JPH11166076A - Antibacterial and antifungal resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial and antifungal resin composition having good thermal stability, good bleedout resistance, and excellent antibacterial and antifungal properties. SOLUTION: This antibacterial and antifungal resin composition comprises 100 pts.wt. of at least one selected from the group consisting of a polypropylene resin, a polyethylene resin, a polystyrene resin, and an acrylonitrile/butadiene/ styrene terpolymer resin, 0.2-30 pts.wt. of an ammonium salt expressed by the below-described formula [either one of R<1> , R<2> and R<3> is a 5-24C alkyl group, and the others are 1-5C alkyl groups which may be same or different; R<4> is a 2-4C alkylene group; (n) is an integer of 1-15; X is an anion expressed by Cl<-> , C1O3 <-> or ClO4 <-> ], and 0.3-130 pts wt. of an ester compound having an ether structure in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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] In order to prevent the propagation of bacteria and fungi, methods of kneading an antibacterial / antifungal agent into various plastic molded articles and applying a solution of the antibacterial / antifungal agent to the surface of the plastic molded article have been used. I have.

[0005] Antibacterial and antifungal agents for plastic molded articles include organic arsenic antibacterial and antifungal agents (10,10'-oxybisphenoxyarsine) having strong bactericidal activity and good heat stability, and inorganic silver. -Based antibacterial and antifungal agents are mainly used (for example, published by the Industrial Research Institute Co., Ltd. (first edition, second printing)
Practical Plastics Dictionary, pp. 869-871).

However, the organic arsenic antibacterial and fungicide (10,10'-oxybisphenoxyarsine) is
It must be used with care and safety, which is problematic. In addition, inorganic silver-based antibacterial and antifungal agents promote deterioration and discoloration by light, and the resin is liable to discolor. on the other hand,
Quaternary ammonium salts are known as antibacterial and antifungal agents that have strong bactericidal activity and are harmless to the human body.

[0007]

However, when a quaternary ammonium salt is kneaded as an antibacterial and antifungal agent into various molded articles made of synthetic resin, the quaternary ammonium salt has poor thermal stability. In addition, the color of the resin composition changes during thermoforming, and if the color becomes severe, the resin composition may be blackened and molding may not be performed.

When a quaternary ammonium salt solution is applied to the surface of various molded articles made of synthetic resin as an antibacterial and antifungal agent, the quaternary ammonium salt is removed from the surface by washing the molded article with water or aging. Thus, there is a problem that the durability of the antibacterial and antifungal properties is reduced.

The present invention solves the above problems,
It is an object of the present invention to provide an antibacterial / antifungal resin composition having good thermal stability and bleed-out resistance, particularly excellent antibacterial / antifungal properties, and also having excellent antistatic properties. .

[0010]

The antibacterial / antifungal resin composition of the present invention comprises a polypropylene resin, a polyethylene resin, a polystyrene resin, and an acrylonitrile / butadiene / styrene copolymer resin (hereinafter referred to as ABS resin). At least one selected from the group consisting of the following (synthetic resin (a)): 100 parts by weight; ammonium salt represented by the following general formula (1): 0.2 to 30 parts by weight; And 0.3 to 130 parts by weight of an ester compound having an ether structure.

Embedded image (Wherein, ^one of R ¹ , R ² and R ³ represents an alkyl group having 5 to 24 carbon atoms, and the other two have 1 carbon atoms.
Represents up to 5 alkyl groups, all of which may be the same or different. R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, and n represents an integer of 1 to 15. X is Cl ^-,
ClO ₃ ^- or ClO ₄ ^- is an anion represented by. )

The synthetic resin (a) is a polypropylene resin, a polyethylene resin, a polystyrene resin, AB
S resin or a mixture thereof. These are resins that are widely used as materials for ordinary daily necessities.

In the present invention, an ammonium salt represented by the above general formula (1) is used as an antibacterial / antifungal agent. Here, when any one of R ¹ , R ² and R ³ has less than 5 carbon atoms, the antibacterial and antifungal properties are significantly reduced. (A)
Is significantly reduced, and is exuded on the surface of the molded article, 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.

If the alkylene group of R ₄ has less than 2 carbon atoms, sufficient antibacterial and antifungal properties cannot be obtained.
If it exceeds, the compatibility with the synthetic resin (a) is remarkably reduced, and the resin is leached on the surface of the molded article to deteriorate the appearance. Especially,
The number of carbon atoms 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.

The ammonium salt represented by the above general formula (1) is added in an amount of 0.2 to 100 parts by weight of the synthetic resin (a).
It is contained in the range of up to 30 parts by weight.

When the content of the ammonium salt is less than 0.2 parts by weight, the antibacterial and antifungal properties of the molded article become insufficient. Conversely, when the content of the ammonium salt exceeds 30 parts by weight, the above-mentioned synthetic resin becomes insufficient. The compatibility with the resin (a) is remarkably reduced, and the resin is leached out to the surface of the molded article to deteriorate the appearance, and the bleed-out resistance and the water resistance are reduced. In particular, the content of the ammonium salt is preferably 0.5 to 10 parts by weight.

In the present invention, an ester compound having an ether structure in the molecule is used together with the ammonium salt. When the above-mentioned ammonium salt is used alone, the resin composition is discolored at the time of thermoforming, and if the resin composition becomes severe, the resin composition may be blackened and molding may not be performed. Thereby, the thermal stability at the time of thermoforming can be remarkably improved. Such an ester compound is a polyvalent carboxylic acid,
It is obtained by an esterification reaction of a glycol with a monoalkyl ether.

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 a glycol 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.

