JPH11116822A - Antimicrobial nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject nonwoven fabric, excellent in antimicrobial properties, having high heat resistance capable of resisting cooked process, and stability against water and oil by adding a specific acidic organic phosphoric acid ester compound to a high molecular material constituting the nonwoven fabric. SOLUTION: The objective nonwoven fabric is obtained by adding (B) 0.001-10 pts.wt., preferably 0.005-5 pts.wt. cyclic organic phosphoric acid ester compound of formula I [R<1> to R<3> are each H, a 1-18C linear or branched alkyl; R<4> is H or methyl; (n) is 1 or 2, and when (n) is 1, M is H or an alkali metal, and when (n) is 2, M is an alkaline earth metal, Zn or Cu], (for example; a compound of formula II) to (A) 100 pts.wt. high molecular material composing the nonwoven fabric. A polyolefin-based resin, a polyester-based resin, a polyamide-based resin, etc., are preferably used as the component A. A well- known inorganic and/or organic antifungal and antibacterial agent can be used together with the above components in the nonwoven fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial nonwoven fabric obtained by adding a specific acidic organic phosphoric acid ester or a metal salt thereof to a polymer material, and a product using the same.

[0002]

2. Description of the Related Art A kitchen,
In a humid place such as a bathroom or a wash basin, or in a place where humidity is easily increased such as a futon or a bed, bacteria and fungi easily propagate and become unsanitary. In particular, in recent years, houses have high airtightness and air-conditioning has become widespread, which makes the environment suitable for bacteria and fungi, and enables the growth of microorganisms throughout the year. For this reason, microorganisms propagate not only in ordinary humid places but also in living rooms, contaminating wallpaper, fusuma paper, etc., as well as in terms of hygiene such as causing atopic dermatosis and other allergic symptoms. It is a problem.

In particular, in recent years, there has been an increasing demand for hygiene, such as beddings such as futons, pillows and sheets, interior goods such as carpets, curtains and wallpapers, and medical hygiene goods such as masks, gauze, bandages, white coats and diapers. Also, building materials such as flooring materials and sound insulation materials, and air conditioning equipment such as air conditioner filters, which have antibacterial properties, are preferred.

[0004] In medical facilities such as hospitals, wall materials, floor materials, ceiling materials, and air conditioning are used to prevent the propagation of dangerous pathogenic bacteria and the like, and to obtain a safe and sanitary environment for sick persons with reduced immunity. The demand for materials having antibacterial properties as materials for equipment and the like has become higher.

At present, in the above products, antibacterial properties are imparted to each product by kneading an antibacterial agent or the like in a nonwoven fabric as a material.

In order to impart antibacterial properties to nonwoven fabrics, it has been proposed to include inorganic and organic antibacterial agents,
For example, JP-A-5-57002 and JP-A-5-15
No. 3874, JP-A-8-325915,
It is proposed to use an inorganic antibacterial agent using a metal having antibacterial properties such as silver, and to use an organic antibacterial agent in, for example, JP-A-5-186945 and JP-A-8-511520. Have been.

It has long been known that a specific metal such as silver has an antibacterial action as an inorganic antibacterial agent, and it is also known that the antibacterial action of these metals is derived from a trace amount of ions dissolved from the metal surface. Have been. As antibacterial agents using these metals, inorganic antibacterial agents in which various inorganic compounds such as zeolite, silica gel, hydroxyapatite and the like are denatured with the above metals, or the above metal salts of various organic acids are known. However, the antibacterial action of these metal-based antibacterial agents is not yet satisfactory, and the use of silver has a disadvantage that the discoloration due to light is remarkable, so that its use is limited.

[0008] Organic compounds containing phenol, halogen and sulfur are known as organic antibacterial agents. However, although these organic compounds have excellent antibacterial properties, they are often harmful to the human body, and have poor heat resistance and stability compared to inorganic antibacterial agents. Not only does it decompose when it comes into contact with water or oil during use or during use, it loses its efficacy by escaping from the product, but also has undesired effects such as generation of odor and deterioration of physical properties of polymer materials. Therefore, the use has been limited.

