.
- thermoplastic resin composition could be stably processed into an antibacterial fiber, an antibacterial film, or the like, which requires excellent flexibility.
- a polyethylene terephthalate resin has a feature that the rate of crystallization is low compared to a polybutylene terephthalate resin, crystallization does not proceed when the temperature is not high, and the strength is increased by heat treatment and stretching treatment.
- the antibacterial fiber when a polyethylene terephthalate resin is used, the antibacterial fiber has high transparency as well as excellent heat resistance and practical strength and also has excellent recyclability, and therefore, it is also advantageous in the economic efficiency.
- plastic products formed from a polyethylene terephthalate resin are currently distributed in large quantities and are very cheap compared to other resin materials.
- the polyethylene terephthalate resin may also be a copolymerized polyester containing other copolymerized components.
- thermoplastic resin is a polypropylene resin
- the thermoplastic resin has excellent mechanical strength such as tensile strength, impact strength, and compression strength, and the mechanical strength could be adjusted according to the use application.
- a polypropylene resin has excellent abrasion resistance and chemical resistance and has excellent quick dry ability and warming performance, it is thought that a polypropylene resin could be suitably used for antibacterial fibers.
- thermoplastic resin composition in the course of producing and molding an antibacterial fiber could be suppressed effectively, and the thermoplastic resin composition could be stably processed into an antibacterial fiber, an antibacterial film, or the like.
- thermoplastic resin that serves as a main component is a polyethylene terephthalate resin, a polypropylene resin, or the like, it is preferable that the number average molecular weight thereof is adjusted to a value within the range of 5,000 to 80,000.
- the reason for this is that when the number average molecular weight of the polyethylene terephthalate resin, the polypropylene resin, or the like is adjusted to a value within such a range, the compatibility with a resin that serves as a sub-component of the thermoplastic resin that will be described below could be enhanced, hydrolysis of the resin could be effectively suppressed, and the antibacterial glass could be dispersed more uniformly.
- the number average molecular weight of the thermoplastic resin is adjusted to a value within the range of 10,000 to 60,000, and even more preferably to a value within the range of 20,000 to 50,000.
- the melting point of the thermoplastic resin that serves as a main component is adjusted to a value within the range of 150°C to 350°C.
- thermoplastic resin composition when the melting point is 150°C or higher, the mechanical characteristics such as tensile strength and tear strength of the thermoplastic resin composition could be sufficiently secured, and since appropriate viscosity is obtained when the thermoplastic resin composition is heated and melted, appropriate processability is obtained.
- thermoplastic resin composition is satisfactory, and the thermoplastic resin could be easily mixed with resin components other than the thermoplastic resin that will be described below.
- the melting point of the thermoplastic resin as a main component is adjusted to a value within the range of 200°C to 300°, and even more preferably to a value within the range of 230°C to 270°C.
- the melting point of the resin could be measured according to ISO 3146.
- the glass transition point is adjusted to a value within the range of 150°C to 350°C.
- the amount of incorporation of the polyethylene terephthalate resin or polypropylene resin is adjusted to a value within the range of 80 to 99.4 parts by weight in a case in which the total amount of the thermoplastic resin composition is designated as 100 parts by weight.
- the reason for this is that when the amount of incorporation of the polyethylene terephthalate resin or polypropylene resin is adjusted to a value within such a range, hydrolysis of the resin could be effectively suppressed, and the thermoplastic resin composition could be easily processed into an antibacterial fiber or an antibacterial film.
- the amount of incorporation of the polyethylene terephthalate resin or polypropylene resin is adjusted to a value within the range of 85 to 99 parts by weight, and even more preferably to a value within the range of 90 to 98 parts by weight, when the total amount of the antibacterial resin composition is designated as 100 parts by weight.
- the tensile strength of the resin that serves as a main component is adjusted to a value within the range of 20 to 100 MPa, in a case in which the tensile strength is measured according to JIS L 1015.
- the reason for this is that when the tensile strength of the resin is below 20 MPa, cutting of the fiber may occur at the time of stretching, or a manufactured product produced using an antibacterial fiber may break open at the time of washing the manufactured product.
- the tensile strength of the resin is adjusted to a value within the range of 25 to 95 MPa, and even more preferably to a value within the range of 30 to 90 MPa.
- thermoplastic resin according to the present embodiment is prepared as a mixing resin including a polybutylene terephthalate resin as another resin component.
- a polybutylene terephthalate resin has high oleophilic compared to a polyethylene terephthalate resin and a smaller number of ester bonds contained per unit weight, it is thought that the polybutylene terephthalate resin does not easily undergo hydrolysis.
- the polybutylene terephthalate resin according to the present embodiment basically refers to a polymer obtainable by a polycondensation reaction between terephthalic acid or an ester-forming derivative thereof as an acid component and 1,4-butanediol or an ester-forming derivative thereof as a glycol component.
- the total amount of acid components is designated as 100 mol%
- another acid component may also be included as long as the amount has a value within the range of 20 mol% or less.
- the amount of incorporation of a polybutylene terephthalate resin is adjusted to a value within the range of 0.5 to 25 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate resin.
- thermoplastic resin having hydrolysis resistance and having excellent dispersing properties for the antibacterial glass could be obtained, while a polyethylene terephthalate resin that could be processed into an antibacterial fiber or an antibacterial film is used as a main component.
- the amount of incorporation of the polybutylene terephthalate resin is adjusted to a value within the range of 2 to 15 parts by weight, and even more preferably to a value within the range of 3 to 10 parts by weight, with respect to 100 parts by weight of the polyethylene terephthalate resin.
- the types of the thermoplastic resins used in the core portion and the sheath portion may be identical to each other or different from each other.
- the core portion and the sheath portion have high compatibility, and an antibacterial fiber could be stably obtained.
- the mechanical characteristics such as tensile strength and tear strength of the antibacterial fiber thus obtainable could be enhanced by using a resin having higher mechanical strength in the core portion.
- the antibacterial fiber according to the present embodiment contains antibacterial glass, and the antibacterial glass contains silver ions as an antibacterial active ingredient.
- the antibacterial glass is highly safe and maintains antibacterial action for a long period of time, and since the antibacterial glass also has high heat resistance, the antibacterial glass has excellent adaptability as an antibacterial agent that is to be incorporated into the antibacterial fiber.
- the type of the antibacterial glass is produced from both or either of a phosphate-based antibacterial glass and a borosilicate-based glass.
- the glass composition of the phosphate-based antibacterial glass includes Ag 2 O, ZnO, CaO, B 2 O 3 , and P 2 O 5 , and that when the total amount is designated as 100% by weight, the amount of incorporation of Ag 2 O is adjusted to a value within the range of 0.2% to 5% by weight, the amount of incorporation of ZnO is adjusted to a value within the range of 2% to 60% by weight, the amount of incorporation of CaO is adjusted to a value within the range of 0.1% to 15% by weight, the amount of incorporation of B 2 O 3 is adjusted to a value within the range of 0.1% to 15% by weight, the amount of incorporation of P 2 O 5 is adjusted to a value within the range of 30% to 80% by weight, and the weight ratio of ZnO/CaO is adjusted to a value within the range of 1.1 to 15.
- Ag 2 O is an essential constituent component as an antibacterial ion-releasing substance in glass composition 1, and since the glass composition includes Ag 2 O, when glass components are melted, silver ions could be slowly eluted at a predetermined rate, and thus excellent antibacterial properties could be exhibited for a long period of time.
- the amount of incorporation of Ag 2 O is adjusted to a value within the range of 0.2% to 5% by weight.
- the antibacterial glass may not be easily discolored, and since the cost could be suppressed, it is economically advantageous.
