JP2010248124A - Antibacterial composition, antibacterial resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial composition and an antibacterial resin composition that exhibit excellent antibacterial properties on various kinds of fungi and bacteria while permitting the suppression of the added amount of an antibacterial agent when used in the manufacture of a molded product (commodity) to reduce the manufacturing cost, are prepared with excellent productivity rate and hardly exert bad influences on the external appearances of the molded product, and to provide a molded product using the antibacterial composition and the antibacterial resin composition having these advantages. <P>SOLUTION: The antibacterial composition includes an organic silver antibacterial agent and an organic antibacterial agent. The antibacterial agent containing a 10-30C fatty acid silver salt as the organic silver antibacterial agent is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antibacterial composition, an antibacterial resin composition, and a molded product.

There are many microorganisms in the human living environment, and due to global warming factors that have been pointed out in recent years, prokaryotes such as bacteria, eukaryotes such as mold and yeast, The environment (especially hot and humid areas) where many moss and algae are easy to reproduce is increasing.
Also, in response to recent energy saving requirements, legal revisions and security needs, changes in the living environment such as indoor sealing due to the spread of aluminum sashes made of double-layered glass, and maintenance of indoor temperature or humidity due to the widespread use of air conditioners As a result, an environment suitable for breeding is given to microorganisms, and it has been suggested that there is an adverse effect on the human body due to the occurrence of bacteria and fungi and an increase in allergic symptoms in recent years.
Therefore, in the electrical / electronic field, OA / home appliance field, automobile field, sanitary field such as toilet seat / kitchen / bathroom area, etc. In many cases, various countermeasures against microorganisms have been taken, and in general, various antibacterial agents are added to the resins used in these fields. It was.

Here, as the organic antibacterial agent blended in the resin, diiodomethyl-p-trisulfone, 2,4,5,6-tetrachloroisophthalonitrile, 2,3,5,6-tetrachloro-4-methylsulfonyl Known are pyridine, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2- (4-thiazolyl) -benzimidazole, and the like.
Examples of inorganic antibacterial agents include inorganic compounds such as cuprous oxide, copper, zinc sulfate, and copper-nickel alloys, those in which metals are supported on inorganic substances such as calcium phosphate and zeolite, and titanium oxide. The thing using a photocatalytic function is mentioned.

  However, many of the conventional antibacterial agents have a slow onset of antibacterial effects including organic antibacterial agents, and there are limits to the types of bacteria that can be handled. Furthermore, some constituents are water-soluble, and in this case, the sustainability of the effect has been a problem.

  On the other hand, in order to solve the problems of such organic antibacterial agents, composite organic antibacterial compositions comprising a plurality of organic antibacterial agents have been studied, for example, nitrile antibacterial agents, pyridine An antibacterial composition containing an antibacterial agent, a haloalkylthio antibacterial agent, an organic iodine antibacterial agent, a thiazole antibacterial agent, or a benzimidazole antibacterial agent as an active ingredient is provided (for example, Patent Document 1).

  Furthermore, an antibacterial composition characterized by containing an organic antibacterial agent and an inorganic antibacterial agent is known. A pyridine antibacterial agent and a benzimidazole antibacterial agent as an organic antibacterial agent, and an inorganic antibacterial agent As an antibacterial agent, an antibacterial composition containing a metal-supported zirconium or a salt thereof or a zeolite (particularly, zirconium phosphate or a salt thereof or a zeolite supporting silver or copper) has been proposed (for example, Patent Document 2). ). As a result, the antibacterial spectrum is broad, the types of fungi that can be handled are dramatically increased, and the antibacterial effect is excellent. In addition, by adding an inorganic antibacterial agent, the initial antibacterial performance and the sustainability of the antibacterial effect will be improved, and since the amount of elution will be reduced, environmental pollution can be suitably suppressed, It is described that the resin moldability is also good because it is suitable for blending.

JP-A-8-92012 JP 2006-52205 A

However, the composite organic antibacterial composition disclosed in Patent Document 1 described above is not yet sufficient, although the types of fungi that can be handled are expanded compared to conventional antibacterial agents.
On the other hand, inorganic antibacterial agents are also known that have a metal such as silver and copper supported on a carrier so as to have an antibacterial effect while suppressing elution. Direct contact with the metal is required. In order to obtain a sufficient antibacterial effect in such a system, it is necessary that the antibacterial agent is densely distributed in the material. However, the inorganic antibacterial structure in which the metal atom is supported on the carrier as described above. Since the agent is a fine particle having a large particle size, it is difficult to distribute the agent precisely in the material, and it is necessary to add a large amount of an inorganic antibacterial agent.

