JP2006273738A - Antibacterial agent for resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial agent for a resin, making it possible that the resin exhibits more excellent antibacterial properties than ever and an antibacterial molded product of the resin is scarcely discolored. <P>SOLUTION: This antibacterial agent contains a quaternary ammonium superacid salt expressed by general formula (1) (R<SP>1</SP>and R<SP>2</SP>are each a 1-22C aliphatic hydrocarbon group; R<SP>3</SP>is a 1-22C aliphatic hydrocarbon group or a 7-22C arylalkyl or arylalkenyl group; R<SP>4</SP>is a 8-22C aliphatic hydrocarbon group; and X<SP>-</SP>is a superacid anion). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antibacterial agent for resin and an antibacterial resin composition. More specifically, the present invention relates to an antibacterial agent for resin containing a quaternary ammonium salt type antibacterial agent, an antibacterial resin composition containing the antibacterial agent, and a molded article formed by molding the composition.

Conventionally, antibacterial properties have been imparted by blending an antibacterial agent with a resin for hygienic needs. Antibacterial agents to be added include inorganic antibacterial agents such as silver, copper and zinc zeolite (see Patent Document-1), organic antibacterial agents such as imidazole antibacterial agents (see Patent Document-2), and thiazoline-based antibacterial agents. Antibacterial agents (see Patent Documents 3 and -4) and salts of anionic polymers and quaternary ammonium salts (see Patent Document 5) are known.
JP-A-6-116458, JP-A-52-7435, JP-A-8-310903, JP-A-11-207880, JP 2000-154105 A.

However, the conventional antibacterial agent cannot exert its effect unless a large amount of the antibacterial agent is added to the resin, and coloring of the resin or deterioration of the physical properties of the molded product easily occur due to the addition of a large amount. In particular, quaternary ammonium salt antibacterial agents often contain a relatively large amount of free primary, secondary or tertiary amine compounds, and resin molding using these antibacterial agents The body was liable to cause a decrease in antibacterial properties and coloring of the molded body due to heat history during resin molding.
An object of the present invention is to add a quaternary ammonium salt-based antibacterial agent for resin, the antibacterial agent for resin that suppresses a decrease in antibacterial property due to heat history during resin molding and coloring of the molded product, and the antibacterial agent. An antibacterial resin composition, and a molded article obtained by molding the composition.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above object. That is, the present invention provides an antibacterial agent for resin containing a quaternary ammonium super strong acid salt (A) and having a total amine value of 0.5 mgKOH / g or less; a thermoplastic resin and / or thermosetting An antibacterial resin composition comprising a resin and an antibacterial agent for the resin; and an antibacterial resin molded article formed by molding the antibacterial resin composition.

The antibacterial resin molded article containing the antibacterial agent for resin of the present invention is:
1. An antibacterial resin molded product that can exhibit sufficient antibacterial properties even when the amount of the antibacterial agent is small is provided.
2. The content of amine compounds derived from antibacterial agents contained in antibacterial resin moldings is less than that of conventional antibacterial resin moldings, so the moldings are less colored, and the antibacterial agent has the physical properties of the resin moldings. There is little decrease.

  In the present invention, the quaternary ammonium superacid salt (A) includes a quaternary ammonium superacid salt (A1) represented by the following general formula (1); an amide group [alkyl (carbon number: 10 to 24) amide]. A quaternary ammonium superacid salt (A2) having an alkyl (2 to 6 carbon group) or / and a hydroxyalkyl group having 2 to 4 carbon atoms; and a cyclic amine (pyridine, morpholine, etc.) type quaternary ammonium super salt Strong acid salts (A3) are included.

R ¹ and R ² in the general formula (1) represent a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms (such as an alkyl group and an alkenyl group).
As the linear aliphatic hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, Examples include an alkyl group obtained by removing a hydroxyl group from alcohol derived from coconut oil (hereinafter abbreviated as coconut oil alkyl group) and an oleyl group, and examples of the branched hydrocarbon group include an isopropyl group and a 2-ethylhexyl group. . Of these, preferred are those having 1 to 14 carbon atoms, more preferably 1 to 8 carbon atoms, especially 1 or 2 carbon atoms, and most preferred is a methyl group. R1 and R2 may be the same or different, but are preferably the same.