The ester compound having an ether structure in the molecule is contained in an amount of 0.3 to 130 parts by weight based on 100 parts by weight of the synthetic resin (a).

When the content of the ester compound is less than 0.3 parts by weight, the thermal stability during thermoforming is insufficiently improved, and the antistatic performance and the antibacterial / antifungal performance of the molded product are maintained. And the flexibility of the molded article is reduced. Conversely, when the content of the ester compound exceeds 130 parts by weight,
Bleed out to the surface of the molded article, and the surface of the molded article is contaminated. In particular, the content of the ester compound is preferably 5 to 15 parts by weight.

The antibacterial / antifungal composition of the present invention may further contain a plasticizer, a lubricant, a reinforcing agent, a filler, a stabilizer, a coloring agent, an antistatic agent, a flame retardant, a plate-out inhibitor, etc., if necessary. Various known additives can be blended.

Examples of the plasticizer include tricresyl phosphate, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl adipate, dioctyl sebacate and the like. Examples of the lubricant include higher fatty acid esters and low molecular weight polyethylene.

Examples of the reinforcing agent include zinc oxide, magnesium carbonate, carbon black, graphite and fine silica. As a filler, calcium carbonate,
Examples include talc, clay, calcium silicate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate and the like.

Examples of the stabilizer include phenol-based and amine-based antioxidants, sulfide-based and phosphorus-based hydroperoxide decomposers, salicylate-based, benzophenone-based, benzotriazole-based, and hindered amine-based light stabilizers. Is mentioned. Examples of the coloring agent include titanium oxide, carbon black, phthalocyanine green, and chrome yellow.

[0027]

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

Examples 1 to 6 and Comparative Examples 1 to 6 A polypropylene resin (Mitsubishi Kasei Co., Ltd., 6
800JP), polyethylene resin (Nihon Unicar Co., Ltd.)
GRSN-7340), an ester having an ether bond in the molecule represented by the formula (2), and an ammonium salt represented by the formula (3) are mixed for 8 minutes with a small tabletop kneader, and the antibacterial / antifungal resin composition is mixed. I got something. The obtained resin composition was
After kneading for 6 minutes with a 6 inch roll heated to 80 ° C,
Using a desktop press machine, 185 ° C, 150kgf / cm
The sheet was formed into a sheet having a thickness of 1 mm under press conditions of ² and 6 minutes. The obtained sheets were evaluated for the following performances 1 to 5, and the results are shown in Table 1.

[0029]

Embedded image

[0030]

Embedded image

1. Antibacterial performance In accordance with JIS L1902, a halo test method was used to observe whether or not a clear zone (halo) for inhibiting the growth of microorganisms appeared around the evaluation sheet, and the halo appeared. Those were indicated by ○. Measurement medium: Heart Infusion Ager (40 g / L purified water, manufactured by DIFCO) was used. Test method: After cooling and drying 20 ml of the sterilized measurement medium (121 ° C. × 20 minutes) in a petri dish, the following colonies were applied to the entire surface of the medium, and the evaluation sheet (4
(0 mm square). After culturing at 30 ° C for 24 hours,
It was observed whether or not a clear zone (halo) for inhibiting the growth of microorganisms appeared around the evaluation sheet. · Escherichia coli (E. coli) about 10 ⁵ cells / ml · Staphylococcus aureus (S. aureus) about 10 ⁷ cells / ml

2. Antifungal Performance In accordance with JIS L1902, the halo test method was used to observe whether or not a clear zone (halo) for inhibiting the growth of microorganisms was developed around the evaluation sheet, and the halo expression was evaluated. Certain ones are indicated by ○. Measurement medium: Potato Dextrose Ager (39 g / L purified water, manufactured by DIFCO) was used. Test method: After cooling and drying 20 ml of the sterilized measurement medium (121 ° C. × 20 minutes) in a petri dish, the following colonies were applied to the entire surface of the medium, and the evaluation sheet (4
(0 mm square). After culturing at 30 ° C for 24 hours,
It was observed whether or not a clear zone (halo) for inhibiting the growth of microorganisms appeared around the evaluation sheet.・ Cladosporium

3. Bleed-out property After heating the obtained sheet at 70 ° C for 7 days (168 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 "O", and those having bleed-out were indicated by "X".

4. Surface resistivity Measured according to JIS K6911. The unit is Ω / □
Displayed with. 5. Volume resistivity Measured according to JIS K6911. The unit is Ω ・ c
Indicated by m.

[0035]

[Table 1]

[0036]

As described above, the antibacterial and antifungal resin composition of the present invention has good heat stability and bleed-out resistance during molding, has excellent antibacterial and antifungal properties, and further has antistatic properties. Is also excellent.

Therefore, the growth of bacteria and molds is prevented, and the quality of the molded product is prevented from deteriorating due to bleed-out. Further, 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 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.

Claims (1)

[Claims] 1. A polypropylene-based resin, a polyethylene-based resin, a polystyrene-based resin, and acrylonitrile /
100 parts by weight of at least one selected from the group consisting of butadiene / styrene copolymer resins, 0.2 to 30 parts by weight of an ammonium salt represented by the following general formula (1),
And an antibacterial composition comprising 0.3 to 130 parts by weight of an ester compound having an ether structure in the molecule.
Antifungal resin composition. Embedded image (Wherein, ^one of R ¹ , R ² and R ³ represents an alkyl group having 5 to 24 carbon atoms, and the other two have 1 carbon atoms.
Represents up to 5 alkyl groups, all of which may be the same or different. R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, and n represents an integer of 1 to 15. X is Cl ^-,
ClO ₃ ^- or ClO ₄ ^- is an anion represented by. )