- the amount of incorporation of Ag 2 O is adjusted to a value within the range of 0.5% to 4% by weight, and it is even more preferable that the amount of incorporation is adjusted to a value within the range of 0.8% to 3.5% by weight.
- P 2 O 5 is an essential constituent component in glass composition 1 and basically functions as a network-forming oxide; however, in addition to that, in the invention, P 2 O 5 is also involved in a function of improving the transparency of the antibacterial glass or uniform release properties for silver ions.
- the amount of incorporation of P 2 O 5 is adjusted to a value within the range of 30% to 80% by weight.
- the amount of incorporation of P 2 O 5 is adjusted to a value within the range of 35% by 75% by weight, and it is even more preferable that the amount of incorporation is adjusted to a value within the range of 40% to 70% by weight.
- ZnO is an essential constituent component in the glass composition 1, has a function as a network-modifying oxide for the antibacterial glass, prevents yellowing, and also has a function of enhancing the antibacterial properties.
- the amount of incorporation of ZnO is adjusted to a value within the range of 2% to 60% by weight with respect to the total amount.
- the reason for this is that when the amount of incorporation of ZnO as such has a value of 2% by weight or more, a yellowing preventing effect and an effect of enhancing the antibacterial properties are easily exhibited. On the other hand, it is because when the amount of incorporation of ZnO as such has a value of 60% by weight or less, the transparency of the antibacterial glass is not easily lowered, and mechanical strength could be easily secured.
- the amount of incorporation of ZnO is adjusted to a value within the range of 5% to 50% by weight, and it is even more preferable that the amount of incorporation is adjusted to a value within the range of 10% to 40% by weight.
- the amount of incorporation of ZnO is determined by taking the amount of incorporation of CaO that will be described below into consideration.
- the weight ratio represented by ZnO/CaO is adjusted to a value within the range of 1.1 to 15.
- the weight ratio represented by ZnO/CaO is adjusted to a value within the range of 2.0 to 12, and it is even more preferable that the weight ratio is adjusted to a value within the range of 3.0 to 10.
- CaO is an essential constituent component for glass composition 1, and CaO basically accomplishes a function as a network-modifying oxide, and could lower the heating temperature at the time of producing the antibacterial glass or exhibit a yellowing preventing function together with ZnO.
- the amount of incorporation of CaO is adjusted to a value within the range of 0.1% to 15% by weight with respect to the total amount.
- the reason for this is that when the amount of incorporation of CaO as such is 0.1% by weight or more, a yellowing preventing function and an effect of lowering the melting temperature are easily exhibited. On the other hand, it is because when the amount of incorporation of CaO as such is 15% by weight or less, deterioration of the transparency of the antibacterial glass could be easily suppressed.
- the amount of incorporation of CaO is adjusted to a value within the range of 1.0% to 12% by weight, and it is more preferable that the amount of incorporation is adjusted to a value within the range of 3.0% to 10% by weight.
- B 2 O 3 is an essential constituent component for glass composition 1, and basically accomplishes a function as a network-forming oxide.
- B 2 O 3 is a component that is involved in the transparency-improving function of the antibacterial glass as well as uniform release properties for silver ions.
- the amount of incorporation of B 2 O 3 is adjusted to a value within the range of 0.1% to 15% by weight with respect to the total amount.
- the amount of incorporation of B 2 O 3 is adjusted to a value within the range of 1.0% to 12% by weight, and it is more preferable that the amount of incorporation is adjusted to a value within the range of 3.0% to 10% by weight.
- CeO 2 , MgO, Na 2 O, Al 2 O 3 , K 2 O, SiO 2 , BaO, and the like as optional constituent components for glass composition 1 are added in predetermined amounts within the scope of the object of the invention.
- the glass composition of the phosphate-based antibacterial glass includes Ag 2 O, CaO, B 2 O 3 , and P 2 O 5 , while ZnO is not substantially included therein, and when the total amount is designated as 100% by weight, the amount of incorporation of Ag 2 O is adjusted to a value within the range of 0.2% to 5% by weight, the amount of incorporation of CaO is adjusted to a value within the range of 15% to 50% by weight, the amount of incorporation of B 2 O 3 is adjusted to a value within the range of 0.1% to 15% by weight, the amount of incorporation of P 2 O 5 is adjusted to a value within the range of 30% to 80% by weight, and the weight ratio of CaO/Ag 2 O is adjusted to a value within the range of 5 to 15.
- the amount of incorporation of Ag 2 O is adjusted to a value within the range of 0.2% to 5% by weight, more preferably to a value within the range of 0.5% to 4.0% by weight, and even more preferably to a value within the range of 0.8% to 3.5% by weight.
- the antibacterial glass could basically accomplish a function as a network-modifying oxide and could also lower the heating temperature at the time of producing antibacterial glass or exhibit a yellowing preventing function.
- the amount of incorporation of CaO is adjusted to a value within the range of 15% to 50% by weight with respect to the total amount.
- the amount of incorporation of CaO is adjusted to a value within the range of 20% to 45% by weight, and it is even more preferable that the amount of incorporation is adjusted to a value within the range of 25% to 40% by weight.
- the amount of incorporation of CaO is determined by taking the amount of incorporation of Ag 2 O into consideration, and specifically, it is preferable that the weight ratio represented by CaO/Ag 2 O is adjusted to a value within the range of 5 to 15.
- the weight ratio represented by CaO/Ag 2 O is adjusted to a value within the range of 6 to 13, and it is even more preferable that the weight ratio is adjusted to a value within the range of 8 to 11.
- components such as CeO 2 , MgO, Na 2 O, Al 2 O 3 , K 2 O, SiO 2 , and BaO are added in predetermined amounts as optional constituent components similarly to glass composition 1, within the scope of the purpose of the invention.
- the glass composition of borosilicate glass includes B 2 O 3 , SiO 2 , Ag 2 O, and alkali metal oxides, and when the total amount is designated as 100% by weight, the amount of incorporation of B 2 O 3 is adjusted to a value within the range of 30% to 60% by weight, the amount of incorporation of SiO 2 is adjusted to a value within the range of 30% to 60% by weight, the amount of incorporation of Ag 2 O is adjusted to a value within the range of 0.2% to 5% by weight, the amount of incorporation of the alkali metal oxides is adjusted to a value within the range of 5% to 20% by weight, the amount of incorporation of Al 2 O 3 is adjusted to a value within the range of 0.1% to 2% by weight, and in a case in which the total amount is below 100% by weight, other glass components (alkaline earth metal oxides, CeO 2 , CoO, and the like) are included as balance components at a value within the range of 0.1% to 33% by weight.
- other glass components alkaline earth metal oxide
- B 2 O 3 basically accomplishes a function as a network-forming oxide; however, in addition to that, B 2 O 3 is also involved in a function of improving transparency and uniform release properties for silver ions.
- SiO 2 accomplishes a function as a network-forming oxide in an antibacterial glass and also has a function of preventing yellowing.
- Ag 2 O is an essential constituent component for an antibacterial glass, and as the glass components are melted and thereby silver ions are eluted, excellent antibacterial properties could be exhibited for a long period of time.
- Alkali metal oxides for example, Na 2 O and K 2 O, basically accomplish a function as network-modifying oxides, also exhibit a function of adjusting the melt characteristics of antibacterial glass, reduce the water-resistance of antibacterial glass, and could thereby adjust the amount of elution of silver ions from an antibacterial glass.
- alkaline earth metal oxides for example, when MgO or CaO is added, a function as network-modifying oxides could be accomplished, and similarly to alkali metal oxides, a function of improving the transparency of the antibacterial glass and a function of adjusting the melting temperature could be exhibited.
- the elution rate of antibacterial ions from the antibacterial glass is adjusted to a value within the range of 1 ⁇ 10 2 to 1 ⁇ 10 5 mg/Kg/24 Hr.