R ³ represents a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms or an arylalkyl or arylalkenyl group having 7 to 22 carbon atoms. Examples of the linear or branched aliphatic hydrocarbon group include those exemplified above, examples of the arylalkyl group include a benzyl group and a phenethyl group, and examples of the arylalkenyl group include a styryl group and a cinnamyl group.
R ³ is preferably a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms or an arylalkyl or arylalkenyl group having 7 to 15 carbon atoms, more preferably 6 to 14 carbon atoms. A linear or branched aliphatic hydrocarbon group.

R ⁴ represents a linear or branched aliphatic hydrocarbon group having 8 to 22 carbon atoms (such as an alkyl group and an alkenyl group).
Examples of the linear aliphatic hydrocarbon group include octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, coconut oil alkyl group and oleyl group, and branched aliphatic hydrocarbon groups. Examples of the group include a 2-ethylhexyl group. R ⁴ is preferably a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms, and more preferably a linear or branched aliphatic hydrocarbon group having 10 to 16 carbon atoms. X ⁻ represents an anion of a super strong acid described later.

As a specific example of the quaternary ammonium group constituting (A1), when R ³ is an aliphatic hydrocarbon group, for example, one having one long-chain alkyl group (trimethyldodecyl ammonium, trimethyl tetradecyl ammonium, Trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl coconut oil alkyl ammonium, trimethyl-2-ethylhexyl ammonium, dimethyl ethyl dodecyl ammonium, dimethyl ethyl tetradecyl ammonium, dimethyl ethyl hexadecyl ammonium, dimethyl ethyl octadecyl ammonium, dimethyl ethyl coconut oil alkyl ammonium , Dimethylethyl-2-ethylhexylammonium, methyldiethyldodecylammonium, methyldiethyltetradecylan Nium, methyldiethylhexadecylammonium, methyldiethyloctadecylammonium, methyldiethyl palm oil alkylammonium and methyldiethyl-2-ethylhexylammonium) having two long chain alkyl groups (6 to 22 carbon atoms) (dimethyldihexylammonium, Dimethyl dioctyl ammonium, dimethyl didecyl ammonium and dimethyl didodecyl ammonium) and those having one long chain alkenyl group (8 to 22 carbon atoms) (trimethyl oleyl ammonium, dimethyl ethyl oleyl ammonium and methyl diethyl oleyl ammonium).
When R ³ is an arylalkyl group, for example, dimethyldecylbenzylammonium, dimethyldodecylbenzylammonium, dimethyltetradecylbenzylammonium, dimethylhexadecylbenzylammonium, dimethyl coconut oil alkylbenzylammonium, dimethyloleylbenzylammonium and dimethyl-2 -Ethylhexylbenzylammonium.

  Of these, trimethylhexadecylammonium, dimethyldidecylammonium, dimethyldodecylbenzylammonium and dimethyltetradecylbenzylammonium are preferable from the viewpoint of antibacterial properties.

Examples of the quaternary ammonium group constituting (A2) include oleamidoethyldiethylmethylammonium, stearamideethyldiethylbenzylammonium, and stearamidopropyldimethylhydroxyethylammonium groups.

The quaternary ammonium group constituting (A3) includes an alkyloxy (carbon number 8-24) methylpyridinium group (for example, stearyloxymethylpyridinium group), an alkyl (carbon number 8-24) oxymethylpyridinium group (for example, , Hexadecyloxymethylpyridinium group) and alkyl (C10-24) pyridinium group (for example, tetradecylpyridinium group).