For example, in an antibacterial composition containing an organic antibacterial agent and an inorganic antibacterial agent as disclosed in Patent Document 2 described above, the antibacterial spectrum is wide, and the types of fungi that can be handled are dramatically increased. Although the antibacterial effect is excellent, the inorganic antibacterial agent is a fine powder in the form of the inorganic antibacterial agent used to support metals such as silver and copper exhibiting antibacterial properties on zirconium phosphate and zeolite. The particle size ranges from 0.5 to 3 μm. For this reason, for example, a number of techniques such as adding a dispersant such as metal soap (for example, zinc stearate, magnesium stearate, lithium stearate, etc.) have been studied, but it is not sufficient and exhibits antibacterial properties. When the inorganic antibacterial agent is added to the resin to form a resin composition, the added amount of the inorganic antibacterial agent is required to be about 0.5 to 3.0% by mass with respect to the total amount of the resin composition. As a result, when the resin composition is injection molded, coarse particles and secondary aggregated particles of inorganic antibacterial agent accumulate on the filter of the injection molding machine, and the pressure of the molding machine rises, so the amount of molten resin discharged varies. Or the frequency of replacement of the filter increases, causing a problem that the productivity of the resin molded product is significantly deteriorated.
Moreover, since the inorganic antibacterial agent having a large particle size is added at a high concentration to the obtained resin molded product, the color of the inorganic antibacterial agent main body remains in the molded product or it becomes opaque. Inconvenience often occurs.

  Some metals generate active oxygen, and this active oxygen may exhibit antibacterial activity. However, light energy is required for the generation of active oxygen, or the generated active oxygen is bacteria. Since it is easily erased by organic substances other than those, it was not sufficient as an antibacterial effect.

Therefore, the object of the present invention is to provide an antibacterial agent when used in the production of a molded product (commodity) while having a wide range of antibacterial properties not only at the initial stage but also after the lapse of time against various types of fungi and bacteria. An object of the present invention is to provide an antibacterial composition and an antibacterial resin composition that can reduce the production cost by being able to suppress the addition amount, are excellent in productivity, and are unlikely to adversely affect the appearance of the molded product.
Another object of the present invention is to provide a molded product using the antibacterial composition or the antibacterial resin composition having the above-mentioned advantages.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using the following antibacterial composition.
That is, the present invention is as follows.

[1]
An antibacterial composition containing an organic silver antibacterial agent and an organic antibacterial agent.

According to the antibacterial composition described in [1] above, since it contains an organic silver antibacterial agent and an organic antibacterial agent, the antibacterial spectrum is wide and excellent against many types of fungi and bacteria. Has antibacterial properties. In addition, since organic silver-based antibacterial agents are used in particular, when an antibacterial composition and a resin are used to obtain a molded product by, for example, an injection molding method, the organic silver-based antibacterial agent melts into the resin and becomes organic The silver antibacterial agent is dispersed in the resin at the molecular level. Thereby, the organic silver-based antibacterial agent can be densely and uniformly distributed on the surface of the molded product, and excellent antibacterial properties can be expressed with a small amount of the antibacterial agent added. Moreover, since the addition amount of an antibacterial agent is small, the manufacturing cost of a molding can be reduced.
Furthermore, since the organic silver-based antibacterial agent is dispersed in the resin at the molecular level, the antibacterial agent does not accumulate on the filter of the injection molding machine during injection molding, and the amount of molten resin discharged may fluctuate, Since the problem of increasing the replacement frequency is eliminated, the productivity of the molded product can be improved.
In addition, since the organic silver-based antibacterial agent is dispersed in the resin at the molecular level, the molded product can be made highly transparent, so that the appearance of the obtained molded product is hardly adversely affected.

[2]
The antibacterial composition according to [1] above, wherein the organic silver-based antibacterial agent is fatty acid silver having 10 to 30 carbon atoms.
[3]
The antibacterial composition according to [1] or [2], wherein the organic antibacterial agent is a phthalimide antibacterial agent, a sulfamide antibacterial agent, a benzimidazole antibacterial agent, or a triazole antibacterial agent.
[4]
The antibacterial composition according to any one of claims 1 to 3, further comprising a coloring inhibitor represented by the following general formula (I).
Q- (Y) n-C (Z ₁ ) (Z ₂ ) X General formula (I)
In the general formula (I), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, and Z ₁ and Z ₂ each independently represent a halogen atom. Represents an atom, and X represents a hydrogen atom or an electron-withdrawing group.
[5]
The antibacterial resin composition containing the antibacterial composition in any one of said [1]-[4], and resin.
[6]
The sum of the content of the organic silver antibacterial agent and the organic antibacterial agent with respect to the total amount of the antibacterial resin composition is 0.01% by mass or more and 70.0% by mass or less, 5] The antibacterial resin composition.
[7]
A molded article obtained by using the antibacterial composition according to any one of [1] to [4] or the antibacterial resin composition according to [5] or [6].

According to the present invention, the production cost can be reduced by suppressing the amount of antibacterial agent added when used in the production of a molded article (product) while having excellent antibacterial properties against various types of fungi and bacteria. In addition, it is possible to provide an antibacterial composition and an antibacterial resin composition that are excellent in productivity and that do not adversely affect the appearance of the molded product.
Moreover, according to this invention, the molding using the antibacterial composition or antibacterial resin composition which has the said advantage can be provided.

Hereinafter, the present invention will be described in detail.
In this specification, the term “antibacterial (antibacterial effect)” refers to the antibacterial effect itself of preventing growth and reproduction against fungi such as mold and microorganisms including eubacteria. It also includes fungi / antifungal effects and anti-algae effects, and includes, for example, antibacterial activity against bacteria defined in JIS Z2801, and antifungal activity defined in JIS Z2911.

