JPH10279794A - Antimicrobial resin composition and molded article using the same - Google Patents

Abstract

(57) [Problem] The present invention has extremely low toxicity to the human body,
An antibacterial resin composition having excellent antibacterial properties, which can be suitably used for a long period of time in medical hygiene materials, tableware, lifestyle-related materials, automotive interior materials, household appliances, films, sheets, textile products, etc. An object of the present invention is to provide a molded article using the composition. SOLUTION: An antibacterial resin composition in which a mixture of ε-polylysine or a salt thereof and a surfactant is added to a synthetic resin, a molded article using the composition, and ε-polylysine or a derivative thereof in a thermoplastic resin. Salt and dispersant or ε-
An antibacterial resin composition to which polylysine or a salt thereof, a surfactant and a dispersant are added, and a molded article obtained by molding the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a synthetic resin,
An antimicrobial resin composition and a thermoplastic resin to which a mixture of a polylysine or ε-polylysine salt (hereinafter collectively referred to as an antimicrobial agent) and a surfactant are added, and the antimicrobial agent and a dispersant or a thermoplastic resin are added to the mixture. The present invention relates to an antibacterial resin composition containing an antibacterial agent, a dispersant, and a surfactant. More specifically, the present invention relates to an antibacterial resin composition which can be widely used in the production of molded articles such as medical hygiene materials, living-related materials, interior materials, home appliances, tableware, films, sheets, and textile products, and molded articles using the same. .

[0002]

2. Description of the Related Art In our living space, various microorganisms such as bacteria and molds are present. These microorganisms often give us discomfort by spoiling food and causing malodors. In addition, it may cause various diseases such as food poisoning and skin disorders such as ringworm, and may even kill the life of infants and elderly people with weak resistance. In order to lead a hygienic and comfortable life, the control of microbial growth is an important issue, and it is desired to add an antibacterial function to various medical supplies, daily necessities, clothing and the like around us.

On the other hand, with the development of petrochemicals, synthetic resins containing various thermoplastic resins have been developed. These synthetic resins are light and strong, and can be molded freely according to the purpose. Widely used in However, most synthetic resins by themselves do not have an antimicrobial function.

As a method for imparting antibacterial properties to a synthetic resin, an attempt to impart antibacterial properties by adding a compound containing a metal such as silver, copper, or zinc to the synthetic resin has been made, for example, in JP-A-54-1.
No. 47220, for example. An attempt to add zeolite-based solid particles ion-exchanged with silver ions and copper ions to a synthetic resin has been made, for example, in JP-A-59-13.
It is proposed in Japanese Patent No. 3235 and the like.

[0005] However, these methods may cause discoloration of the synthetic resin due to the metal compound, which may impair the appearance and commercial value of the synthetic resin product. In addition, in the presence of chloride ions, silver ions that should exhibit antibacterial properties,
Since metal ions such as copper ions form chlorides, sufficient antibacterial performance cannot be obtained. Further, the synthetic resin products obtained by these methods may cause skin damage to the human body, particularly to infants with weak skin or people with allergic constitution, depending on the intended use.

[0006] As a method for obtaining an antibacterial resin product having high safety to the human body, allyl isothiocyanate extracted from mustard and wasabi, protamine extracted from mature testis such as salmon and trout, and microorganisms belonging to the genus Streptomyces A method of applying a naturally occurring food preservative, such as ε-polylysine, obtained from Co., Ltd. to a synthetic resin product on the surface is considered.

However, the antibacterial resin products obtained by applying the above-mentioned preservatives on the surface lack cleaning resistance, and are durable consumables used for a long period of time, household goods such as tableware which are repeatedly washed, There are difficulties in full-scale use for clothing and the like. In addition, mustard,
There is a problem that the odor adheres to the synthetic resin product when the surface is applied because of a stimulating odor peculiar to wasabi.

[0008] A method of obtaining an antibacterial resin composition by directly adding the above preservative to the resin is also conceivable. However, since allyl isothiocyanate is volatilized by heat processing at the time of molding a synthetic resin product, a necessary and sufficient antibacterial agent is obtained. In order to obtain an antibacterial resin composition having performance, it is necessary to add a high concentration,
Further, since protamine is a protein, it is susceptible to heat and has a problem that it cannot withstand thermal processing during molding.