- the elution rate of antibacterial ions from the antibacterial glass is adjusted to a value within the range of 1 ⁇ 10 3 to 5 ⁇ 10 4 mg/Kg/24 Hrs, and even more preferably to a value within the range of 3 ⁇ 10 3 to 1 ⁇ 10 4 mg/Kg/24 Hr. Meanwhile, such an elution rate of antibacterial ions could be measured under the following measurement conditions.
- volume average particle size (volume average primary particle size, D50) of the antibacterial glass is adjusted to a value within the range of 0.1 to 5.0 ⁇ m.
- the reason for this is that when the volume average particle size of the antibacterial glass is adjusted to a value within such a range, the antibacterial glass could be dispersed more uniformly, and it is because a thermoplastic resin containing antibacterial glass could be processed into an antibacterial fiber or an antibacterial film more stably.
- the volume average particle size of the antibacterial glass is 0.1 ⁇ m or greater, mixing and dispersing of the antibacterial glass into the resin component are easily achieved, light scattering is suppressed, or transparency could be easily secured.
- the volume average particle size of the antibacterial glass is 5.0 ⁇ m or less, since the antibacterial glass is uniformly dispersed in the resin component, the mechanical strength of the antibacterial fiber could be easily secured.
- the volume average particle size of the antibacterial glass is adjusted to a value within the range of 0.5 to 4.0 ⁇ m, and even more preferably to a value within the range of 1.0 to 3.0 ⁇ m.
- the volume average particle size (D50) of the antibacterial glass could be calculated from the particle size distribution obtainable using a laser type particle counter (according to JIS Z 8852-1) or a sedimentation type particle size distribution meter, or from the particle size distribution obtainable by performing image processing based on electron microscopic photographs of the antibacterial glass.
- the specific surface area of the antibacterial glass is adjusted to a value within the range of 10,000 to 300,000 cm 2 /cm 3 .
- the specific surface area of the antibacterial glass is adjusted to a value within the range of 15,000 to 200,000 cm 2 /cm 3 , and it is even more preferable that the specific surface area is adjusted to a value within the range of 18,000 to 150,000 cm 2 /cm 3 .
- the specific surface area (cm 2 /cm 3 ) of the antibacterial glass could be determined from the results of particle size distribution measurement, and under an assumption that the antibacterial glass has a spherical shape, the specific surface area could be calculated as a surface area (cm 2 ) per unit volume (cm 3 ) from the actually measured data of the particle size distribution.
- the shape of the antibacterial glass is made into a polyhedron, that is, a polyhedron configured to have a plurality of corners and faces, for example, a polyhedron configured to have 6 to 20 faces.
- the reason for this is that when the shape of the antibacterial glass is made into a polyhedron as described above, unlike spherical-shaped antibacterial glass, light could easily advance in-plane in a fixed direction. It is also because since light scattering attributed to the antibacterial glass could be effectively prevented, transparency of the antibacterial glass could be enhanced.
- the antibacterial glass is made into a polyhedron as such, mixing and dispersing into the resin component is facilitated, and particularly in a case in which an antibacterial fiber is produced using a spinning apparatus or the like, the antibacterial fiber has a feature that the antibacterial glass is easily oriented in a fixed direction.
- the antibacterial glass could be easily dispersed uniformly in the resin component, and at the same time, scattering of light by the antibacterial glass in the resin component is effectively prevented so that excellent transparency could be exhibited.
- the shape of the antibacterial glass is a polyhedron as such, external additives that will be described below could easily adhere thereto, and the antibacterial glass may not easily reaggregate during production or during use or the like. Therefore, control of the average particle size and the variation during the production of the antibacterial glass is facilitated.
- the surface of the antibacterial glass is treated with a polyorganosiloxane-silicone resin, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like.
- aggregated silica particles dry silica or wet silica are externally added to the antibacterial glass.
- aggregated silica particles constitute a main component
- combination thereof with one of titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium carbonate, shirasu balloons, quartz particles, glass balloons, and the like, or with two or more kinds thereof is also preferable.
- aggregated silica particles dry silica or wet silica
- colloidal silica which is an aqueous dispersion of the aggregated silica particles
- these materials have a small number average primary particle size and highly excellent dispersibility in the antibacterial glass.
- silica particles adhere to the periphery of the antibacterial glass and could uniformly disperse the antibacterial glass even in the resin component. As the result, the antibacterial glass could be uniformly dispersed evenly within the antibacterial fiber.
- the number average secondary particle size of the aggregated silica as an external additive is adjusted to a value within the range of 1 to 15 ⁇ m.
- the reason for this is that when the number average secondary particle size of such an external additive has a value of 1 ⁇ m or more, dispersibility of the antibacterial glass 10 is improved, light scattering is suppressed, and transparency could be secured.
- the number average secondary particle size of the external additive is adjusted to a value within the range of 5 to 12 ⁇ m, and it is even more preferable that the number average secondary particle size is adjusted to a value within the range of 6 to 10 ⁇ m.
- the number average secondary particle size of the external additive could be measured using a laser type particle counter (according to JIS Z 8852-1) or a sedimentation type particle size distribution meter.
- the number average secondary particle size of the external additive could be calculated by subjecting an electron microscopic photograph of these particles to image processing.
- the number average primary particle size in a state in which the aggregates are loosened is adjusted to a value within the range of 0.005 to 0.5 ⁇ m.
- the reason for this is that when the number average primary particle size of the external additive has a value of 0.005 ⁇ m or greater, an effect of enhancing the dispersibility of the antibacterial glass could be easily obtained, light scattering is suppressed, and deterioration of transparency could be suppressed.
- the number average primary particle size of the external additive is adjusted to a value within the range of 0.01 to 0.2 ⁇ m, and it is even more preferable that the number average primary particle size is adjusted to a value within the range of 0.02 to 0.1 ⁇ m.
- the number average primary particle size of the external additive could be measured by a method similar to that used for the number average secondary particle size.
- the amount of addition of aggregated silica as an external additive is adjusted to a value within the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the antibacterial glass.
- the reason for this is that when the amount of addition of the external additive as such has a value of 0.1 parts by weight or more, dispersibility of the antibacterial glass is improved.
- the amount of addition of the external additive as such has a value of 50 parts by weight or less, the external additive could be uniformly mixed with the antibacterial glass, and the transparency of the antibacterial resin composition thus obtainable is not easily deteriorated.
- the amount of addition of the external additive is adjusted to a value within the range of 0.5 to 30 parts by weight, and even more preferably to a value within the range of 1 to 10 parts by weight, with respect to 100 parts by weight of the antibacterial glass.
- the content of the moisture is adjusted to a value within the range of 1 ⁇ 10 -4 to 5 parts by weight with respect to 100 parts by weight of the solid components of the antibacterial glass.
- thermoplastic resin composition when the moisture content is adjusted to a value within such a range, at the time of producing a thermoplastic resin composition, hydrolysis of the thermoplastic resin is effectively suppressed even in a case in which a step of drying the antibacterial glass is omitted, and the antibacterial glass could be uniformly dispersed.
- the moisture content of the antibacterial glass is adjusted to a value within the range of 1 ⁇ 10 -3 to 1 parts by weight, and even more preferably to a value within the range of 1 ⁇ 10 -2 to 1 ⁇ 10 -1 parts by weight, with respect to 100 parts by weight of the solid components of the antibacterial glass.
- the measurement of the moisture content in the antibacterial glass could be carried out by, for example, a weight loss on heating method at 105°C with an electronic moisture meter, or could also be carried out using a Karl-Fischer method.