Therefore, the antibacterial agent has a high heat resistance and a stability against moisture or oil which can withstand the heat processing in the production of the nonwoven fabric, has no coloring which impairs the value of the product, and is highly safe for the human body. It has been strongly desired to find an antibacterial nonwoven fabric to which such an antibacterial agent is added.

JP-A-58-1736 describes that an aromatic cyclic phosphate metal salt is used as a nucleating agent for a crystalline resin, but these compounds are effective as antibacterial agents. It is not even suggested.

Accordingly, an object of the present invention is to provide a nonwoven fabric having excellent antibacterial properties, which can be used to form an antibacterial molded article.

[0012]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific acidic organic phosphoric acid ester or a metal salt thereof exhibits excellent antibacterial properties, and that it can be used for heat treatment of a polymer material. It has been found that it has high heat resistance and stability against moisture or oil content, has no coloration that impairs the value of the product, and has high safety to the human body. The present inventors have further studied based on this finding, and as a result, it has been found that the above-mentioned object can be achieved by adding the above specific acidic organic phosphate compound to a polymer material constituting a nonwoven fabric. Was found.

The present invention has been made based on the above findings, and 100 parts by weight of a polymer material is represented by the following general formula (I). An antibacterial nonwoven fabric comprising a polymer material composition to which 0.001 to 10 parts by weight of a phosphoric acid ester compound is added is provided.

[0014]

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[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the antibacterial nonwoven fabric of the present invention will be described in detail.

First, the polymer material composition constituting the antibacterial nonwoven fabric of the present invention will be described in detail. In the cyclic organic phosphate compound represented by the general formula (I) used in the polymer material composition, the alkyl groups represented by R ¹ , R ² and R ³ include methyl, ethyl and propyl ,
Isopropyl, butyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, octyl, 2-ethylhexyl, isooctyl, tert-octyl, nonyl, decyl,
Dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and the like.

The alkali metal represented by M includes sodium, potassium, lithium and the like, and the alkaline earth metal includes calcium, magnesium, barium and strontium. In particular, M is an alkali metal atom or What is a zinc atom has a large effect, and is preferable.

Accordingly, specific examples of the above-mentioned cyclic organic phosphate compound include compound No. 1 shown in the following [Chemical Formula 3] to [Chemical Formula 10]. 1 to No. 8 and the like.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The cyclic organic phosphate compound is added in an amount of 0.001 to 1 based on 100 parts by weight of the polymer material.
0 parts by weight, preferably 0.005 to 5 parts by weight. If the amount is less than 0.001 part by weight, a sufficient antibacterial effect cannot be obtained. If the amount exceeds 10 parts by weight, the effect is not so much improved and it is economically disadvantageous.

The above-mentioned cyclic organophosphate compound used in the present invention not only has excellent stability but also has good dispersibility in a polymer material, and thus can be directly blended with the polymer material. Can be used by being supported on various carriers or dispersed in a solvent or a liquid additive.

The polymer material used in the polymer material composition constituting the antibacterial nonwoven fabric of the present invention can be arbitrarily selected as long as it can be foamed or spun so as to satisfy applications and required characteristics. For example, α-olefin polymers such as high-density, low-density or linear low-density polyethylene, polypropylene, polybutene-1, poly-3-methylpentene, etc., ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, etc. Polyolefins and their copolymers, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chloride rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, chloride Vinyl-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-cyclohexylmaleimide copolymer ,
Halogen-containing resin such as vinyl chloride-cyclohexylmaleimide copolymer, petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, Copolymers with phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc. (for example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral,
Thermoplastic synthesis of linear polyesters such as polyethylene terephthalate and polytetramethylene terephthalate, polyamides such as polyphenylene oxide, polyphenylene sulfide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, branched polycarbonate, polyacetal, polyurethane, and cellulose resin. Resins and blends thereof, and thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins can be given. Among the polymer materials, polyolefin-based resins,
Desirable are polyester resins and polyamide resins.

The effect of the polymer material composition constituting the antibacterial nonwoven fabric of the present invention is enhanced by using a known inorganic and / or organic antibacterial agent and fungicide in combination. And / or the antimicrobial spectrum can be broader.

