JP2000344611A - Antimicrobial, antifungal and antistatic composition and antimicrobial, antifungal and antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in antimicrobial and antifungal properties and further antistatic properties and water, detergent and weather resistances, etc., by including a specific compound, a specified ammonium salt and an organic compound-based antifungal agent. SOLUTION: This composition is obtained by including (A) an ester compound having an ether structure in the molecule, (B) an ammonium salt represented by the formula (any one of R1 to R3 is a 5-24C alkyl and the others are each a 1-5C alkyl; R4 is a 2-4C alkylene; n is 1-15; X is an anion of hydrochloric acid, chloric acid or perchloric acid) as an antimicrobial agent and (C) an organic compound-based antifungal agent. The ingredient A is prepared by carrying out an esterifying reaction of (i) a polyfunctional carboxylic acid with (ii) a monoalkyl ether of glycols. A dichlofluanid-N-haloalkylthio-based compound, a phenol ether derivative, an imidazole derivative, a sulfonyl derivative, etc., are cited as the ingredient C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial / antifungal / antistatic resin composition and an antibacterial / antifungal / antistatic resin composition.

[0002]

2. Description of the Related Art Various molded articles made of synthetic resin are widely used in household articles, electric parts, industrial articles, building materials, and the like. affect.

[0003] For example, spots caused by bacteria and fungi
Not only the external effects such as discoloration, but also the deterioration and deterioration of the interior materials, and the microorganisms that have propagated further become food for mites and cause allergic diseases, which is a major social problem. .

[0004] Therefore, in order to prevent the propagation of bacteria and fungi, a method of kneading an antibacterial / antifungal agent into various plastic molded articles or applying a solution of the antibacterial / antifungal agent to the surface of the plastic molded article has been used. ing.

[0005] Antibacterial and antifungal agents for plastic molded products include organic arsenic antibacterial and antifungal agents (10,10'-oxybisphenoxyarsine), which have strong bactericidal activity and good heat stability, copper, and copper. Inorganic metal-based antibacterial and antifungal agents such as silver and mercury are mainly used (for example, Japanese Patent Application Laid-Open No. 64-46644 and Japanese Patent Application Laid-Open No. 1-113051).

[0006]

However, the above-mentioned organic arsenic antibacterial and antifungal agents (10,10'-oxybisphenoxyarsine) must be used with care and safety in health and safety. The antibacterial and antifungal agents have a problem that the resin is easily discolored, the antibacterial and antifungal properties are poor in water resistance and detergent resistance, and the antibacterial and antifungal properties are not maintained.
In addition, antibacterial and antifungal resin compositions used for household articles, electric parts, industrial articles, building materials and the like are required to have antibacterial and antifungal properties as well as antistatic properties.

In view of the above problems, an object of the present invention is to provide excellent antibacterial and antifungal properties as well as excellent antistatic properties.
An object of the present invention is to provide an antibacterial, antifungal and antistatic composition which can maintain antibacterial and antifungal properties over a long period of time, and is excellent in water resistance, detergent resistance and weather resistance.

[0008]

The invention of claim 1 comprises an ester compound having an ether structure in the molecule, an ammonium salt represented by the following general formula (1), and an organic compound-based fungicide. An antibacterial / antifungal / antistatic composition characterized by the following:

[0009]

Embedded image

(In the formula, ^one of R ¹ , R ² and R ³ represents an alkyl group having 5 to 24 carbon atoms;
The same or different, and represents an alkyl group having 1 to 5 carbon atoms.
R ⁴ represents an alkylene group having 2 to 4 carbon atoms. n is 1
Represents an integer of ~ 15. X represents an anion derived from hydrochloric acid, chloric acid or perchloric acid)

The invention according to claim 2 is the antibacterial / antifungal / antistatic composition according to claim 1, wherein the organic fungicide is a cyclofluanid-N-haloalkylthio compound. .