- the amount of incorporation of the antibacterial glass is preferably such that when the content of the antibacterial glass in the core portion is designated as Q1 (weight%) with respect to the total amount of the antibacterial fiber, and the content of the antibacterial glass in the sheath portion is designated as Q2 (weight%) with respect to the total amount of the antibacterial fiber, Q1 is adjusted to 0 or 0% to below 1% by weight (provided that 0% by weight is excluded), and Q2 is adjusted to a value within the range of 1% to 10% by weight.
- the reason for this is that when the amount of incorporation of the antibacterial glass is adjusted to a value within such a range, hydrolysis of the thermoplastic resin is effectively suppressed, the antibacterial glass is uniformly dispersed in the resin component, and an excellent antibacterial effect could be obtained.
- the content of the antibacterial glass in the core portion could be regulated to be smaller than the content of the antibacterial glass in the sheath portion, and excellent antibacterial properties could be exhibited even when a small amount of incorporation is used with respect to the total amount of the antibacterial fiber.
- thermoplastic resin could be easily processed into an antibacterial fiber or an antibacterial film.
- Q1 is adjusted to 0 or below 0.5% by weight
- Q2 is adjusted to a value within the range of 1.5% to 9% by weight.
- Q1 is adjusted to 0 or below 0.1% by weight
- Q2 is adjusted to a value within the range of 2% to 8% by weight.
- Antibacterial fiber 1 includes, as shown in the electron microscopic photograph (SEM image) of Fig. 1 and the schematic diagram of Fig. 2 , a core portion 20 and a sheath portion 30, in which the content of the antibacterial glass 10 in the core portion 20 is smaller than the content of the antibacterial glass 10 in the sheath portion 30.
- the average diameter of the antibacterial fiber is adjusted to a value within the range of 1 to 50 ⁇ m.
- the average diameter of the antibacterial fiber has a value of 1 ⁇ m or greater, the mechanical strength of the antibacterial fiber could be easily secured, and the antibacterial fiber could be stably produced.
- the average diameter of the antibacterial fiber is adjusted to a value within the range of 2 to 49 ⁇ m, and even more preferably to a value within the range of 3 to 48 ⁇ m.
- the diameter could be actually measured at several points (for example, five points) using an electron microscope, a micrometer, or vernier calipers, and an average value thereof could be adopted. Furthermore, the average diameter could also be determined as an equivalent circle diameter.
- thermoplastic resin used in the core portion the above-mentioned thermoplastic resin could be used. Furthermore, it is also preferable that the number average molecular weight and the melting point of the thermoplastic resin are adjusted to values within the above-mentioned ranges.
- the average diameter ⁇ of the core portion of the antibacterial fiber 1 according to the present embodiment is adjusted to a value within the range of 0.3 to 40 ⁇ m.
- the average diameter of the core portion is adjusted to a value within the range of 0.5 to 35 ⁇ m, and even more preferably to a value within the range of 0.7 to 30 ⁇ m.
- the diameter could be actually measured at several points (for example, five points) using an electron microscope or a micrometer, and an average value thereof could be adopted.
- thermoplastic resin used in the sheath portion the above-mentioned thermoplastic resin could be used. Furthermore, it is also preferable that the number average molecular weight and melting point of the thermoplastic resin are adjusted to values within the above-mentioned ranges.
- the thickness t of the sheath portion of the antibacterial fiber 1 according to the present embodiment is adjusted to a value within the range of 0.7 to 49.7 ⁇ m.
- the thickness of the sheath portion is adjusted to a value within the range of 1 to 45 ⁇ m, and even more preferably to a value within the range of 5 to 40 ⁇ m.
- t is actually measured at several points (for example, five points) using an electron microscope or a micrometer, and an average value thereof could be adopted.
- Q1 content of the antibacterial glass in the core portion
- Q2 content of the antibacterial glass in the sheath portion
- the antibacterial fiber could have a concentration distribution of the antibacterial glass and could exhibit excellent antibacterial properties.
- Q1 and Q2 satisfy the following relational expression (2): 0 ⁇ Q 2 ⁇ Q 1 ⁇ 10
- concentration distribution of the antibacterial glass in the antibacterial fiber could be thereby adjusted to be in an optimal range.
- Q1 and Q2 that satisfy such a relational expression, it is preferable that Q1 is adjusted to 0 or below 1% by weight (provided that 0% by weight is excluded), and it is preferable that Q2 is adjusted to a value within the range of 1% to 10% by weight. Furthermore, it is more preferable that Q1 is adjusted to 0 or below 0.5% by weight, and it is more preferable that Q2 is adjusted to a value within the range of 1.5% to 9% by weight. Furthermore, it is even more preferable that Q1 is adjusted to 0 or below 0.1% by weight, and it is even more preferable that Q2 is adjusted to a value within the range of 2% to 8% by weight.
- the antibacterial fiber according to the present embodiment from the viewpoint of imparting sufficient strength to a manufactured product when the antibacterial fiber is processed into a woven fabric or the like, it is preferable that the tensile strength (cN/dtex) measured according to JIS L 1015 is adjusted to a value within the range of 3 to 50 cN/dtex.
- the reason for this is that when the tensile strength (cN/dtex) of the antibacterial fiber is below 3 cN/dtex, cutting of the fiber may occur at the time of stretching, or a manufactured product that uses the antibacterial fiber may break open at the time of washing of the manufactured product or the like.
- the antibacterial fiber may not have sufficient flexibility, and the use application may be excessively limited.
- the tensile strength (cN/dtex) of the antibacterial fiber is adjusted to a value within the range of 3.5 to 30 cN/dtex, and even more preferably to a value within the range of 4.5 to 20 cN/dtex.
- the apparent degree of weaving and the number of windings of the antibacterial fiber are not particularly limited and could be adjusted as appropriate according to the use application of the antibacterial fiber.
- the apparent degree of weaving of the antibacterial fiber could be adjusted as appropriate according to the use application; however, for example, it is preferable that the apparent degree of weaving is adjusted to a value within the range of 0.1 to 50 dtex, more preferably to a value within the range of 0.5 to 30 dtex, and even more preferably to a value within the range of 1 to 10 dtex.
- the number of windings of the antibacterial fiber could be adjusted according to the use application from the viewpoints of imparting elastic force, tactile sensation, and the like, and as the number of windings is larger, the antibacterial fiber becomes richer in elastic force.
- the number of windings of the antibacterial fiber may be usually adjusted to 5 to 90 windings per 25 mm of the fiber, and for a use application that requires elasticity, it is preferable that the number of windings is adjusted to 50 to 90.
- the antibacterial fiber according to the present embodiment includes a dispersion aid for the antibacterial glass.
- the antibacterial fiber includes a dispersion aid, the antibacterial glass could be dispersed more uniformly.
- the type of the dispersion aid is not particularly limited, and for example, an aliphatic amide-based dispersion aid, a hydrocarbon-based dispersion aid, a fatty acid-based dispersion aid, a higher alcohol-based dispersion aid, a metal soap-based dispersion aid, an ester-based dispersion aid, or the like could be used. However, above all, an aliphatic amide-based dispersion aid is particularly preferred.
- Aliphatic amide-based dispersion aids are roughly classified into fatty acid amides such as stearic acid amide, oleic acid amide, and erucic acid amide; and alkylene fatty acid amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide. However, it is more preferable to use an alkylene fatty acid amide.
- ethylenebisstearic acid amide among the alkylene fatty acid amides.
- the amount of incorporation of the dispersion aid is adjusted to a value within the range of 1 to 20 parts by weight with respect to 100 parts by weight of the antibacterial glass.
- the amount of incorporation of the dispersion aid has a value of 1 part by weight or more, the dispersibility of the antibacterial glass in the antibacterial fiber could be sufficiently enhanced.
- the amount of incorporation of the dispersion aid is 20 parts by weight or less, mechanical characteristics such as tensile strength and tear strength of the antibacterial resin composition could be sufficiently secured, and bleed-out of the dispersion aid from the antibacterial resin composition does not easily occur.