Examples of the above-mentioned inorganic antibacterial agents and fungicides include metals such as silver, copper and zinc which can impart antibacterial and / or antifungal properties, or oxides, hydroxides and phosphoric acids thereof. Salts, thiosulfate salts, silicates and inorganic compounds supporting these are mentioned. More specifically, silver or copper zeolites, silver zirconium phosphate, silver hydroxyapatite, silver phosphate glass, silver phosphate Phosphate ceramics, silver calcium phosphate, zinc oxide, zinc hydroxide,
Examples include calcium oxide and calcium hydroxide. Among the inorganic antibacterial agents and fungicides, oxides or hydroxides of alkaline earth metals or zinc are preferable.

Examples of the alkaline earth metal or zinc oxide or hydroxide include calcium, magnesium, barium, strontium and zinc oxides and hydroxides, and particularly calcium hydroxide, zinc oxide and the like. And zinc hydroxide are preferred because of their large effect.

The amount of the alkaline earth metal or zinc oxide or hydroxide to be added is not particularly limited, but is usually 0.1 to 100 parts by weight of the polymer material to be added.
001 to 10 parts by weight are preferable, and 0.005 to 5 parts by weight is more preferable. If the amount is less than 0.001 part by weight, a sufficient antibacterial effect cannot be obtained, and if it exceeds 10 parts by weight, the effect is not so much improved, and the properties of the polymer material may be adversely affected. Further, other additives are also added within the above-mentioned range.

The alkaline earth metal or zinc oxide or hydroxide is preferably used in powder form from the viewpoint of dispersibility in a polymer material, and the particle size is not particularly limited. It is preferable to use those having an average particle size of 0.1 to 100 μm so as not to deteriorate the physical properties of the polymer material. Further, the powder can be directly blended with the polymer material, but if necessary, can be dispersed in a solvent or a liquid additive or used as a paste.

The above-mentioned organic antibacterial agents and fungicides include organic nitrogen-sulfur antibacterial agents, organic bromide antibacterial agents, organic nitrogen-based antibacterial agents, and other antibacterial agents. As an organic nitrogen sulfur-based antibacterial agent, an alkylenebisthiocyanate compound such as methylenebisthiocyanate,
5-chloro-2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one,
Isothiazoline compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, chloramine T,
Sulfonamide compounds such as N, N-dimethyl-N ′-(fluorodichloromethylthio) -N′-phenylsulfamide, thiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole 2-mercaptobenzothiazole, 2-pyridinethiol-1-oxide and its metal salt, 2- (4-thiazolyl) benzimidazole, 3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazine-2-thione, N- (fluoro Dichloromethylthio) phthalimide, dithio-2,2′-bis (benzmethylamide) and the like, and examples of the organic bromide antibacterial agent include 2-bromo-2-nitropropane-1,
3-diol, 1,1-dibromo-1-nitro-2-propanol, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-diacetoxypropane, β-bromo-β -Nitrostyrene 5-bromo-
Organic bromonitro compounds such as 5-nitro-1,3-dioxane, organic bromocyano compounds such as 2,2-dibromo-3-cyanopropionamide, 1,2-bis (bromoacetoxy) ethane, 1,4-bis (bromo Bromoacetic acid compounds such as acetoxy) -2-butene and bromoacetamide; organic bromosulfone compounds such as bistribromomethylsulfone; and organic nitrogen-based antibacterial agents include hexahydro-1,3,5-triethenyl-s-. S-Triazine compounds such as triazine, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, N, 4-dihydroxy-α-oxobenzeneethanimidoyl chloride, α-chloro-O-acetoxy Halogenated oxime compounds such as benzaldoxime,
Chlorinated isocyanuric acid compounds such as trichloroisocyanurate and sodium dichloroiisocyanurate; quaternary ammonium compounds such as benzalkonium chloride and decalinium chloride; carbamic acid compounds such as 2-methylcarbonylaminobenzimidazole; 1- [2- (2,4
-Dichlorophenyl)]-2 ′-[(2,4-dichlorophenyl) methoxy] ethyl-3- (2-phenylethyl) -1H-imidazolium chloride and other imidazole compounds; 2-chloroacetamide and other amide compounds;
N- (2-hydroxypropyl) aminomethanol, 2
Amino alcohol compounds such as-(hydroxymethylamino) ethanol; and nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile. Other antibacterial agents include methyl 4-hydroxybenzoate and ethyl benzoate. Propyl benzoate, isopropyl benzoate and the like.