[Antimicrobial composition]
The antibacterial composition according to the embodiment of the present invention contains an organic silver antibacterial agent and an organic antibacterial agent. Hereinafter, each component of the antibacterial composition will be described.

(Organic silver antibacterial agent)
Examples of the organic silver antibacterial agent used in the antibacterial composition include silver acetate, silver benzoate, silver lactate, silver pyrophosphate, silver citrate, silver behenate, silver diethylcarbamate, silver stearate, silver carboxylate , Silver tartrate, silver metasulfonate, silver trifluoroate, phosphoric acid or phosphorous acid alkyl ester, phenyl ester or silver salt of alkyl phenyl ester, silver fluorinated silver, phthalocyanine silver, ethylenediaminetetraacetic acid silver, protein silver, etc. be able to. Among these, preferred is silver carboxylate, and among these, higher fatty acid silver having 10 or more carbon atoms is more preferred.

  Examples of silver carboxylate include the following silver salts of carboxylic acid.

(1) C1-C30, preferably C2-C22 aliphatic saturated monocarboxylic acid such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid, behen Acid (2) C2-C34, preferably C2-C8 aliphatic saturated dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid (3) C1-C34, preferably 2 -22 aliphatic unsaturated carboxylic acids such as oleic acid, erucic acid, maleic acid, fumaric acid (4) carbocyclic carboxylic acids such as benzoic acid, phthalic acid, cinnamic acid, hexahydrobenzoic acid, abietic acid Hydrogenated abietic acid (5) Hydrocarboxylic acid such as lactic acid, malic acid, tartaric acid, citric acid, salicylic acid (6) aminocarboxylic acid such as asparagine , Glutamic acid

  In the present invention, preferable carboxylic acid silver salts include, for example, (1) a silver salt of an aliphatic saturated monocarboxylic acid, particularly silver laurate, silver stearate, silver behenate, and (3) an aliphatic unsaturated carboxylic acid. And (4) a silver salt of a carbocyclic carboxylic acid, particularly silver benzoate and silver hydrogenated abietic acid.

  Examples of the phosphoric acid or phosphorous acid alkyl ester, the phenyl ester, or the silver salt of the alkyl phenyl ester include the following.

(A) Monosilver salt or disilver salt of ester of monoalkyl phosphate (C1-22) (b) Monosilver salt or disilver salt of ester of monoalkyl phosphite (C1-22) c) Monosilver salt of dialkyl phosphate (C1-22) ester (d) Monosilver or disilver salt of monophenyl phosphate (e) Monosilver or disilver salt of monophenyl phosphite Salt (f) Monosilver salt of diphenyl phosphate (g) Mono- or di-silver salt of mono [alkyl (carbon number 1 to 22) phenyl] ester of phosphoric acid (h) Mono [alkyl (carbon number) of phosphorous acid 1 to 22) mono- or di-silver salt of phenyl] ester (i) mono-silver salt of di [alkyl (carbon number 1 to 22) phenyl] ester

  Among them, preferred silver salts are (1) mono- or di-silver salts of monoalkyl phosphates, particularly those having an alkyl group having 6 to 22 carbon atoms, more preferably disilver salts of stearyl phosphate, (3) monosilver salt of phosphoric acid dialkyl ester, particularly one having an alkyl group having 6 to 22 carbon atoms, more preferably monosilver salt of dioctel phosphate, and (9) one di (alkylphenyl) phosphate ester A silver salt, particularly one having an alkyl group having 4 to 22 carbon atoms, more preferably a monosilver salt of di (4-t-butylphenyl) phosphate or a monosilver salt of di (nonylphenyl) phosphate.

  The organic silver-based antibacterial agent is preferably fatty acid silver having 10 to 30 carbon atoms from the viewpoint of antibacterial properties. When the number of carbon atoms is 10 or more, the heat resistance of the obtained molded product can be further improved. Moreover, from the viewpoint of ease of production or availability, the number of carbon atoms of the fatty acid silver is preferably 30 or less as described above. Here, the fatty acid group in the fatty acid silver is preferably linear.

  The content of the organic silver-based antibacterial agent with respect to the antibacterial composition is preferably 1% by mass to 99% by mass, and more preferably 10% by mass to 90% by mass.