The super strong acid constituting the anion in (A) is an acid having an acid strength stronger than 100% sulfuric acid ("super strong acid / super strong base" by Kozo Tabe, Ryoji Noyori, published by Kodansha Scientific, p1). Yes, Hammett's acidity function (H ₀ ) is less than -11.93 of 100% sulfuric acid, and examples include proton acids and acids composed of proton acids and Lewis acids.
Specific examples of the protonic acid, trifluoromethanesulfonic acid (H ₀ = -14.10), pentafluoroethane sulfonic acid (H ₀ = -14.00), and the like.
Examples of the protonic acid used in the combination of the protonic acid and the Lewis acid include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), and examples of the Lewis acid include boron trifluoride and pentafluoride. Phosphorous fluoride, antimony pentafluoride, arsenic pentafluoride, taurine pentafluoride and the like.
A combination of a protonic acid and a Lewis acid is arbitrary, but specific examples of super strong acids obtained by combining them include boron tetrafluoride acid, hexafluorophosphoric acid, chlorofluoroboronic acid, hexafluoroantimonic acid, hexa Examples thereof include fluorinated arsenic acid and taurine hexafluoride.
Among the above super strong acids, from the viewpoint of heat resistance of the quaternary ammonium salt (A) represented by the general formula (1) of the present invention, Hammett's acidity function (H ₀ ) is preferably −12. 00 or less, such as trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, boron tetrafluoride, phosphorus hexafluoride, chlorofluoroboric acid, antimony hexafluoride, arsenic hexafluoride, taurine hexafluoride, etc. Further preferred are trifluoromethanesulfonic acid, tetrafluoroboric acid and hexafluorophosphoric acid, and particularly preferred are trifluoromethanesulfonic acid and boron tetrafluoroboric acid.

  Among (A), from the viewpoint of heat resistance, the ability to exhibit antibacterial properties with addition of a small amount, and the sustainability of antibacterial properties, (A1) is preferable, and dimethyldidecylammonium boron tetrafluoride is particularly preferable. Acid salts, didecyldimethylammonium trifluoromethanesulfonate, trimethylhexadecylammonium tetrafluoroborate, dimethyl coconut oil alkylbenzylammonium tetrafluoroborate and dimethyl coconut oil alkylbenzylammonium trifluoromethanesulfonate.

The antibacterial agent for resin of the present invention has a total amine value of usually 0.5 mgKOH / g or less, preferably 0.3 mgKOH / g or less, particularly preferably 0.2 mgKOH / g or less, particularly preferably 0.1 mgKOH / g or less. It is. When the total amine value exceeds 0.5 mgKOH / g, the antibacterial agent itself, the antibacterial resin composition containing the antibacterial agent, and the molded article formed by molding the antibacterial resin composition are likely to be colored.
The total amine value can be measured by potentiometric titration using perchloric acid.
Specifically, about 7 g of the sample is precisely weighed in a beaker, and 50 ml of acetic acid is added to dissolve the sample. Using a 0.01 mol / L perchloric acid titration solution, titration is performed with a potentiometric titrator, and the total amine value is calculated by the following equation.

Total amine number = (A−B) × f × 0.56111 / S
Here, A: ml number of 0.01 mol / L perchloric acid titration solution required for this test B: ml number of 0.01 mol / L perchloric acid titration solution required for blank test f: 0 .01 mol / L titration of perchloric acid titration solution S: sampling amount (g)