The above-mentioned polymer material composition constituting the antibacterial nonwoven fabric of the present invention may be added, if necessary, together with the cyclic organic phosphate compound represented by the above general formula (I), if necessary. Can be added.

Examples of the additives include phenol-based, phosphorus-based, sulfur-based antioxidants, metal soap-based stabilizers, metal alkyl phosphate-based stabilizers, inorganic metal salt-based stabilizers, and perchloric acid-based stabilizers. Acid salt compound, organotin stabilizer, polyol compound, β-diketone compound, epoxy compound, plasticizer,
Foaming agent, ultraviolet absorber, hindered amine light stabilizer,
Fillers, colorants, pigments, crosslinking agents, antistatic agents, antifoggants,
Lubricants, processing aids, flame retardants and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis (3-tert-butyl-
4-hydroxy-5-methylphenyl) propionate, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane-bis (3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionate, 4,
4'-thiobis (6-tert-butyl-m-cresol),
4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-methylenebis (6-tert-butyl-
p-cresol), 2-tert-butyl-4-methyl-6-
(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4) -Hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate,
3,5-tris (2,6-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, pentaerythritol-tetra (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate and the like.

As the above-mentioned phosphorus antioxidants, for example,
Triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (mono, di-mixed nonylphenyl) phosphite, diphenylacid phosphite, diphenyldecyl phosphite, Phenyldidecyl phosphite, tridecyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-
Tri (tert-butylphenyl) pentaerythritol diphosphite, tetra (C _12-15 mixed alkyl) bisphenol A-diphosphite, tetra (tridecyl) -4,
4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)-
1,1,3-tris (2-tert-butyl-5-methylphenol) triphosphite, 2-butyl-2-ethylpropylene-2,4,6-tritert-butylphenylphosphite, 9,10- And dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Examples of the sulfur-based antioxidants include:
Examples thereof include dialkylthiodipropionates such as dilauryl, dimyristyl and distearyl esters of thiodipropionic acid, and polyol esters of β-alkylmercaptopropionic acid such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the metal soap-based stabilizer include Group Ia metals such as sodium, potassium and lithium;
Regular salts, acidic salts, basic salts, and overbased salts of aliphatic or aromatic carboxylic acids of Group IIa metals such as calcium, magnesium, barium and strontium or Group IIb metals such as zinc, etc. Group Metal Stone Ken / IIb
Used as a combination of group metal soaps.

Examples of the aliphatic or aromatic carboxylic acids constituting the metal soap stabilizer include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid and lauric acid. , Myristic acid, palmitic acid, stearic acid,
Isostearic acid, 12-hydroxystearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid,
Arachinic acid, behenic acid, brassic acid and tallow fatty acid, coconut oil fatty acid, soybean oil fatty acid, fatty acid mixture obtained from natural oils such as cottonseed oil fatty acid, benzoic acid, toluic acid, ethylbenzoic acid, p-tert-butylbenzoic acid, Xylyl acid and the like.

Examples of the metal alkyl phosphate stabilizers include mono- and / or mono- and / or mono-group metals such as group Ia metals such as sodium and potassium, group IIa metals such as calcium, magnesium, barium and strontium, and group IIb metals such as zinc.
Or dioctyl phosphate, mono and / or dilauryl phosphate, mono and / or distearyl phosphate.

Examples of the above-mentioned inorganic metal salt-based stabilizer include Group Ia metals such as sodium and potassium, and IIa metals such as calcium, magnesium, barium and strontium.
Oxides or hydroxides of Group IIb metals or Group IIb metals such as zinc; basic inorganic acids (carbonic acid, phosphoric acid, phosphorous acid, silicic acid, boric acid, sulfuric acid, etc.); aluminosilicates of the above metals having a zeolite crystal structure And the like: Hydrotalcite-like compounds represented by the following formulas and the like.