(Organic antibacterial agent)
Preferred examples of the organic antibacterial agent used in the antibacterial composition include a phthalimide antibacterial agent, a sulfamide antibacterial agent, a benzimidazole antibacterial agent, and a triazole antibacterial agent. More specifically, synthetic organic type and natural organic type are mentioned. As synthetic organic type, nitrogen-containing heterocyclic type and 5-membered imidazole type (2- (4-thiazolyl) benzimidazole [TBZ], 2- Methyl benzimidazole carbamate [BCM], 2-methylcarbonylaminobenzimidazole, etc.), thiazole isothiazoline (2- (4-thiocyanomethylthio) benzthiazole [TCMTB], 2-n-octyl-4-isothiazoline-3- ON [OIT], etc.), 6-membered pyridine-based [2,3,5,6-tetrachloro-4- (methylsulfone) pyridinebis (pyridine-2-thiol-1-oxide) zinc acid [ZPT], 2-pyridinethiol-1-oxide sodium salt, 2,2′-dithiobispyridine-1-oxide, Gin-based (hexahydro-1,3,5-tris (2-hydroxyethyl) -S-triazine), aldehyde-based (α-bromocinnamaldehyde [BCA], formalin, etc.), phenol-based (2,4,4′- Trichloro-2'-hydroxydiphenyl ether [triclosan], 3-methyl-4-isopropylphenol [biosol], 2-isopropyl-5-methylphenol [thymol], carboxylic acid, etc.), biguanides (chlorhexidine gluconate [hibiten], etc.) Nitrile (2,4,5,6-tetrachloroisophthalonitrile [TPN] etc.), halogen (organic iodo) (3-iodo-2-propylbutylcarbamate [IPBC] etc.), anilide (trichloro Carbanilide), disulfide (tetramethylthio) Ram disulfide), thiocarbamate (sodium N-methyldithiocarbamate [carbam], etc.), organosilicon quaternary ammonium salt (octadecyldimethyl (3-trimethoxypropyl) ammonium chloride, etc.), quaternary ammonium salt ( Cationic activator) (benzalkonium chloride, benzethonium chloride, etc.), amino acid (amphoteric activator) (alkyldiaminoglycine hydrochloride, etc.), organic metal (organic compounds containing metals other than silver, such as organic arsenic) 10,10'-oxybisphenoxyarsine (OBPA, vinylazine), organic copper-based oxine 8-hydroxyquinoline (oxine copper), organic zinc-based zinc pyrithione (ZPT), etc., alcohol-based (ethanol, propanol, etc.), carvone Acid system (propionic acid Etc.), ester (p- hydroxybenzoic acid esters, fatty acid monoglycerides, such as sucrose fatty acid esters), as a natural organic, hinokitiol, chitin / chitosan-based, mustard extract system, eucalyptus extract system, and the like.

  Among them, as benzimidazole compounds, methyl 1H-2-benzimidazole carbamate (generic name: carbendazim), 2- (4-thiazolyl) -1H-benzimidazole (generic name: thiabendazole [TBZ]), triazole type The compounds include (RS) -1-p-chlorophenyl-4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (generic name: tebuconazole), all -Rac-1- (biphenyl-4-yloxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol (generic name: viteltanol), phthalimide type N- (dichlorofluoromethylthio) phthalimide (generic name: fluorophorpet), sulfamide-based (N- (dichlorofluoromethylthio) -N ′, N′-dimethyl-N-phenylsulfamide (generic name: dichlorofluoranide), N- (dichlorofluoromethylthio) -N ′ , N′-dimethyl-Np-tolylsulfamide (generic name: tolufuranide) is preferred.

  The content of the organic antibacterial agent with respect to the antibacterial composition is preferably 1% by mass to 99% by mass, and more preferably 10% by mass to 90% by mass.

(Anti-coloring agent)
The antibacterial composition preferably further contains an anti-coloring agent, which can more reliably suppress discoloration (yellowing) due to the organic silver-based antibacterial agent of the obtained molded product.
As the anti-coloring agent, a compound represented by the following general formula (I) is more preferable.
Q- (Y) n-C (Z ₁ ) (Z ₂ ) X General formula (I)
In the general formula (I), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, and Z ₁ and Z ₂ each independently represent a halogen atom. Represents an atom, and X represents a hydrogen atom or an electron-withdrawing group.

In general formula (I), Q is preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a heterocyclic group containing at least one nitrogen atom (pyridine, quinoline group, etc.).
In the general formula (I), when Q is an aryl group, Q preferably represents a phenyl group substituted with an electron-withdrawing group having a positive Hammett substituent constant σp. For Hammett's substituent constants, see Journal of Medicinal Chemistry, 1973, Vol. 16, no. 11, 1207-1216 etc. can be referred to. Examples of such an electron withdrawing group include a halogen atom, a heterocyclic group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, and the like, or an alkyl group substituted with these groups, or An aryl group. Particularly preferred as the electron withdrawing group are a halogen atom, a carbamoyl group and an arylsulfonyl group, and a carbamoyl group is particularly preferred.
X is preferably an electron withdrawing group. Preferred electron withdrawing groups in X are halogen atom, aliphatic / aryl or heterocyclic sulfonyl group, aliphatic / aryl or heterocyclic acyl group, aliphatic / aryl or heterocyclic oxycarbonyl group, carbamoyl group, sulfamoyl group More preferably a halogen atom or a carbamoyl group, and particularly preferably a bromine atom.
Z ₁ and Z ₂ are preferably a bromine atom or an iodine atom, more preferably a bromine atom.
n represents 0 or 1, and is preferably 1. When n is 0,-(Y) n- represents a single bond.
Y preferably represents -C (= O) -, - SO -, - SO 2 -, - C (= O) N (R) -, or _-SO 2 N (R) -, more preferably -C (═O) —, —SO ₂ —, or —C (═O) N (R) —, particularly preferably —SO ₂ — or —C (═O) N (R) —. R here represents a hydrogen atom, an aryl group or an alkyl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
In general formula (I), when Q is an alkyl group, preferred Y is —C (═O) N (R) —, and when Q is an aryl group or a heterocyclic group, preferred Y is —SO ₂ —. is there.
In the general formula (I), a form in which residues obtained by removing a hydrogen atom from the compound are bonded to each other (generally referred to as bis type, tris type, tetrakis type) can also be preferably used.
In the general formula (I), a dissociable group (for example, a COOH group or a salt thereof, a SO ₃ H group or a salt thereof, a PO ₃ H group or a salt thereof), a group containing a quaternary nitrogen cation (for example, an ammonium group or a pyridinium group) Etc.), those having a polyethyleneoxy group, a hydroxyl group or the like as a substituent are also preferred.