- the amount of incorporation of the dispersion aid is adjusted to a value within the range of 3 to 12 parts by weight, and even more preferably to a value within the range of 5 to 8 parts by weight, with respect to 100 parts by weight of the antibacterial glass.
- additives such as a stabilizer, a mold release agent, a nucleating agent, a filler, a dye, a pigment, an antistatic agent, an oil solution, a lubricating agent, a plasticizer, a sizing agent, an ultraviolet absorber, an antifungal agent, an antiviral agent, a flame retardant, and a flame retardant aid; another resin; an elastomer, and the like as optional components to the antibacterial fiber as necessary, to the extent that does not impair the original purpose.
- additives such as a stabilizer, a mold release agent, a nucleating agent, a filler, a dye, a pigment, an antistatic agent, an oil solution, a lubricating agent, a plasticizer, a sizing agent, an ultraviolet absorber, an antifungal agent, an antiviral agent, a flame retardant, and a flame retardant aid; another resin; an elastomer, and the like as optional components to the antibacterial fiber as necessary, to the
- the method of adding these optional components into the antibacterial fiber is not particularly limited, and for example, it is also preferable to perform the addition by melt kneading the optional components into a thermoplastic resin together with antibacterial glass.
- the antibacterial fiber according to the present embodiment is processed into a cotton form or a sheet-like molded article such as a woven fabric, nonwoven fabric, a textile fabric, a felt, or a web.
- processing may be carried out using only the antibacterial fiber of the present embodiment; however, it is also preferable that a fiber of another kind and the antibacterial fiber of the present embodiment are subjected to yarn mixing and mixed spinning to be processed into a plied yarn, a covering yarn, or a braided cord.
- Examples of the other kind of fiber include synthetic fibers of nylon, polyester, polyurethane, or the like; natural fibers of cotton yarn, silk yarn, or the like; carbon fibers; and glass fibers.
- a product obtained by subjecting the antibacterial fiber and another type of fiber to yarn mixing and mixed spinning, and processing the resultant into a plied yarn, a covering yarn, or a braided cord also has antibacterial properties that are equivalent to those of the antibacterial fiber of the present embodiment, and has an excellent feature that such a product maintains antibacterial properties even when washed repeatedly.
- the antibacterial fiber according to the present embodiment or a processed product such as cotton, a woven fabric, or a knit fabric, which is obtained by processing the antibacterial fiber according to the use application is further subjected to dyeing or various finish processing (crease resistance, anti-fouling, flame retardance, insect-proofing, mildew-proofing, deodorization, moisture absorption, water repellency, calendaring, anti-pilling, and the like).
- the use application of the sheet-like molded article is not particularly limited; however, examples include clothes, bedding, interior tools, absorption cloth, packaging materials, miscellaneous goods, and filtration media.
- clothes examples include underwear, a shirt, sportswear, an apron, socks, insoles, stockings, tights, tabi socks, kimono items, a necktie, a handkerchief, a scarf, a muffler, a hat, gloves, and a mask for domestic or medical use.
- the bedding examples include a futon cover, padding in a futon, a pillowcase, padding in a pillow, a towelket, a sheet, and external cladding of a mattress.
- the sheet-like molded article is appropriate for the use in bedding that is difficult to wash, such as a down quilt or a down pillow.
- Examples of the interior tools include a curtain, a mat, a carpet, a rug, a floor cushion, a cushion, a tapestry, wall cladding, tablecloth, and moquette.
- absorption cloth examples include a towel, dishcloth, a handkerchief, a mop, a diaper, a tampon, a sanitary napkin, and adult incontinence articles.
- packaging materials include a wrapping cloth, wrapping paper, and a food package.
- miscellaneous goods examples include various brushes such as a toothbrush, a dish scrubber, and a brush; a carrier bag, a luncheon mat, a pen case, a purse, an eyeglasses case, an eyeglasses wiper, a shop curtain, a coaster, a mouse pad, inner cotton for stuffed toys, and a pet bed.
- filtration media examples include filters for use in an air conditioner, a ventilating fan, an air hatch, and an air cleaner, and filters for water purification, and these could be applied to filters for domestic use, industrial use, automobile use, and the like.
- Examples of other uses include artificial hair, a tent, a light-shielding sheet such as a weed preventing sheet, a soundproof material, an acoustic material, and a buffer material.
- a second embodiment is a method for producing the antibacterial fiber described in the first embodiment and is a method for producing an antibacterial fiber having a core portion and a sheath portion and containing a thermoplastic resin and an antibacterial glass as mixing components, and it is a method for producing an antibacterial fiber, the method including the following steps (1) to (3):
- the antibacterial fiber according to the present embodiment could be produced by a production method having at least the steps (1) to (3) described above, and if necessary, the following steps (4) to (6) may be added.
- Step (1) Step of preparing antibacterial glass
- Step (1) is a step of producing an antibacterial glass from glass raw materials including an antibacterial active ingredient.
- the antibacterial glass could be produced by a conventionally known method, and for example, it is preferable to produce the antibacterial glass by a method including the following (1)-1 to (1)-3.
- glass raw materials are accurately weighed and then uniformly mixed, subsequently the mixture is melted using, for example, a glass melting furnace, and thus a glass melt is produced.
- a mixing machine such as a universal stirrer (planetary mixer), an alumina porcelain crusher, a ball mill, or a propeller mixer, and for example, in the case of using a universal stirrer, it is preferable that the glass raw materials are stirred and mixed by setting the speed of revolution to 100 rpm and the speed of rotation to 250 rpm, under the conditions of 10 minutes to 3 hours.
- the melting temperature is adjusted to 1,100°C to 1,500°C and the melting time is adjusted to a value within the range of 1 to 8 hours.
- the glass melt is injected into flowing water and cooled, and water pulverization is combined to obtain a glass body.
- the glass body thus obtained is pulverized, and an antibacterial glass that is composed of polyhedrons and has a predetermined volume average particle size is produced.
- classification is further carried out after pulverization, and it is also preferable to perform sieve treatment or the like.
- the glass body In the crude pulverization, it is preferable to pulverize the glass body so as to obtain a volume average particle size of about 10 mm.
- a predetermined volume average particle size by performing water granulation when a glass melt in a molten state is converted into a glass body, or performing pulverization an amorphous glass body with bare hands or using a hammer or the like.
- the antibacterial glass obtained after crude pulverization is pulverized so as to obtain a volume average particle size of about 1 mm.
- the antibacterial glass having a volume average particle size of about 10 mm is produced into an antibacterial glass having a volume average particle size of about 5 mm using a ball mill, and subsequently, an antibacterial glass having a volume average particle size of about 1 mm is obtained using a rotary mortar or a rotating roll (roll pulverizer).
- the antibacterial glass obtained after intermediate pulverization includes polyhedrons having corners.
- the antibacterial glass obtained after intermediate pulverization is pulverized so as to obtain a volume average particle size of 1.0 to 5.0 ⁇ m, in a state in which aggregated silica particles have been added as an external additive having a volume average particle size of 1 to 15 ⁇ m.
- pulverize the antibacterial glass using a rotary mortar, a rotating roll (roll pulverizer), a vibrating mill, a vertical mill, a dry ball mill, a planetary mill, a sand mill, or a jet mill.
- dry pulverizing machines it is more preferable to use a vertical mill, a dry ball mill, a planetary mill, and a jet mill in particular.
- a vessel is rotated at a rate of 30 to 100 rpm using zirconia balls or alumina balls as pulverizing media, and the antibacterial glass obtained after intermediate pulverization is subjected to a pulverization treatment for 5 to 50 hours.