Li _x1 Mg _x2 Zn _x3 Al _y (OH) _{x1 + 2 (x2 + x3) + 3y-2}
(CO ₃ ) _{1-z / 2} (ClO ₄ ) _z · mH ₂ O (where x1, x2, x3, y and z each represent a number represented by the following formula, and m is 0 or any 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 10, 0 ≦ x3 ≦ 10, 1
≦ y ≦ 10, 0 ≦ z ≦ 1, 0 <x1 + x2)

As the above perchlorate compound, for example,
Sodium, potassium, calcium, magnesium,
Metals such as barium, strontium and zinc, or perchlorates such as ammonia and organic amines, and those obtained by adsorbing perchloric acid to an inorganic porous substance can be used.

Examples of the organotin-based stabilizer include mono- and / or dimethyl tin, carboxylate of mono- and / or dialkyltin such as mono- and / or dibutyltin, mono- and / or dioctyltin, mercaptides, and the like. And sulfides.

As the polyol compound, for example,
Glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, tris (2-
(Hydroxyethyl) isocyanurate and partial ester compounds of these aliphatic or aromatic monovalent or polyvalent carboxylic acids.

Examples of the β-diketone compound include benzoylacetone, benzoylpivaloylmethane, benzoylpalmitoylmethane, benzoylstearoylmethane, dibenzoylmethane, ditert-butyldibenzoylmethane, benzoylcyclohexanone, and zinc, Metal complex salts such as calcium and magnesium can be mentioned.

Examples of the epoxy compound include polyglycidyl ethers of polyhydric phenols such as bisphenol A-diglycidyl ether and novolak polyglycidyl ether; vinylcyclohexene dioxide;
Alicyclic epoxy compounds such as 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate; epoxidized natural oils such as epoxidized soybean oil and epoxidized linseed oil; alkyl esters of epoxidized unsaturated carboxylic acids; can give.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didecyl phthalate, trioctyl trimellitate, tetraoctyl pyromellitate, tetraoctyl biphenyl tetracarboxylate, dioctyl adipate, diisononyl adipate, dioctyl sebacate, Dioctyl azelate,
Alkyl esters of aliphatic or aromatic polycarboxylic acids such as trioctyl citrate: Phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylyl phosphate; aliphatic or aromatic polycarboxylic acids and glycols Polyester obtained by condensation and, if necessary, the terminal is blocked with a monohydric alcohol and / or a monocarboxylic acid; chlorinated paraffin.

Examples of the foaming agent include azo foaming agents such as azodicarboxylic amide, azobisisobutyronitrile, diazodiaminobenzene, diethylazodicarboxylate; and nitroso foaming agents such as dinitrosopentamethylenetetramine. Benzenesulfonyl hydrazide;
hydrazide-based foaming agents such as p-toluenesulfonylhydrazide, toluenesulfonylazide, and bis (benzenesulfonylhydrazide) ether; semicarbazide-based foaming agents such as toluenesulfonylsemicarbazide; and triazine-based foaming agents such as trihydrazinotriazine.

As the above-mentioned ultraviolet absorber, for example, 2-
(2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3
-Tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole,
2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-
Benzotriazole ultraviolet absorbers such as octyl alcohol or polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-octoxybenzophenone, 5,
Benzophenone-based ultraviolet absorbers such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2
And triazine-based ultraviolet absorbers such as-(2-hydroxy-4-hexyloxy) -4,6-diphenyltriazine and 2- (2-hydroxy-4-octoxy) -4,6-dixylyltriazine.

Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4).
-Piperidinyl) sebacate, bis (1,2,2,6,
6-pentamethyl-4-piperidinyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) Butanetetracarboxylate, bis (2,2,
6,6-tetramethyl-4-piperidinyl) ditridecylbutanetetracarboxylate, bis (1,2,2
2,6,6-pentamethyl-4-piperidinyl) ditridecylbutanetetracarboxylate, butanetetracarboxylic acid and 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10 -Tetraoxaspiro [5.5] undecane and 2,2,6,6-tetramethyl-4-piperidinol or 1,2,2,6,6-
Polycondensate with pentamethyl-4-piperidinol, 1-
Polycondensate of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and diethyl succinate, 1,6-bis (2,2,6,6-tetramethyl-4
Polycondensation product of -piperidinylamino) hexane and dibromoethane, 1,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) hexane and 2,4-dichloro-6- Polycondensate with tertiary octylaminotriazine, 1,6-bis (2,2,6,6-tetramethyl-4
-Piperidinylamino) hexane and 2,4-dichloro-
Polycondensates with 6-morpholinotriazine, 1,5,8,
12-tetrakis [2,4-bis (N-butyl-N-
(2,2,6,6-tetramethyl-4-piperidinyl)
Amino) -s-triazin-6-yl] -1,5,8,
12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidinyl) amino)-
[s-triazin-6-yl] -1,5,8,12-tetraazadodecane and the like.

The antibacterial nonwoven fabric of the present invention can be produced, for example, by the following method. The method for producing the antibacterial nonwoven fabric of the present invention is not limited to these. After spinning the polymer material composition with a spinning machine, the fiber is drawn. Next, the fibers can be manufactured by subdividing the fibers, randomly accumulating the fibers into a sheet, and further embossing. The polymer material composition can be manufactured by forming a filament into a filament, heat-sealing the filament, and calendering the filament.

The antibacterial nonwoven fabric of the present invention can be prepared by any known processing method such as a wet method, an air lay method, a card method, a spun bond method, a melt blown method, a binder bonding method, a needle punch method, a spun lace method, and a stitch bond method. Films, sheets, and other antibacterial molded products are formed by combining any known adhesive methods such as the thermal bonding method or the thermal bonding method, and bedding such as futons, pillows, sheets, and interior goods such as carpets, curtains, and wallpapers. It is used for medical hygiene articles such as masks, gauze, bandages, white coats, diapers, etc., building materials such as flooring materials and sound insulation materials, and air conditioning equipment such as air conditioner filters.

[0057]

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

Example 1 The following formulation was kneaded at 180 ° C. with an extruder to give a particle size of about 4
A pellet having a diameter of 1 mm was prepared, and the pellet and the polyester resin were mixed at a ratio of 1: 2, and then spun and drawn by a spinning machine to prepare a polyester fiber having a thickness of 6 denier.
The fibers were subdivided, randomly accumulated, formed into a sheet, and then subjected to hot embossing to prepare a nonwoven fabric. This polyester nonwoven fabric was cut into a size of 20 × 20 mm to obtain a test piece. Using this test piece, the antibacterial property of bacteria and fungi was evaluated by the following method. Bacteria: A bacterial culture solution was applied on a test piece, a polyethylene wrap film was adhered thereto, and the number of bacteria after culturing at 35 ° C. for 2 days was measured and evaluated according to the following criteria. ◎: Only less than 0.1% of the number of bacteria before the test survived. Good: 0.1% or more and less than 1% of the number of bacteria before the test are alive. B: 1% or more and less than 10% of the number of bacteria before the test are alive. X: 10% or more of the number of bacteria before the test is alive. Fungi: Place a test piece in the center of a Petri dish, pour a normal agar medium so that the test piece is covered thinly, apply a culture solution of the fungus on the agar medium, and culture for 1 week at 35 ° C. Was observed, and the results were evaluated according to the following criteria. ◎: No growth of bacteria on the upper part of the test piece. ：: Bacteria growing on the upper part of the test piece had less than 30% of the surface area △: Bacteria growing on the upper part of the test piece had 30% or more of the surface area 7
Less than 0% ×: Bacteria growing on the upper part of the test piece is 70% or more of the surface area.

[Blending] Parts by weight Polyester resin 98 Zinc oxide 1 Test compound (see [Table 1] below) 1

[0060]

[Table 1]

Example 2 The following components were kneaded at 220 ° C. in an extruder, and filaments were extruded from a spinneret. After the filaments were thermally fused on a running belt, they were calendered to form a nonwoven fabric. This polypropylene nonwoven fabric is 20 × 20
The test piece was cut into mm. The same test as in Example 1 was performed using this test piece.