  Specific examples of the compound of the general formula (I) in the present invention are shown below.

  Other anti-coloring agents that can be used in the present invention include U.S. Pat. Nos. 3,874,946, 4,756,999, 5,340,712, 5,369,000, 5,464,737, 6,506,548, and JP-A-50-137126, 50-89020, 50-119624, 59-57234, JP-A-7-2781, 7-5621, 9-160164, 9-244177, 9-244178, 9-160167, 9-319022, 9-258367, 9-265150, 9-319022, 10-197988, 10-197989, 11-242304, JP 2000 -2963, JP-A 2000-11270, JP-A 2000-284410, JP-A 2000-28 4,12, JP-A-2001-33911, JP-A-2001-31644, JP-A-2001-312027, and JP-A-2003-50441 are preferably used as polyhalogen compounds. In particular, compounds specifically exemplified in JP-A-7-2781, JP-A-2001-33911, and JP-A-2001-312027 are preferred.

  The content of the coloring inhibitor with respect to the organic silver-based antibacterial agent is preferably 0.01% by mass to 1000% by mass, and more preferably 0.1% by mass to 500% by mass. By making it 0.01% by mass or more, coloring of the molded product can be more reliably suppressed, and by being 1000% by mass or less, it is possible to suppress impairing the antibacterial properties of the antibacterial composition, or at high temperatures. Smoke and odor when used will be suppressed.

(Other additives)
The antibacterial composition can contain other additives as required. Other additives include known coupling agents, flame retardants, antioxidants, plasticizers, colorants, lubricants, antistatic agents, silicone oils, glass fibers, carbon fibers, metal fibers, glass Examples include fillers such as beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass fleli, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whisker, potassium titanate whisker, One type or two or more types can be used.
Among the fillers, glass fibers and carbon fibers preferably have an average fiber diameter of 1 to 100 μm and an average fiber length of 0.05 mm to 10 mm.
Although content with respect to the antimicrobial composition of another additive is not specifically limited unless the effect of this invention is impaired, For example, 0.005 mass%-98 mass% are preferable.
In particular, the content of the filler relative to the antibacterial composition is usually preferably 0.04 to 60% by mass.

[Antimicrobial resin composition]
The antibacterial resin composition according to the embodiment of the present invention contains the above-described antibacterial composition and resin.

(resin)
Examples of the resin include thermoplastic plastic, thermosetting plastic, and thermoplastic elastomer.
Thermoplastics include vinyl chloride resin, polyethylene, polypropylene, polystyrene, ABS resin, AS resin, nylon, polyacetal, methacrylic resin, polycarbonate, thermoplastic polyester, polyvinyl acetate, fluororesin, polyvinyl alcohol, polyurethane, etc. As the thermoplastic plastic, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin (silicone), epoxy resin, diallyl phthalate, etc. As thermoplastic elastomer, polystyrene elastomer, polyolefin elastomer, polyurethane elastomer, polyester Elastomer, butyl rubber grafted polyethylene, 1,2-polybutadiene, trans-1,4-polyisoprene, ethylene-α- Refin copolymer, eye monomer, thermoplastic NBR, rayon, cupra, acetate, natural rubber, synthetic rubber, EVA resin, microbial biopolyester, bacterial cellulose, microbial polysaccharide, chemically synthesized aliphatic polyester (poly Caprolactone, polybutylene succinate, polyethylene succinate, polyglycolic acid, polylactic acid, etc.), polyamino acids, polyurethane, nylon oligomer, natural product-based chitosan, cellulose, starch, etc. Mention may be made of at least one resin.
Depending on the required performance, other polymers such as polyamide, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, liquid crystal polymer, polyvinylidene fluoride, styrene-vinyl acetate copolymer and the like are appropriately blended. be able to.

  The content of the resin with respect to the antibacterial resin composition is preferably 30% by mass to 99.99% by mass, and more preferably 30% by mass to 99.95% by mass.

(Anti-coloring agent)
The antibacterial resin composition preferably contains the above-described anti-coloring agent, which can suppress discoloration (yellowing) due to the organic silver-based antibacterial agent of the obtained molded product.
The preferable range of the content of the anti-coloring agent relative to the organic silver-based antibacterial agent in the antibacterial resin composition is the same as that described above for the antibacterial agent composition.