- acceleration is achieved in a vessel, and antibacterial glass particles obtained after intermediate pulverization are caused to collide with one another at a pressure of 0.61 to 1.22 MPa (6 to 12 Kgf/cm 2 ).
- the antibacterial glass obtained after performing fine pulverization using a dry ball mill, a jet mill, or the like is composed of polyhedrons having more numerous corners than the antibacterial glass obtained after intermediate pulverization, and the volume average particle size (D50) and the specific surface area could be easily adjusted to predetermined ranges.
- fine pulverization is performed using a planetary mill or the like, it is preferable to perform fine pulverization substantially in a dry state (for example, the relative humidity is 20%RH or less).
- a classification apparatus such as a cyclone could be attached to a planetary mill or the like, and the antibacterial glass could be circulated without causing the antibacterial glass to aggregate.
- the volume average particle size and the particle size distribution for the antibacterial glass could be easily adjusted to desired ranges by controlling the number of times of circulation, and at the same time, a drying step after fine pulverization could be omitted.
- antibacterial glass that is smaller than or equal to a predetermined range, when the antibacterial glass is in a dry state, the antibacterial glass could be easily removed using a bag filter.
- the antibacterial glass obtained in the pulverization step is dried in a drying step.
- thermoplastic resin may cause hydrolysis
- the drying step it is preferable to also perform a drying treatment after performing a solid-liquid separation treatment, and the facilities used for these treatments are not particularly limited.
- a centrifuge or the like could be used for the solid-liquid separation, and a dryer, an oven, or the like could be used for drying.
- the aggregated antibacterial glass is disintegrated using a disintegrator.
- Step (2) Step of preparing spinning dopes
- Step (2) is a step of producing spinning dopes using the antibacterial glass obtained in step (1).
- Step (2) it is preferable that a spinning dope is produced by melting and kneading antibacterial glass or a masterbatch obtained by dispersing antibacterial glass in a thermoplastic resin with resin pellets or regenerated resin flakes.
- step (2) it is also preferable to further add additives such as a colored masterbatch, an oxidation inhibitor, an internal lubricating agent, and a crystallizing agent.
- additives such as a colored masterbatch, an oxidation inhibitor, an internal lubricating agent, and a crystallizing agent.
- step (2) the antibacterial glass thus obtained is mixed and dispersed such that when the content of the antibacterial glass in the core portion is designated as Q1 (weight%) with respect to the total amount of the antibacterial fiber, and the content of the antibacterial glass in the sheath portion is designated as Q2 (weight%) with respect to the total amount of the antibacterial fiber, Q1 and Q2 satisfy the following relational expression (1), and a spinning dope for the core portion and the spinning dope for the sheath portion are prepared.
- Q1 weight%
- Q2 weight% with respect to the total amount of the antibacterial fiber
- Q1 is adjusted to 0 or below 1% by weight (provided that 0% by weight is excluded), and Q2 is adjusted to a value within the range of 1% to 10% by weight.
- thermoplastic resin in the case of using a polyethylene terephthalate resin as a main component, it is preferable that a polybutylene terephthalate resin is mixed and dispersed therein.
- Step (3) Step of producing antibacterial fiber
- the antibacterial fiber according to the invention could be produced by a method similar to a conventionally known method applicable to composite fibers.
- spinning include melt spinning and solution spinning; however, the method is selected depending on the resin to be used.
- step (3) it is preferable that a core-sheath composite spinneret is used, a molten spinning dope for the core portion is introduced into the core portion, while a molten spinning dope for the sheath portion is introduced as the sheath portion, and the spinning dopes are discharged through the spinneret and then produced into fibers by thermal stretching.
- the spinning dope for the core portion and the spinning dope for the sheath portion refer, in the case of melt spinning, to molten resins obtained by melting resins by heating, and in the case of solution spinning, to dopes in a state in which resins have been dissolved in solvents.
- the yarn lines discharged through the spinneret are usually cooled; however, the cooling method is not particularly limited, and a method of blowing cold air against the spun yarn lines could be preferably mentioned as an example.
- spun yarn it is also preferable that a two-step method of first winding the yarn and canning yarn in a can is employed as necessary, and then the yarn is subjected to a stretching treatment.
- any conventionally known apparatus could be used.
- a pressure melter type spinning machine or a single-screw or twin-screw extruder type spinning machine.
- the shape of the spun yarn is not particularly limited; however, the shape may be a circular shape or a flat shape, or may be a polygonal shape such as a hexagonal shape or a star shape.
- the spinning temperature is preferably, for instance, from 240°C to 320°C, and the winding speed is preferably from 100 m/min to 6,000 m/min.
- the stretching step could be carried out using conventionally known methods and apparatuses, and for example, it is preferable to employ a direct spinning and stretching method or a roller stretching method. In a case in which spinning and stretching are performed separately, it is preferable to use a warm water bath.
- the direct spinning and stretching method is carried out by first cooling the fibers to a temperature lower than or equal to the glass transition point after spinning, subsequently causing the fibers to travel inside a tubular heating apparatus at a temperature ranging from the glass transition temperature to the melting point, and winding the fibers.
- the roller stretching method is carried out by taking over the spun yarn by winding around a take-over roller that rotates at a predetermined speed, an stretching the yarn thus taken over in one stage or in multiple stages such as two or more stages, by means of a group of rollers set to a temperature ranging from the glass transition temperature to the melting point of the thermoplastic resin.
- the warm water bath is carried out by immersing the fibers in warm water at 60°C to 90°C, and preferably around 80°C.
- the stretch ratio it is preferable that the stretch ratio is 1.2 times or higher from the viewpoint of increasing the mechanical strength.
- the upper limit of the stretch ratio is not particularly limited; however, from the viewpoint of preventing breakage of the yarn caused by excessive stretching, it is preferable that the stretch ratio is 7 times or less.
- Step (4) Crimping step
- the crimping step of step (4) is an optional process and is a step of guiding the stretched yarn obtained in step (3) into a crimping apparatus, subjecting the yarn to false twisting, and imparting bulkiness and stretch-ability to the yarn.
- a heated fluid crimping apparatus that subjects a yarn to false twisting by bringing the yarn into contact with a heated fluid.
- the heated fluid crimping apparatus is an apparatus that gives crimps to yarn lines by spraying a heated fluid such as, for example, vapor, to the yarn lines and forcing in the yarn lines together with the heated fluid into a compression adjustment unit.
- a heated fluid such as, for example, vapor
- the temperature of the heated fluid is adjusted to a value within the range of 100°C to 150°C.
- the temperature of the heated fluid is adjusted to a value within the range of 110°C to 145°C, and it is even more preferable that the temperature is adjusted to a value within the range of 115°C to 140°C.
- Step (5) Post-treatment step
- the post-treatment step of step (5) is also an optional process and is a step of applying an oil agent to the crimped yarn obtained in step (4), drying the crimped yarn with a dryer, subsequently guiding the crimped yarn to a thermosetting roller, and adjusting the degree of elongation by means of the heating temperature.
- the temperature of the thermosetting roller is a temperature within the range of 130°C to 160°C, from the viewpoint of preventing troubles between winding rolls or defective shrinkage at the time of processing the fibers or in the case of producing base cloth.
- the temperature of the thermosetting roller is adjusted to a value within the range of 135°C to 155°C, and it is even more preferable that the temperature is adjusted to a value within the range of 140°C to 150°C.
- the dyeing step of step (6) is also an optional process and is a step of dyeing the antibacterial fibers that have been stretched and then subjected to crimping and/or thermosetting as necessary, under alkaline conditions or acidic conditions.
- the dyeing solution includes, along with a dye, dyeing aids such as a level dyeing agent, a dye accelerant aid, and a metal sequestering agent, a dye-fixing agent, and a fluorescent brightening agent, as necessary.