The free primary to tertiary amine compounds that contribute to the total amine value of the antibacterial agent for resin of the present invention are usually by-products and / or during the production of the quaternary ammonium salt superacid salt (A) in the present invention. Alternatively, it is derived from impurities, and the free primary to tertiary amine compounds are usually amine compounds having a hydrocarbon group, arylalkyl group and / or arylalkenyl group constituting (A).
The content of the free primary to tertiary amine compound in the antibacterial agent for resin of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less, particularly 200 ppm or less.
Examples of the free primary to tertiary amine compounds include the following compounds.
Primary amine compounds;
Examples include aliphatic monoamines having 1 to 22 carbon atoms (such as methylamine, ethylamine, butylamine, octylamine, decylamine, dodecylamine, and octadecylamine) and arylalkylamines (such as benzylamine).
Secondary amine compounds;
Dialkylamines having an alkyl group having 1 to 22 carbon atoms (such as dimethylamine, diethylamine, dibutylamine, dioctylamine, didecylamine, didodecylamine, dioctadecylamine, methylethylamine, methyldecylamine, methyldodecylamine, and methyloctadecylamine) And amines having 1 to 22 carbon atoms and arylalkyl groups (such as methylbenzylamine and ethylbenzylamine).
Tertiary amine compounds;
Trialkylamines having an alkyl group having 1 to 22 carbon atoms (trimethylamine, triethylamine, methyldioctylamine, methyldidecylamine, methyldidodecylamine, methyldioctadecylamine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine and dimethyl Octadecylamine) and amines having 1 to 22 carbon atoms and arylalkyl groups (such as dimethylbenzylamine and diethylbenzylamine).

In the antibacterial agent for resin of the present invention, the content of carbonate ester based on the weight of (A) is preferably 200 ppm or less, more preferably 100 ppm or less, and particularly preferably 50 ppm or less.
When a large amount of carbonate ester remains, a phenomenon such as generation of carbon dioxide gas during kneading with the resin or over time tends to cause a decrease in the strength of the resin. If the carbonic acid ester is 200 ppm or less, it is preferable because the resin strength of a molded article formed by molding the antibacterial resin composition described later of the present invention is less likely to decrease.
The carbonate ester is usually contained when a part of the raw material carbonic acid dialkyl ester used in the production method described below is unreacted or remains as an intermediate.
Examples of the carbonic acid dialkyl ester include dimethyl carbonate and diethyl carbonate, and the content of the carbonate can be measured by gas chromatography.

Examples of the production method (A) include the following methods [I] and [II].
The method [II] is preferable from the viewpoint that there are few various impurities.

[I]: An alkali metal salt (sodium salt or potassium salt) of the super strong acid is added to an aqueous solution (20 to 70% by weight) of a quaternary ammonium salt [for example, a salt composed of chloranion] (quaternary ammonium salt). The equivalent ratio of salt / super strong acid salt is usually 1/1 to 1 / 1.5, preferably 1 / 1.05 to 1 / 1.3), and an aqueous solution obtained by stirring and mixing at room temperature for about 2 hours is 70 to After stirring at 80 ° C. for about 1 hour, the lower layer (aqueous layer) which was allowed to stand and liquid-separated was removed, and stripped under reduced pressure (stripping step-1) until the water content in the upper layer was 0.3% or less. A crude product is obtained. Thereafter, 3 to 10% of water is added based on the weight of the crude product, and the degree of vacuum is -0.09 MPaG or less, 105 to 120 ° C. x 3 to 6 hours, and stripping under reduced pressure (stripping step-2). To obtain the desired quaternary ammonium salt.

[II]; Carbonic acid dialkyl ester (alkyl group having 1 to 5 carbon atoms) of the same amount or more (preferably 1.1 to 5.0 equivalents) as the tertiary amine in the presence of a solvent (for example, methanol) 10 to 1,000% by weight based on the weight of the tertiary amine) or in the absence, at a reaction temperature of 80 to 200 ° C., preferably 100 to 150 ° C. to form a quaternary ammonium salt, Add super strong acid (1.0-1.2 equivalents based on equivalents of quaternary ammonium) and stir at 10-50 ° C. for 1 hour to salt exchange. The solvent is stripped under reduced pressure at 80 to 120 ° C. (stripping step-1) to obtain a crude product. Thereafter, 3 to 10% of water is added based on the weight of the crude product, and the degree of vacuum is 0.09 MPaG or less, 105 to 120 ° C. × 3 to 6 hours, and the vacuum stripping (stripping step− 2) to obtain the desired quaternary ammonium salt.