(Other additives)
The antibacterial resin composition can contain one or more of the other additives described above in the section of the antibacterial composition.
The content of the other additives with respect to the antibacterial resin composition is not particularly limited as long as the effects of the present invention are not impaired. For example, the content is the same as that described above for the antibacterial agent composition.

The content of the organic silver-based antibacterial agent with respect to the antibacterial resin composition is preferably 0.01% by mass to 70% by mass, and more preferably 0.05% by mass to 70% by mass.
The content of the organic antibacterial agent with respect to the antibacterial resin composition is preferably 0.01% by mass to 70% by mass, and more preferably 0.05% by mass to 70% by mass.

  The sum of the contents of the organic silver antibacterial agent and the organic antibacterial agent is preferably 0.01% by mass or more and 70.0% by mass or less, and 0.05% by mass with respect to the total amount of the antibacterial resin composition. More preferably, it is 70.0 mass% or less. Thereby, an antibacterial, antifungal and antialgal function can be more reliably imparted to the antibacterial resin composition.

  When forming a molded product using the antibacterial resin composition as it is, the sum of the content of the organic silver antibacterial agent and the organic antibacterial agent with respect to the total amount of the antibacterial resin composition substantially prevents the resin from being discolored. From the viewpoint of being able to do, it is preferably 0.05% by mass or more and 10.0% by mass or less, more preferably 0.05% by mass or more and 5.0% by mass or less, and 0.05% by mass or more and 1.% by mass. More preferably, it is 0 mass% or less.

  On the other hand, the antibacterial resin composition may be in the form of a masterbatch containing an antibacterial agent at a high concentration. The master batch is, for example, a pellet, and can be melt-mixed with a desired resin to obtain a molded product. In particular, in the case of such a master batch, the sum of the content of the organic silver antibacterial agent and the organic antibacterial agent with respect to the total amount of the antibacterial resin composition is 0.1% by mass or more and 70.0% by mass or less. It is preferable that it is 0.5 mass% or more and 50.0 mass% or less, and it is more preferable that it is 1.0 mass% or more and 20.0 mass% or less.

[Molded product]
The molded product according to the embodiment of the present invention is obtained using the antibacterial composition described above or the antibacterial resin composition described above.
The content of the organic silver-based antibacterial agent is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, and further 0.1% by mass. It is preferable that it is% -5 mass%. By setting it as 0.01 mass% or more, the antibacterial effect which an organic silver type antibacterial agent acts can be expressed more, and by setting it as 20 mass% or less, impact resistance can be made more favorable and molding. The influence on the appearance of the object can be further suppressed.
More specifically, the molded product can be obtained by any of the following methods, for example.
(1) The above-described antibacterial composition and resin (specifically, those exemplified in the above section [Antibacterial resin composition]) are melt-mixed to obtain a molded product by an injection molding method or the like.
(2) On the surface of a molded product molded in advance by an injection molding method or the like, a liquid material of the above-described antibacterial composition (for example, the antibacterial composition and the resin exemplified in the above [antibacterial resin composition]) To obtain a molded product.
(3) The antibacterial resin composition described above is melted as it is, and a molded product is obtained by an injection molding method or the like.
(4) The above-described antibacterial resin composition (especially in the case of a masterbatch) and a further resin (specifically, those exemplified in the section of the above [antibacterial resin composition] can be mentioned) Are melt-mixed to obtain a molded product by an injection molding method or the like.
(5) The surface of a molded product molded in advance by an injection molding method or the like is coated with a melt of the antibacterial resin composition to obtain a molded product.
(6) By emulsion polymerization, the resin is dispersed in water as spherical polymer particles to form a latex, and then an antibacterial composition finely dispersed in advance by a bead mill method or the like is mixed. After coating the liquid, it is dried and solidified, and heated to 120 ° C. or higher to obtain a molded product.

In the case of (1) above, the range of the mass ratio between the antibacterial composition and the resin is preferably, for example, 0.05: 99.55 to 10.0: 90.0.
In the case of (4) above, the range of the mass ratio between the antibacterial resin composition and the further resin is preferably, for example, 5:95 to 30:70.
In the case of a molded product obtained by mixing an antibacterial composition and a resin (in the above, (1), (3), (4)), the content of the organic silver-based antibacterial agent is 0. The content is preferably 01% by mass to 20% by mass, and more preferably 0.05% by mass to 10% by mass. When it is 0.01% by mass or more, the antibacterial effect of the action of the organic silver-based antibacterial agent can be further expressed, and when it is 20% by mass or less, the influence on the appearance of the molded product can be further suppressed.

  When the antibacterial composition according to the embodiment of the present invention is used, the organic silver antibacterial agent is melted in the resin, and the organic silver antibacterial agent is dispersed in the resin at the molecular level. As a result, the organic silver-based antibacterial agent can be densely and uniformly distributed on the surface of the molded product, so that even with such a small amount of antibacterial agent added, excellent antibacterial properties can be expressed. Moreover, since there is little addition amount of an antibacterial agent, it can be set as the molded object with which manufacturing cost was reduced.