- dyeing aids such as a level dyeing agent, a dye accelerant aid, and a metal sequestering agent, a dye-fixing agent, and a fluorescent brightening agent, as necessary.
- the pH could be adjusted to 7.5 to 10.5, and it is preferable to use a carbonic acid salt such as calcium carbonate, sodium hydroxide, or the like for the adjustment of pH.
- a carbonic acid salt such as calcium carbonate, sodium hydroxide, or the like for the adjustment of pH.
- the pH could be adjusted to 3.5 to 6.5, and it is preferable to use an organic acid such as acetic acid, citric acid, malic acid, fumaric acid, or succinic acid, and salts thereof for the adjustment of pH.
- an organic acid such as acetic acid, citric acid, malic acid, fumaric acid, or succinic acid, and salts thereof for the adjustment of pH.
- the conditions that are implemented for conventional polyester fibers could be employed, and in the case of reduction washing, a reducing agent, an alkali, and sodium hydrosulfite could be used respectively in an amount of 0.5 to 3 g/L. It is preferable to treat the fibers at 60°C to 80°C for 10 to 30 minutes.
- the respective glass raw materials were stirred until the components were uniformly mixed, using a universal mixing machine under the conditions of a speed of rotation of 250 rpm and 30 minutes, such that when the total amount of the antibacterial glass was designated as 100% by weight, the composition ratio of P 2 O 5 would be 50% by weight, the composition ratio of CaO would be 5% by weight, the composition ratio of Na 2 O would be 1.5% by weight, the composition ratio of B 2 O 3 would be 10% by weight, the composition ratio of Ag 2 O would be 3% by weight, the composition ratio of CeO 2 would be 0.5% by weight, and the composition ratio of ZnO would be 30% by weight.
- the glass raw materials were heated using a melting furnace under the conditions of 1,280°C and 3.5 hours, and thereby a glass melt was produced.
- the glass melt taken out from the glass melting furnace was water-granulated by causing the glass melt to flow into still water at 25°C, and crude pulverized glass having a volume average particle size of about 10 mm was obtained.
- the crude pulverized glass that had been treated by primary intermediate pulverization was subjected to secondary intermediate pulverization using a rotary mortar made of alumina (manufactured by CHUO KAKOHKI CO., LTD., PREMAX) under the conditions of a gap of 400 ⁇ m and a speed of rotation of 700 rpm, and an intermediate pulverized glass having a volume average particle size of about 400 ⁇ m was obtained.
- This intermediate pulverized glass was observed with an electron microscope, and as a result, it was confirmed that at least 50% by weight or more was polyhedrons having corners or faces.
- alumina spheres having a diameter of 10 mm as media 20 kg of the intermediate pulverized glass that had been subjected to secondary intermediate pulverization, 14 kg of isopropanol, and 0.2 kg of silane coupling agent A-1230 (manufactured by NUC Corporation) were respectively accommodated in a vibrating ball mill having an internal capacity of 105 liters (manufactured by CHUO KAKOHKI CO., LTD.), and then a fine pulverization treatment was performed for 7 hours under the conditions of a speed of rotation of 1,000 rpm and a vibration width of 9 mm. Thus, a fine pulverized glass was obtained.
- this fine pulverized glass was observed with an electron microscope, and as a result, it was confirmed that at least 70% by weight or more was polyhedrons having corners or faces.
- the fine pulverized glass obtained in the previous step and isopropanol were subjected to solid-liquid separation using a centrifuge (manufactured by KOKUSAN Co., Ltd.) under the conditions of a speed of rotation of 3,000 rpm and 3 minutes.
- the fine pulverized glass was dried using an oven under the conditions of 105° and 3 hours.
- the fine pulverized glass that had been dried and thereby partially agglomerated was crushed using a gear type crusher (manufactured by CHUO KAKOHKI CO., LTD.), and an antibacterial glass (polyhedral glass) having a volume average particle size of 1.0 ⁇ m was obtained.
- the antibacterial glass in this stage was observed with an electron microscope, and as a result, it was confirmed that at least 90% by weight or more was polyhedrons having corners or faces.
- a polyethylene terephthalate resin having a number average molecular weight of 34,000 was mixed and dispersed using a bulk molding compound (BMC) injection molding apparatus at a cylinder temperature of 250°C and a speed of screw rotation of 30 rpm, and thus a spinning dope for the core portion was obtained.
- BMC bulk molding compound
- the spinning dope for the core portion was used for the core portion and the spinning dope for the sheath portion was used for the sheath portion at a core-sheath weight ratio of 50/50, and using a core-sheath composite spinneret having 24 circular composite spinning holes having a nozzle diameter of 0.3 mm, antibacterial fibers were discharged through the spinneret at a spinning temperature of 285°C and a winding speed of 3,000 m/min.
- the antibacterial fibers were stretched to three times by stretching while heating the antibacterial fibers to 90°C by passing the fibers through a tubular heating apparatus, and thereby antibacterial fibers having an average diameter of 40 ⁇ m were obtained. Furthermore, the average diameter of the core portion was 30 ⁇ m.
- the antibacterial fibers thus obtained were observed using a scouldning electron microscope (manufactured by JEOL Ltd., JSM-6610LA), and it was confirmed that the antibacterial glass was dispersed as white spots, only in the sheath portion of the antibacterial fibers. Furthermore, black spots are air bubbles. The results are shown in Fig. 3 .
- the presence or absence of metal ions could also be determined by scouldning electron microscopic images and elemental mapping. That is, EDX measurement was performed (manufactured by JEOL Ltd., JED-2300), and the distribution state of constituent elements was qualitatively analyzed by a mapping analysis. The results are shown in Figs. 4(a) to 4(c) .
- Figs. 4(a) to 4(c) show EDX mapping images obtained using characteristic X-radiation of the K-line of elemental P (phosphorus) ( Fig. 4(a) ), the K-line of elemental C (carbon) ( Fig. 4(b) ), and the K-line of elemental 0 (oxygen) ( Fig. 4(c) ).
- the tensile strength was measured according to JIS L 1015, and the tensile strength was evaluated according to the following criteria.
- the initial weighting at the time of measuring the tensile strength was set to 5.88 mN/1 tex, the tensile rate to 20 mm/min, and the length of the specimen between grips to 10 mm.
- the results thus obtained are presented in Table 1.
- the antibacterial fibers as specimens were brought into uniform contact with 0.5 ml of a suspension of Staphylococcus aureus (IFO#12732) and 0.5 ml of a suspension of Escherichia coli (ATCC#8739), respectively.
- a polyethylene film (sterilization) was mounted thereon, and each of the samples was used as a measurement sample for a film covering method.
- Example 2 antibacterial fibers were produced in the same manner as in Example 1, except that the amount of the antibacterial glass in the sheath portion was changed to 10 parts by weight, and the thermoplastic resin was changed to 100 parts by weight of a polypropylene resin having a number average molecular weight of 60,000, and evaluation of the fibers and evaluation of antibacterial properties were carried out in the same manner as in Example 1. The results thus obtained are presented in Table 1.
- Example 2 the antibacterial fibers obtained in Example 2 were observed with a scouldning electron microscope, and similarly to Example 1, antibacterial glass dispersed only in the sheath portion of the antibacterial fibers could be recognized.
- the results are presented in Fig. 1 .
- EDX measurement was performed by a method similar to that of Example 1, and the distribution state of constituent elements was qualitatively analyzed by a mapping analysis. The results are shown in Figs. 5(a) to 5(c) .
- Figs. 5(a) to 5(c) represent EDX mapping images obtained using characteristic X-radiation of the K-line of elemental P (phosphorus) ( Fig. 5(a) ), the K-line of elemental C (carbon) ( Fig. 5(b) ), and the K-line of elemental 0 (oxygen) ( Fig. 5(c) ).