In order to set the total amine value in the antibacterial agent for resin of the present invention to 0.5 mgKOH / g or less, it is preferable to perform the above-described reduced pressure stripping step-2. Since the content of the tertiary amine compound can be reduced, the total amine value can be 0.5 mgKOH / g or less, particularly 0.3 mgKOH / g or less.
When the production amount is small, instead of the reduced pressure stripping step-2, it is spread in a thin film (for example, a thickness of 2 mm or less) in a container having a relatively large area and is the same as the reduced pressure stripping step-2. It may be dried under reduced pressure, heating and time conditions.

  In the production of (A) of the present invention, filtration may be performed in a heated and melted state as necessary after the above-described stripping step-2. Filtration can be performed with a known filter having a 100 to 300 mesh metal net or filter cloth.

(A) in the present invention is usually a solid, and its melting point is usually from 30 to 120 ° C, preferably from 40 to 110 ° C.
The antibacterial agent for resin of the present invention consists of (A) alone or (A) and a free primary to tertiary amine compound giving a total amine value of 0.5 mgKOH / g. The antibacterial agent for resin is usually solid, and its melting point is in the same range as (A).

The antibacterial resin composition of the present invention is a composition containing the above-mentioned antibacterial agent for resin, a thermoplastic resin and / or a thermosetting resin.
Examples of thermoplastic resins include polyolefin resins [eg, polyprolene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, etc.]; polyacrylic resins [eg, polymethyl methacrylate, etc.]; polystyrene Resin [for example, polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate Copolymer (MS resin, etc.); polyester resin [eg, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene Pate etc.]; Polyamide resin [eg nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12 etc.]; Polycarbonate resin [eg polycarbonate, polycarbonate / ABS resin alloy and the like]; polyacetal resin; thermoplastic polyurethane resin and the like.
Among these, preferred are polyacrylic resins, polystyrene resins, polyacetal resins, polyester resins, polycarbonate resins, thermoplastic polyurethane resins, polyamide resins, and particularly preferred are polystyrene resins, polyacetal resins, polyesters. Resin, polycarbonate resin, and thermoplastic polyurethane resin.

  Thermosetting resins include unsaturated polyester resins (such as crosslinked copolymers of glycols and unsaturated polyesters derived from unsaturated and saturated dibasic acids) and epoxy resins (bisphenol type epoxy resins). , Epoxy resins such as novolac epoxy resins and cycloaliphatic epoxy resins, cured resins with polyamines, acid anhydrides, etc.), thermosetting polyurethane resins (including polyurethane foams), superabsorbent resins (cross-linked polyacrylamides) Partial hydrolysates, cross-linked acrylic acid-acrylamide copolymers, etc.).

  The content of the antibacterial agent for resin relative to the above resin is usually 0.01 to 10% based on the weight of the resin, preferably 0.1 to 10%, more preferably 0.2 from the viewpoint of antibacterial effect and resin physical properties. -5%, particularly preferably 0.3-3%.

  The antibacterial resin composition of the present invention may further contain an additive selected from a pigment, a nucleating agent, a plasticizer, a stabilizer, a filler, a flame retardant, a dispersant, an antioxidant, and an ultraviolet absorber as necessary. it can.

  Examples of pigments include titanium oxide, bengara, yellow lead, cadmium, ultramarine, azo series, phthalocyanine series, vat dye series, quinacridone series, dioxazine series, dyed lake, etc .; nucleating agents such as dibenzylidene sorbitol; plasticizer Phthalates (dioctyl phthalate, etc.), phosphates, adipic acid, sebates, glycolates, polyesters, epoxies, etc .; stabilizers include lead white, basic sulfite Lead, tribasic lead sulfate, dibasic lead phosphite, silica gel lead silicate, liquid metal, laurate organotin, maleate organotin, mercaptide organotin, antimony, epoxy, phosphorous Acid ester, etc .; Fillers include calcium carbonate, talc, clay, silicic acid, silicate, asphalt Strike, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker, titanium whisker, etc .; As a flame retardant, phosphate ester type [tricresyl phosphate, tris (2,3 dibromopropyl) phosphate, etc.], Bromine (such as decabromobiphenyl ether), antimony trioxide, magnesium hydroxide, borate (such as zinc borate and barium metaborate), aluminum hydroxide, red phosphorus, magnesium hydroxide, ammonium polyphosphate, het acid And tetrabromobisphenol A.