[Antibacterial composition, antibacterial resin composition, and method for producing molded article]
The antibacterial composition and the antibacterial resin composition according to the embodiment of the present invention can be obtained by kneading each component using various extruders, Banbury mixers, kneaders, rolls, and the like. A preferred production method is a method using a twin screw extruder. Moreover, when kneading each component, each component may be kneaded in a lump or may be kneaded by a multistage addition method. Using the antibacterial composition and the antibacterial resin composition thus obtained, various molded products by injection molding, sheet extrusion, vacuum forming, profile forming, foam molding, injection press, press molding, blow molding, etc. Can be molded. When obtained by injection molding, antibacterial properties are better when the injection speed is increased. Various molded products obtained by the above molding method can be used for various parts such as electric / electronic field, OA / home appliance field, automobile field, sanitary field such as toilet seat / kitchen / bathroom area, miscellaneous goods, etc. It can be used in the field of injection molding processing such as housing, and the field of film and sheet processing.

  As described above, the antibacterial composition, the antibacterial resin composition and the molded product according to the embodiment of the present invention are sanitary such as electric / electronic field, OA / home appliance field, automobile field, toilet seat / kitchen / bathroom area, etc. It can be used in the fields, parts such as miscellaneous goods, injection molding processing fields such as housing, and film and sheet processing fields, as well as in all fields that need to prevent the generation and growth of microorganisms such as general bacteria, fungi and algae. Is available.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

<Production of Film Sheet 2 (Example)>
Low density polyethylene Sumikacene L405-H (MFR 3.7 (g / 10 min), density 924 (kg / m ³ )) (Sumitomo Chemical Co., Ltd.) 99.6 parts by mass silver behenate (organic silver antibacterial) Agent) and 0.2 parts by mass of Priventol A3 (manufactured by LANXESS) (organic antibacterial agent) were added and mixed. The temperature of the mixture is set to Laboplast mill (MODEL 30C150 [manufactured by Toyo Seiki Seisakusho]) T1 / T2 / T3 / T die = 150/180/200/200 (° C.), filter plate 25 holes, filter configuration 80/200 It was discharged as a melt at 100 rpm under the conditions of / 300/80 (mesh). At this time, the film surface temperature directly under the T die was 195 ° C. The discharged molten film was collected with a square metal mesh to produce a film sheet 2 (Example). The produced film sheet was 8 cm × 30 cm × about 0.6 mm thick.

<Production of Film Sheet 1 (Control), Film Sheets 3-12 (Examples), and Film Sheets 1-14 (Comparative Examples)>
The film sheet 1 (control) and the film sheet 3 are the same except that the types and blending amounts of the organic silver antibacterial agent and the organic antibacterial agent used in the film sheet 2 (Example) are changed as shown in Table 1. To 12 (Example) and film sheets 1 to 14 (Comparative Example) were produced.

<Antimicrobial test method>
The test method was performed according to the following (1) to (4) according to JIS Z2801: 2000 antibacterial processed product-antibacterial test method.
(1) Preparation of test product The entire surface of the test product (the above film sheet) was lightly wiped 2-3 times with absorbent cotton that had absorbed ethanol, and then thoroughly dried to clean the test product.
(2) Preparation of test bacterial solution Frozen stocks were pre-cultured, and the grown colonies were scraped and adjusted to about 10 ⁵ CFU / mL.
(3) Inoculation and Culture of Test Bacterial Solution A cleaned test product was placed in a sterile petri dish, 0.4 mL of the test bacterial solution was inoculated, and a 40 mm square reinforced polyethylene ethylene film was placed on the test bacterial solution and adhered. This was allowed to act at a humidity of 90% RH or more and a temperature of 35 ± 1 ° C. for 24 hours.
(4) Collection of test product and measurement of bacterial count After 24 hours of action, the test product was collected in a sterile bag for stomacher, and 10 mL of SCDLP broth medium (Eiken Chemical) was added to wash out the test bacteria. Using this as a test stock solution, a 10-fold serial dilution series was prepared, and 1 mL each of the sample stock solution and the diluted solution was inorganically transferred to a petri dish and mixed with about 20 mL of agar medium and cultured.
The growth colonies after culturing were counted under the predetermined conditions for each test bacteria, and the number of test bacteria per test product was determined. Moreover, the film sheet (the said film sheet 1 (control)) only of the low density polyethylene Sumikacene L405-H was made into the unprocessed test goods, and the antibacterial activity value of each test goods was calculated | required on the basis of this. (Lower limit of quantification of bacteria count <10 CFU / test product)
In addition, the exponent notation in the table, for example, 1.0 × 10 ² is expressed as 1.0E + 02.

<Transparency evaluation of film sheet>
Film sheet 1 (control), film sheets 2-12 (Examples), and film sheets 1-14 (Comparative Examples) were measured for haze with a direct reading haze meter (model HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.). . The difference between the haze of the film sheet 1 (control) and the haze of the film sheet containing the antibacterial composition was determined, and transparency was judged according to the following criteria.