The invention of claim 3 provides the following general formula (1): 0.01 to 5 parts by weight of an ester compound having an ether structure in a molecule per 100 parts by weight of a thermoplastic resin or a crosslinked rubber. An antibacterial / antifungal / antistatic resin composition comprising 0.01 to 5 parts by weight of an ammonium salt and 0.01 to 3 parts by weight of an organic compound-based fungicide.

In the present invention, an ester compound having an ether structure in the molecule is used. Such an ester compound is obtained by an esterification reaction between a polycarboxylic acid and a monoalkyl ether of a glycol.

The polycarboxylic acids include, for example, aromatic polycarboxylic acids such as phthalic acid, trimellitic acid and pyromellitic acid, and aliphatic polycarboxylic acids such as adipic acid.

The monoalkyl ethers of glycols include, for example, monoalkyl ethers such as ethylene glycol and propylene glycol. Specifically, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-n-hexyl ether, triethylene glycol Examples include ethylene glycol monomethyl ether.

The esterification reaction between the above polycarboxylic acid and the monoalkyl ether of glycols is carried out by a known method. The temperature of this esterification reaction is 80-250.
C is preferable, and 160 to 230 C is more preferable. Temperatures above 230 ° C. should be avoided to minimize thermal decomposition of the reactants.

In the present invention, an ammonium salt represented by the above general formula (1) is used as an antibacterial agent. here,
When any one of R ¹ , R ² and R ³ has less than 5 carbon atoms, the antibacterial activity is significantly reduced. On the other hand, when the number of carbon atoms exceeds 24, the phase with the synthetic resin (a) is poor. The solubility is remarkably reduced, and leaches out onto the surface of the molded product, resulting in poor appearance. Particularly, the carbon number is preferably 8 to 18.

When the carbon number of the other two alkyl groups among R ¹ , R ² and R ³ exceeds 5, the above synthetic resin (a)
Is significantly reduced, and is exuded on the surface of the molded article, resulting in poor appearance. Particularly, the number of carbon atoms is preferably 1 or 2.

On the other hand, if the number of carbon atoms of the alkylene group of R ⁴ is less than 2, sufficient antibacterial properties cannot be obtained, and if the number of carbon atoms exceeds 4, the compatibility with the synthetic resin (a) is significantly reduced. ,
It oozes out on the surface of the molded product and its appearance deteriorates. Particularly, the carbon number is preferably 2 or 3. When n exceeds 15, the compatibility with the synthetic resin (a) is significantly reduced, and leached on the surface of the molded product, resulting in poor appearance. In particular, n is preferably 1 to 5.

As the organic compound-based fungicide, 10 and 10
Phenol ether derivatives such as -oxybishenoxaarsine, 2-n-octyl-4-isothiazoline-
Cyclofluanid N-haloalkylthio-based compounds such as 3-one and 1,2-benzisothiazolone-3-one;
Imidazole derivatives such as 2- (4-thiazolyl) benzimidazole, 2,3,5,6-tetrachloro-4-
Sulfonyl derivatives such as (methylsulfonyl) pyridine are preferred.

As the thermoplastic resin, polyvinyl chloride,
It is a polypropylene resin, a polyethylene resin, a polystyrene resin, an ABS resin, or a mixture thereof. The crosslinked rubbers may be natural rubber or synthetic rubber.

The antibacterial / antifungal / antistatic composition of the present invention may further contain a filler, a plasticizer, a stabilizer, a lubricant,
Various known additives such as antioxidants, ultraviolet inhibitors, and pigments can be added.

The antibacterial / antifungal / antistatic resin composition is formed into a film or sheet and can be used as a wallpaper or a flooring material, and can be used as a paint, a resin coating or a composite material.