  Moreover, as antioxidant, phenolic antioxidant [2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.] Sulfur-based antioxidants [dilauryl 3,3′-thiodipropionate (DLTDP), distearyl 3,3′-thiodipropionate (DSTDP), etc.]; phosphorus antioxidants [triphenyl phosphite (TPP ), Triisodecyl phosphite (TDP), etc.]; amine antioxidants [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, etc.], etc .; UV absorption Examples of the agent include benzophenone (2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4 '-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, etc.), salicylates (phenyl salicylate, 2,4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate), benzotriazole series [(2′-hydroxyphenyl) benzotriazole, (2′-hydroxy-5′-methylphenyl) benzotriazole, (2′-hydroxy- 3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, (2′-hydroxy-5′-methacryloyloxyethylphenyl) benzotriazole and its (co) polymer, etc.], acrylic [ethyl 2-cyano-3,3-diphenyl acrylate, methyl-2-cal Bomethoxy-3- (paramethoxybenzyl) acrylate and the like] and the like.

  The use amount of the above additives is based on the weight of the resin, and the plasticizer and filler are usually 80% or less, preferably 10 to 50%, the flame retardant is usually 40% or less, preferably 10 to 30%, pigment Is usually 40% or less, preferably 1 to 10%, nucleating agents and stabilizers are usually 10% or less, preferably 1 to 5%, antioxidants and UV inhibitors are usually 5% or less, preferably 0.1 to 0.1%. 2%.

  The antibacterial resin molded product of the present invention is obtained by molding the above antibacterial resin composition.

When the resin is thermoplastic, the antibacterial resin composition of the present invention and the method for producing a molded body are obtained by mixing the antibacterial agent for resin and, if necessary, an additive and a solid or solution resin with a mixer. After blending to a predetermined concentration and mixing uniformly, heat melting and kneading with an extruder to obtain an antibacterial resin composition, and then molding with a heat molding machine or injection molding machine, etc. Create a so-called master batch in which the resin antibacterial agent is blended with the resin, then dilute to a predetermined concentration with a resin that does not contain the resin antibacterial agent, and if necessary, blend with other additives, then mold Methods and the like.
When resin is a thermosetting resin, the method of shape | molding after mix | blending an antibacterial agent and an additive in the component which can be mixed is mentioned.
Melt kneading is performed by mixing with a mixer such as a Henschel mixer and then kneading (usually 150 to 250 ° C.) using a twin screw extruder or the like, and is further formed into pellets, powders, fibers or blocks. .
Further, a masterbatch is produced by previously heat-kneading the antibacterial agent for resin with a small amount of resin [(A) in the antibacterial resin composition / resin = 11-60 / 89-40 weight ratio] to produce a masterbatch, and further resin It is also possible to produce an antibacterial resin composition by heat melting and kneading.

The molded product obtained by molding the antibacterial resin composition in the present invention is a method of molding the antibacterial resin composition pellets or powders by a pressure molding machine or an injection molding machine, or antibacterial properties. After each component of the resin composition is heated, melted and kneaded, it is obtained by a method of continuously molding with a pressure molding machine or an injection molding machine. Although the temperature at the time of a shaping | molding process is suitably selected according to the kind of resin, it is 180-250 degreeC normally, Preferably it is 200-230 degreeC.
Since the molded article of the present invention hardly undergoes thermal decomposition at the time of molding, problems such as reduction in antibacterial properties and coloring of the molded article are unlikely to occur.
Further, the molded article of the present invention is hardly colored even when it comes into contact with an oxidant. For example, in the case of a fibrous molded body, even if it is treated with a bleach (oxidizing agent such as hypochlorite), it is less colored than a conventional antibacterial resin molded body.