◎: Haze difference is less than 5% ○: Haze difference is 5% or more and less than 10% △: Haze difference is 10% or more and less than 30% ×: Haze difference is 30% or more

<Evaluation of filter dirt>
The low-density polyethylene Sumikacene L405-H (MFR 3.7 (g / 10 min), density 924 (kg / m ³ )) (manufactured by Sumitomo Chemical Co., Ltd.), the antibacterial of the examples and comparative examples described in Table 1 Each of the functional compositions is dispersed, and this is set to a temperature setting T1 / T2 / T3 / T die = 150/180/200/200 (° C.) of a lab plast mill (MODEL 30C150 [manufactured by Toyo Seiki Seisakusho]), filter plate The sample was discharged at 100 rpm for 1 hour under the conditions of 25 holes and a filter configuration of 80/200/1250/80 (mesh).
After discharging, remove the filter from the filter plate, peel off the 200 mesh filter through which the antibacterial resin composition has passed and the 1250 mesh filter, visually check the dirt (residue) deposited on 1250 mesh, and Judged.

○: Almost no filter dirt △: Less filter dirt ×: Many filter dirt

As is clear from Table 1, since the film sheets of the examples contain an organic silver antibacterial agent and an organic antibacterial agent, they have excellent antibacterial properties against all of Escherichia coli, Staphylococcus aureus and Aspergillus niger. Had. In addition, the film sheets of the examples are such that the organic silver antibacterial agent is melted in the resin, and the organic silver antibacterial agent is dispersed in the resin at the molecular level so that the organic silver antibacterial agent is densely and uniformly formed into a molded product It was found that excellent antibacterial properties can be expressed with a small amount of antibacterial agent added. Thus, the small addition amount of an antibacterial agent can contribute to the reduction of the manufacturing cost of a molding.
Moreover, since the organic silver type antibacterial agent was dispersed in the resin at the molecular level in the film sheet of the example, the antibacterial agent was not deposited on the filter of the injection molding machine at the time of injection molding (there was no filter dirt). Thereby, problems such as fluctuations in the discharge amount of the molten resin and an increase in the frequency of replacement of the filter are eliminated, so that the productivity of the molded product can be improved.
Furthermore, since the organic silver-based antibacterial agent is dispersed in the resin at the molecular level, the transparency of the molded product can be improved. Therefore, it turned out that the antibacterial composition of this invention has the advantage that it is hard to give a bad influence on the external appearance of the molding obtained.
In addition, about Example 10 and 11 containing a coloring inhibitor, coloring was reducing compared with the other examples. The colorability was measured under the following conditions. (Spectrocolorimeter: Model CM-3600d (manufactured by KONICA MINOLTA), Color software: CM-S100W Spectra Magic NX, Measurement method: Reflection, Field of view: 10 °, Main light source: C light source, Geometry: d / 8, Regular reflection (Light treatment: SCI + SCE, measurement diameter: LAV (25.4 mm), UV condition: b * (C) is measured under the condition of 100%)

On the other hand, the film sheets of Comparative Examples 1 to 11 in which only one of the organic silver antibacterial agent and the organic antibacterial agent is used have excellent antibacterial properties against all of Escherichia coli, Staphylococcus aureus and Aspergillus niger. Could not show.
Further, in the film sheets of Comparative Examples 12 to 14 using both the silver antibacterial agent and the organic antibacterial agent, the silver antibacterial agent is not densely and uniformly distributed in the molded product as compared with the organic silver antibacterial agent. For this reason, filter stains occurred and the transparency of the molded product was poor. Moreover, although it was possible to show excellent antibacterial properties against all of Escherichia coli, Staphylococcus aureus and Aspergillus niger, it was necessary to increase the content of silver antibacterial agents (specifically, 1.0 mass%). Therefore, it was found that these film sheets cannot contribute to the reduction of the manufacturing cost of the molded product.

Claims (7)

  An antibacterial composition containing an organic silver antibacterial agent and an organic antibacterial agent.   The antibacterial composition according to claim 1, wherein the organic silver-based antibacterial agent is fatty acid silver having 10 to 30 carbon atoms.   The antibacterial composition according to claim 1 or 2, wherein the organic antibacterial agent is a phthalimide antibacterial agent, a sulfamide antibacterial agent, a benzimidazole antibacterial agent, or a triazole antibacterial agent. The antibacterial composition according to any one of claims 1 to 3, further comprising a coloring inhibitor represented by the following general formula (I).
Q- (Y) n-C (Z ₁ ) (Z ₂ ) X General formula (I)
In the general formula (I), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, and Z ₁ and Z ₂ each independently represent a halogen atom. Represents an atom, and X represents a hydrogen atom or an electron-withdrawing group.   The antibacterial resin composition containing the antibacterial composition in any one of Claims 1-4, and resin.   The sum of the contents of the organic silver antibacterial agent and the organic antibacterial agent with respect to the total amount of the antibacterial resin composition is 0.01% by mass or more and 70.0% by mass or less. 5. The antibacterial resin composition according to 5.   The molded product obtained using the antibacterial composition in any one of Claims 1-4, or the antibacterial resin composition of Claim 5 or 6.