[Blending] parts by weight Polypropylene resin 100 Phenol antioxidant (ADK STAB AO-60) 0.1 Phosphite antioxidant (ADK STAB 2112) 0.1 Silver zirconium phosphate 0.5 Test compound (see below [ (See Table 2)) 0.5

[0063]

[Table 2]

Example 3 The following components were kneaded at 220 ° C. in an extruder, and filaments were extruded from a spinneret. After the filaments were thermally fused on a running belt, they were calendered to form a nonwoven fabric. This polypropylene nonwoven fabric is 20 × 20
The test piece was cut into mm. The same test as in Example 1 was performed using this test piece.

[Blending] Parts by weight High density polyethylene resin 100 Phenolic antioxidant (ADK STAB AO-60) 0.1 Phosphite antioxidant (ADK STAB 2112) 0.1 Isopropyl 4-hydroxybenzoate 0.5 Test Compound (see [Table 3] below) 0.5

[0066]

[Table 3]

Example 4 The following compound was kneaded at 240 ° C. in an extruder, and a filament was extruded from a spinneret. After the filaments were thermally fused on a running belt, they were calendered to form a nonwoven fabric. This polypropylene nonwoven fabric is 20 × 20
The test piece was cut into mm. The same test as in Example 1 was performed using this test piece.

[Blending] parts by weight Nylon 6 100 Phenolic antioxidant (ADK STAB AO-60) 0.5 Phosphite antioxidant (ADK STAB 2112) 0.25 Zinc oxide 0.25 Test compound (see Table 4 below) ] 1.0)

[0069]

[Table 4]

Example 5 The following components were kneaded at 220 ° C. in an extruder, and filaments were extruded from a spinneret. After the filaments were thermally fused on a running belt, they were calendered to form a nonwoven fabric. This polypropylene nonwoven fabric is 20 × 20
The test piece was cut into mm. The same test as in Example 1 was performed using this test piece.

[Blending] parts by weight Polypropylene 100 Phenolic antioxidant (ADK STAB AO-60) 0.1 Phosphite antioxidant (ADK STAB 2112) 0.1 Compound No. 2 0.5 Test compound 5]) 0.5

[0072]

[Table 5]

As shown in the above tables, when conventional antibacterial agents such as zinc oxide, silver zirconium phosphate or isopropyl 4-hydroxybenzoate were blended alone (Comparative Examples 1-2, 2-2, 3-2, 4-2) have insufficient antibacterial properties, and are mixed in large amounts (Comparative Examples 2-3, 3--2).
No satisfactory effect can be obtained in (3, 4-3). On the other hand, when the cyclic organic phosphate compound represented by the general formula (I) according to the present invention and the above-mentioned conventional antibacterial agent are used in combination with each other in a polymer material (each embodiment), It is evident that even with a small amount of addition, it shows excellent antibacterial properties, and its antibacterial spectrum is extremely broad.

[0074]

The antibacterial nonwoven fabric of the present invention has excellent antibacterial properties and can be used to form an antibacterial molded article.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI D04H 3/00 D04H 3/00 Z // D01F 6/92 301 D01F 6/92 301K

Claims (5)

[Claims] 1. A polymer composition comprising 100 parts by weight of a polymer material and 0.001 to 10 parts by weight of a cyclic organic phosphate compound represented by the following general formula (I): Antibacterial non-woven fabric. Embedded image 2. The antibacterial nonwoven fabric according to claim 1, wherein in the general formula (I), M is an alkali metal atom or a zinc atom. 3. The antibacterial nonwoven fabric according to claim 1, wherein the polymer material is a polyolefin resin. 4. The antibacterial nonwoven fabric according to claim 1, wherein the polymer material is a polyester resin. 5. The polymer material composition according to claim 1, further comprising zinc oxide or hydroxide.
5. The antibacterial nonwoven fabric according to any one of items 4 to 4.