- the antibacterial glass is not distributed in the entirety of the antibacterial fibers, but a plurality of regions in which the antibacterial glass is locally distributed at high concentrations exist in the sheath portion. Furthermore, from Fig. 5(b) , the sheath portion is brighter, and it could be seen that elemental C is distributed more therein. Furthermore, from Fig. 5(c) , the core portion is brighter; however, this is because of elemental 0 of polyethylene terephthalate or polybutylene terephthalate contained in the core portion.
- Example 3 antibacterial fibers were produced in the same manner as in Example 1, except that the spinning dope for the sheath portion was formed from 3 parts by weight of the antibacterial glass, 95 parts by weight of a polyethylene terephthalate resin having a number average molecular weight of 34,000, and 5 parts by weight of a polybutylene terephthalate resin having a number average molecular weight of 26,000, and evaluation of fibers and evaluation of the antibacterial properties were carried out in the same manner as in Example 1. The results thus obtained are presented in Table 1.
- Example 3 the antibacterial fibers obtained in Example 3 were observed with a scouldning electron microscope, and similarly to Example 1, antibacterial glass dispersed only in the sheath portion of the antibacterial fibers could be confirmed.
- Example 4 antibacterial fibers were produced in the same manner as in Example 1, except that the spinning dope for the core portion was formed from 0.5 parts by weight of the antibacterial glass, 95 parts by weight of a polyethylene terephthalate resin having a number average molecular weight of 34,000, and 5 parts by weight of a polybutylene terephthalate resin having a number average molecular weight of 26,000, and evaluation of fibers and evaluation of the antibacterial properties were carried out in the same manner as in Example 1. The results thus obtained are presented in Table 1.
- Example 4 the antibacterial fibers obtained in Example 4 were observed with a scouldning electron microscope, and it was confirmed that antibacterial glass was distributed more in the sheath portion of the antibacterial fibers.
- the invention is expected to contribute noticeably to product quality improvement of antibacterial articles, particularly woven fabrics and nonwoven fabrics, which are molded using antibacterial fibers.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Glass Compositions (AREA)
- Multicomponent Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
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JP2018227219 | 2018-12-04 | ||
PCT/JP2019/021950 WO2020115928A1 (fr) | 2018-12-04 | 2019-06-03 | Fibre antibactérienne, et procédé de fabrication de fibre antibactérienne |
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EP3683341A4 EP3683341A4 (fr) | 2020-07-22 |
EP3683341A1 true EP3683341A1 (fr) | 2020-07-22 |
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US (1) | US20210332502A1 (fr) |
EP (1) | EP3683341A1 (fr) |
JP (1) | JP6707725B1 (fr) |
KR (1) | KR102243796B1 (fr) |
CN (1) | CN111542654A (fr) |
TW (1) | TWI708750B (fr) |
WO (1) | WO2020115928A1 (fr) |
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CN113800772A (zh) * | 2021-07-31 | 2021-12-17 | 广东金发科技有限公司 | 一种长效抗菌玻璃纤维、尼龙模塑组合物及其制备方法和应用 |
JP7030370B1 (ja) * | 2021-08-26 | 2022-03-07 | 株式会社 維研 | 接触冷感機能を有する繊維製品 |
CN114687006B (zh) * | 2022-04-12 | 2023-02-14 | 雅香丽化妆用品(深圳)有限公司 | 一种速干纤丝及其制备方法和牙刷 |
CN115262019B (zh) * | 2022-07-05 | 2023-07-18 | 新凤鸣集团股份有限公司 | 一种抗菌抗黄变ZnO无锑聚酯纤维的制造方法 |
KR102647770B1 (ko) * | 2023-03-20 | 2024-03-14 | 주식회사 케어마일 | 내구성과 유연성을 향상시킨 그래핀 함유 인조모발 및 그 제조방법 |
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EP0448840A3 (en) * | 1990-02-26 | 1993-03-10 | American Cyanamid Company | Bicomponent or blended wound closure device |
JP3435485B2 (ja) * | 1995-07-17 | 2003-08-11 | ダイニック株式会社 | 空調用抗菌フィルタ材 |
JPH11124729A (ja) * | 1997-10-23 | 1999-05-11 | Kuraray Co Ltd | 抗菌性繊維及びその製造方法 |
JPH11158728A (ja) * | 1997-11-25 | 1999-06-15 | Unitika Ltd | 抗菌性を有する吸放湿性複合繊維 |
JPH11158730A (ja) | 1997-11-26 | 1999-06-15 | Nippon Ester Co Ltd | 抗菌性ポリエステル繊維 |
US6037057A (en) * | 1998-02-13 | 2000-03-14 | E. I. Du Pont De Nemours And Company | Sheath-core polyester fiber including an antimicrobial agent |
JP2001247333A (ja) | 1999-12-28 | 2001-09-11 | Ishizuka Glass Co Ltd | 抗菌性付与用ガラス組成物、抗菌性繊維、抗菌性撚糸及び抗菌性布状物 |
AU2003221115A1 (en) * | 2002-04-05 | 2003-10-20 | Kanebo Chemical Industries, Ltd. | Antibacterial glass composition, antibacterial resin composition and process for producing the same |
JP2004190197A (ja) * | 2002-12-13 | 2004-07-08 | Teijin Fibers Ltd | 制菌性繊維及び制菌性繊維製品 |
WO2006120772A1 (fr) * | 2005-05-10 | 2006-11-16 | Koa Glass Co., Ltd | Fibre antimicrobienne et procede de production correspondant |
JP4723558B2 (ja) | 2005-05-10 | 2011-07-13 | 興亜硝子株式会社 | 抗菌性繊維 |
US20070269643A1 (en) * | 2006-05-16 | 2007-11-22 | James Calvin Bennett | Antimicrobial pool filter |
EP2318207A4 (fr) * | 2008-08-28 | 2012-08-15 | Tyco Healthcare | Fibres antimicrobiennes et articles et procédés correspondants |
EP2530120B1 (fr) * | 2011-01-17 | 2014-03-19 | Koa Glass Co., Ltd. | Composition de résine antibactérienne dérivée d'un mélange-mère, fibre antibactérienne, film antibactérien, et procédé de production d'une composition de résine antibactérienne dérivée d'un mélange-mère |
US20150361595A1 (en) * | 2014-06-11 | 2015-12-17 | Noble Fiber Technologies, Llc | Antimicrobial Multicomponent Synthetic Fiber and Method of Making Same |
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2019
- 2019-06-03 JP JP2020504742A patent/JP6707725B1/ja active Active
- 2019-06-03 CN CN201980002401.1A patent/CN111542654A/zh active Pending
- 2019-06-03 KR KR1020197032995A patent/KR102243796B1/ko active IP Right Grant
- 2019-06-03 EP EP19798520.3A patent/EP3683341A1/fr not_active Withdrawn
- 2019-06-03 WO PCT/JP2019/021950 patent/WO2020115928A1/fr unknown
- 2019-06-03 US US16/613,854 patent/US20210332502A1/en not_active Abandoned
- 2019-11-14 TW TW108141410A patent/TWI708750B/zh active
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WO2020115928A1 (fr) | 2020-06-11 |
TWI708750B (zh) | 2020-11-01 |
JPWO2020115928A1 (ja) | 2021-02-15 |
TW202021924A (zh) | 2020-06-16 |
US20210332502A1 (en) | 2021-10-28 |
CN111542654A (zh) | 2020-08-14 |
KR20200070157A (ko) | 2020-06-17 |
EP3683341A4 (fr) | 2020-07-22 |
KR102243796B1 (ko) | 2021-04-23 |
JP6707725B1 (ja) | 2020-06-10 |
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