The compounding ratio of the antibacterial / antifungal / antistatic resin composition is 0.01 to 5 parts by weight of an ester compound having an ether structure in a molecule per 100 parts by weight of a thermoplastic resin or a crosslinked rubber. 0.01 to 5 parts by weight of an ammonium salt represented by the formula (1), 0.0
1 to 3 parts by weight. More preferably, with respect to 100 parts by weight of a thermoplastic resin or a crosslinked rubber, 0.3 to 1.5 parts by weight of an ester compound having an ether structure in a molecule,
0.1 to 2 parts by weight of an ammonium salt represented by the above formula (1) and 0.01 to 2 parts by weight of an organic compound-based fungicide. When the amount of the ester compound having an ether structure in the molecule is less than 0.3 parts by weight, antibacterial properties, antifungal properties, and antistatic properties are all reduced, and when it exceeds 1.5 parts by weight, antifungal properties, Poor detergent resistance and persistent antibacterial properties.

When the amount of the ammonium salt represented by the above formula (1) is less than 0.01 part by weight, the antibacterial property is not sufficient. Does not last.

If the amount of the organic compound-based antifungal agent is less than 0.01 part by weight, the antifungal property is not sufficient, and if it exceeds 3 parts by weight, the water resistance and the detergent resistance are poor and the antifungal property is not maintained.

[0027]

Examples (Examples 1 to 3 and Comparative Examples 1 to 3) (1) Preparation of antibacterial / antifungal / antistatic resin composition Dihexyl glycol adipate and ammonium salt represented by the following formula (2) Chlorate and 2-n-octyl-4-isothiazolin-3-one as an organic compound-based fungicide were added to polyvinyl chloride resin (average degree of polymerization = 1350) in Table 1.
And an antibacterial / antifungal / antistatic resin composition were prepared by mixing at the ratios shown in Table 2.

[0028]

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[0029]

[Table 1]

[0030]

[Table 2]

(2) Performance evaluation of antibacterial / antifungal / antistatic resin composition The antibacterial / antifungal / antistatic resin composition was kneaded with a roll heated to 180 ° C., and then using a tabletop press. 0.1
A sheet having a thickness of mm was prepared.

With respect to the obtained sheet, the following performance evaluations 1 to 5 were performed. 1. Antibacterial property Test method: The antibacterial efficacy of the cells was evaluated according to the film adhesion method (method of the Research Group for Inorganic Antibacterial Agents such as Silver). Test strain: Escherichia coli (Escherichia coli) IF
O3972 · Staphylococcus aureus (S. aureus) IFO12732 bacteria solution adjusted: 18-hr cultured cells inoculated to 37 ° C. The test bacteria on nutrient agar were dispersed in 1/500 nutrient broth medium, about 10 ⁵ CFU / ml of test bacterial solution was prepared. Adjustment of sample: Adjusted to a sheet having a size of 5 cm × 5 cm. Test operation: Inoculate 0.5 ml of the bacterial solution on a sample placed in a sterile petri dish and a polyethylene film (control), cover with a polyethylene film, temperature 35 ° C., relative humidity 90%
This was stored for 24 hours. Controls were stored immediately after inoculation and after storage for 24 hours, and samples were stored for 24 hours after storage in sterile Petri dishes in SCDLP (Soybean Casein Dige).
st Lecithin Polysorbate 8
0) 10 ml of medium was added, and the bacterial solution was washed out. The wash was serially diluted with physiological saline, and the diluted solution was diluted with a standard agar medium, cultured at 35 ° C. for 48 hours, and the number of viable bacteria was counted. Evaluation criteria: ・ ・ ・: The number of colonies is 10 or less. ×: There are 10 ⁵ to 10 ⁶ colonies.