  The shape of the molded body of the present invention is a block-like material, a plate-like material, a sheet, a film, a fiber shape, or the like. Molded articles include sanitary items such as bathtubs and washstands, household appliances such as refrigerators and washing machines, household items such as tables and kitchens, building items such as PVC pipes, and fibers and textiles such as polypropylene, polyester, nylon, and spandex. It can be used in various applications such as packaging products such as polyethylene sheets.

<Example>
Hereinafter, the present invention will be further described with reference to Examples and Production Examples, but the present invention is not limited thereto. The part in an Example shows a weight part.

[Production example of (A)]
Production Example 1
A glass reaction vessel equipped with a heating / cooling device, a stirrer and a dropping funnel was charged with 56 parts of methanol, 163 parts of methyldi-n-decylamine (0.88 mole part), and 144 parts of dimethyl carbonate (1.6 mole part). After reacting at 120 ° C. for 20 hours, a part of methanol and dimethyl carbonate was distilled off to obtain 250 parts (0.52 mole part) of 83% methanol solution of dimethyldi-n-decylammonium methyl carbonate. Furthermore, after raising the temperature to 30 to 60 ° C., 114 parts (0.55 mole part) of 42% aqueous solution of boron tetrafluoride was gradually added over 2 hours while maintaining the temperature. Thereafter, the mixture was further stirred at the same temperature for 1 hour, and then the upper separated liquid was separated and transferred to another glass reaction vessel. Methanol and water were distilled off at 80 to 100 ° C. under reduced pressure to be crude. Product-1 was obtained. Further, 9 parts (0.50 mole part) of water was added, and vacuum stripping was performed (degree of vacuum -0.09 MPaG, 105 ° C. × 3 hours). Thereafter, the mixture was melted at 80 ° C., and the deposited salt was removed by filtration through a 200 mesh wire netting to obtain 206 parts of dimethyldi-n-decylammonium tetrafluoroborate (A-1) solid at room temperature. The total amine value of (A-1) was 0.08 mgKOH / g, and the dimethyl carbonate was below the detection limit (10 ppm).

Production Example 2
To 95 parts of a 83% methanol solution of dimethyldi n-decylammonium methyl carbonate obtained in the same manner as in Production Example 1 (0.52 mole part), 79.5 parts (0.53 mole part) of trifluoromethanesulfonic acid at room temperature. Was added and stirred for 2 hours. Granular caustic potash was added to the reaction solution to neutralize it (pH: 6 to 8), and the precipitated salt was filtered, and then methanol in the filtrate was distilled off. Further, 9 parts (0.50 mole part) of water was added, Stripped under reduced pressure (same conditions as above) and taken out in a molten state at 120 ° C. to obtain 250 parts of dimethyldi n-decylammonium trifluoromethanesulfonate (A-2) solid at room temperature. The total amine value of (A-2) was 0.05 mgKOH / g, and the dimethyl carbonate was below the detection limit (10 ppm).

Comparative antibacterial agent Crude product-1 in Production Example 1 had a total amine value of 0.6 mgKOH / g, and this was used as a comparative antibacterial agent for resin (B-1). The carbonate ester of (B-1) was below the detection limit (10 ppm).
As other comparative antibacterial agents, silver zeolite (B-2), 2- (4′-thiazolyl) -benzimidazole (B-3), and dimethyldi-n-decylammonium chloride (B-4) were used.

Examples 1-5, Comparative Examples 1-5
After mixing the antibacterial agent in the number of parts shown in Table 1 and the resin in the number of parts shown in Table 1 with a Henschel mixer, it is melt-kneaded at 200 ° C. with a vented twin-screw extruder to obtain a pellet-like antibacterial resin composition. It was. Furthermore, these pellets were injection-molded to obtain molded bodies (50 mm × 50 mm × 2 mm) of Examples and Comparative Examples. As the resin, there are transparent ABS resin “TE-10” (hereinafter abbreviated as ABS) manufactured by Denki Kagaku Kogyo Co., Ltd. and polypropylene resin “E-105GM” (hereinafter abbreviated as PP) manufactured by Idemitsu Kosan Co., Ltd. It was.

<Antimicrobial evaluation of antimicrobial resin moldings>
JIS Z 2801 (antibacterial processed product-antibacterial test method / antibacterial effect) Evaluated according to.
That is, a test bacterial solution prepared by diluting a normal broth medium 500 times with sterilized purified water so that the number of bacteria becomes 2.5 × 10 ⁵ to 10 × 10 ⁵ cells / ml is used as a test piece (molded body test). 0.4 ml was dropped on a piece (50 mm × 50 mm × 2 mm), and the film was covered from above so as not to dry, and cultured at a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more for 24 ± 1 hours. Then, the test piece and the film were washed out with 10 ml of SCDLP medium, and the liquid was promptly subjected to viable cell count to determine the viable cell count. The results are shown in Table 1.

<Evaluation of hue of antibacterial resin molding>
About the molded object (Examples 1-5) which consists of an antibacterial resin composition of this invention, and a comparative molded object (Comparative Examples 1-5), cylinder temperature 230 degreeC using an injection molding machine (made by Nissei Plastic Industry). A molded piece of 100 mm × 100 mm × 2 mm was prepared under the above conditions, and the hue was measured using a measurement dye meter manufactured by Nippon Denshoku Industries Co., Ltd. The result is represented by yellowness, and the larger the value, the greater the yellowness and the stronger the coloring.

  From Table 1, the molded bodies (Examples 1 to 5) composed of the antibacterial agent for resin of the present invention have superior antibacterial properties compared to conventional antibacterial agents (such as those that are not super strong acid salts). Even if it is a quaternary ammonium super strong acid salt, it turns out that there are few changes of a hue compared with the thing with a large total amine number, and there is little coloring.

  The antibacterial resin composition obtained using the antibacterial agent for resin of the present invention is molded into an antibacterial resin molded body. These molded products are in the form of antibacterial pellets, blocks, plates, sheets, films, threads, etc., which are further sanitary items such as bathtubs and washstands, and household appliances such as refrigerators and washing machines It can be used in various applications such as household items such as dining tables and kitchens, building supplies such as PVC pipes, fibers and textiles such as polypropylene, polyester, nylon and spandex, and packaging items such as polyethylene sheets.

Claims (7)

  An antibacterial agent for resin comprising a quaternary ammonium super strong acid salt (A) and having a total amine value of 0.5 mgKOH / g or less.   The antibacterial agent for resin according to claim 1, wherein the content of carbonate ester based on the weight of (A) is 200 ppm or less. The antibacterial agent for resins according to claim 1 or 2, wherein (A) is a quaternary ammonium superacid salt represented by the general formula (1).

(Wherein R ¹ and R ² are the same or different, a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, and R ³ is a linear or branched aliphatic group having 1 to 22 carbon atoms. (A hydrocarbon group or an arylalkyl or arylalkenyl group having 7 to 22 carbon atoms, R ⁴ represents a linear or branched aliphatic hydrocarbon group having 8 to 22 carbon atoms, and X ⁻ represents an anion of a super strong acid.)   An antibacterial resin composition comprising a thermoplastic resin and / or a thermosetting resin, and the antibacterial agent for resin according to any one of claims 1 to 3.   Furthermore, the antibacterial resin composition of Claim 4 containing 1 or more types chosen from the group which consists of a pigment, a nucleating agent, a plasticizer, a stabilizer, a filler, a flame retardant, antioxidant, and a ultraviolet absorber.   An antibacterial resin molded article obtained by molding the antibacterial resin composition according to claim 4 or 5.   The molded article according to claim 6, which is in a fibrous form.