2. Test method for antifungal property: The antifungal effect of a sample was evaluated according to ISO 846. Test bacteria: ・ Aspergillus niger (Aspergillus) ・ Chaetomium globosum (Petromyces) ・ Paecilomyces variotii (Pesiromyces) ・ Penicilium funiculosum
(Blue mold)-Tricoderma virid (Thick mold) Sample adjustment: Adjusted to a sheet having a size of 4 cm x 4 cm. Preparation of spore suspension: The test strain was cultured on a potato dextrose medium for one week, and the spores were NaNO ₃ : 2 g, KH
₂ PO ₄ : 0.7 g, K ₂ HPO ₄ : 0.3 g, KC
1: 0.5 g, MgSO ₄ .7H ₂ O: 0.5 g, Fe
_{SO 4 · 7H 2 O: 0.01g} , wetting agents: 0.1 g, glucose: 30 g, water: dispersed in the lubricant solution consisting of 1000 ml, to prepare a spore suspension. Test operation: The sample was NaNO ₃ : 2 g, KH ₂ PO ₄ :
0.7 g, K ₂ HPO ₄ : 0.3 g, KCl: 0.5
_{g, MgSO 4 · 7H 2 O} : 0.5g, FeSO 4 · 7
H ₂ O: 0.01 g, glucose: 30 g, agar: 15
g, water: 1000 ml, placed at the center on an ISO-designated inorganic salt agar medium, inoculated with a fungal mixed spore suspension, and cultured at a temperature of 28 ° C. and a relative humidity of 90% or more. After a lapse of 4 weeks, the sample was observed with a microscope, and the fungicide efficacy was evaluated based on the following criteria. Evaluation criteria: ・ ・ ・: no mold was observed in the visual field of the microscope. ×: Mold is observed on most or the entire surface of the visual field of the microscope.

3. Persistence of antibacterial and antifungal properties (a) Water resistance The obtained sheet was immersed in distilled water at 20 ° C. for 5 days, and then evaluated for antibacterial and antifungal properties. (B) Detergent resistance The obtained sheet was immersed in a 5% aqueous detergent solution at 20 ° C. for 5 days, and then evaluated for antibacterial and antifungal properties. (C) Weather resistance The obtained sheet was placed in a fade meter at 63 ° C. for 20 minutes.
After leaving for 0 hour, the antibacterial property and the antifungal property were evaluated.

4. Surface resistivity Measured according to JIS K6911. The unit is Ω / □
Displayed with.

5. Bleed-out resistance After heating the obtained sheet at 70 ° C for 24 hours, the presence or absence of bleed-out on the sheet surface was visually observed.
In the table, those having no bleed-out were indicated by “○”, and those having bleed-out were indicated by “x”.

Table 3 shows the evaluation results of the sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 3, respectively.

[0038]

[Table 3]

[0039]

As described above, the antibacterial / antifungal / antistatic resin composition of the present invention is excellent in antibacterial / antifungal water resistance, detergent resistance, and antistatic properties. In addition, antibacterial and antifungal properties are maintained for a long time.

Therefore, the growth of bacteria and mold is prevented, and the quality of the molded product is prevented from deteriorating due to bleed-out. The molded product is transparent without any discoloration and is colored to an arbitrary color by a colorant. Can be obtained. Further, when static electricity is charged to a human due to friction or the like, the static electricity is quickly eliminated through the molded article.

Therefore, the antibacterial / antifungal / antistatic resin composition of the present invention is suitable for applications requiring antibacterial / antifungal properties and antistatic properties such as household goods, electric parts, industrial goods and building materials. is there.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/16 104 C09K 3/16 104B

Claims (3)

[Claims] 1. An antibacterial, antifungal, and electrostatic charge comprising an ester compound having an ether structure in the molecule, an ammonium salt represented by the following general formula (1), and an organic compound antifungal agent. Inhibitory composition. Embedded image (In the formula, any one of R ¹ , R ² , and R ³ represents an alkyl group having 5 to 24 carbon atoms, and the other represents the same or different and represents an alkyl group having 1 to 5 carbon atoms. R ⁴ represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 15. X represents an anion derived from hydrochloric acid, chloric acid or perchloric acid. 2. The antibacterial / antifungal / antistatic composition according to claim 1, wherein the organic compound-based fungicide is a cyclofluanid-N-haloalkylthio-based compound. 3. An ester compound having an ether structure in a molecule of 0.01 to 5 parts by weight and an ammonium salt of 0.1 to 5 parts by weight based on 100 parts by weight of a thermoplastic resin or a crosslinked rubber. An antibacterial, antifungal and antistatic resin composition comprising from 0.01 to 5 parts by weight and 0.01 to 3 parts by weight of an organic compound-based fungicide.