The antimicrobial agent of ε-polylysine or a salt thereof has no problem in volatility and thermal stability, but has poor compatibility with synthetic resins, so that secondary agglomeration easily occurs in the resin at the time of molding processing, and the resin is often used. Impairs product appearance. Further, the antibacterial agent is difficult to disperse uniformly in the resin, and may not be able to obtain a sufficient antibacterial effect. Further, in applications requiring washing resistance, it is necessary to add a high concentration of the antibacterial agent to the resin. Occurs and there is a problem in cost.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have repeatedly studied to solve the above-mentioned problems of the prior art. As a result, by mixing the antibacterial agent and the surfactant and adding them to the synthetic resin, or by adding and using the antibacterial agent and the dispersant together, the dispersing property of the antibacterial agent in the resin is improved. Improved, the use of a surfactant and a dispersant together with the antimicrobial agent makes it easier to elute the antimicrobial agent than a resin composition to which these antimicrobial agents are added alone, and has an antimicrobial property at a low additive concentration. Was found to be effective for maintaining the antibacterial effect after washing, and the present invention was completed.

As is apparent from the above description, an object of the present invention is to provide extremely low toxicity to the human body, excellent antibacterial properties, medical hygiene materials, tableware, living-related materials, automobile interior materials, and household use. It is an object of the present invention to provide an antibacterial resin composition capable of obtaining a molded product that can be suitably used for a long period of time as an electric appliance, a film, a sheet, a fiber product, and the like, and a molded product thereof.

[0012]

The present invention is constituted as follows. (1) An antibacterial resin composition in which ε-polylysine or a mixture of ε-polylysine salt and a surfactant is added to a synthetic resin. (2) An antimicrobial resin composition wherein 0.001 to 10% by weight of a mixture of ε-polylysine or ε-polylysine salt and a surfactant is added to a synthetic resin. (3) The antibacterial property according to any one of (1) to (2) above, wherein the mixture of ε-polylysine or ε-polylysine salt and the surfactant is a mixture having a mixing ratio of 9: 1 to 1: 9. Resin composition. (4) The antibacterial resin composition according to any one of (1) to (3) above, wherein the ε-polylysine salt is a salt of an inorganic acid or an organic acid of ε-polylysine. (5) The first surfactant, wherein the surfactant is at least one surfactant selected from a fatty acid ester of glycerin, a fatty acid ester of sorbit, a fatty acid ester of sorbitan, and a polyhydric alcohol-type nonionic surfactant of alkyl glucoside. Item 4. The antibacterial resin composition according to any one of Items 3 to 3. (6) The above-mentioned items 1 to 3, wherein the surfactant is at least one kind of a polyethylene glycol type nonionic surfactant.
Item 14. The antibacterial resin composition according to any one of the above items. (7) The antibacterial resin composition according to any one of the above items (1) to (3), wherein the surfactant is at least one of betaine-type amphoteric surfactants. (8) The antibacterial resin composition according to any one of the above items (1) to (3), wherein the surfactant is at least one kind of a quaternary ammonium salt type cationic surfactant. (9) The surfactant according to any one of the above items 6 to 8
4. The antimicrobial resin composition according to any one of the above items 1 to 3, which is at least two or more surfactants selected from the surfactants described in the above item. (10) The antibacterial resin composition according to any one of the above items 1 to 9, wherein the synthetic resin is a thermoplastic resin. (11) The antibacterial resin composition according to any one of the above items 1 to 9, wherein the synthetic resin is a thermosetting resin. (12) A molded article obtained by using the antibacterial resin composition according to any one of (1) to (11).

(13) An antibacterial resin composition containing ε-polylysine or ε-polylysine salt and a dispersant in a thermoplastic resin. (14) ε-polylysine or ε-polylysine salt is added to the thermoplastic resin in an amount of 0.001 to 10% by weight based on the composition, and ε-polylysine or ε-polylysine salt contains 100: An antimicrobial resin composition contained in the range of 1-1: 100. (15) The above item 13 or the thermoplastic resin, wherein the thermoplastic resin is a polyolefin resin, a thermoplastic polyester resin, a polyamide resin, a polystyrene resin, a vinyl chloride resin, a vinylidene chloride resin, a thermoplastic elastomer or a mixture thereof. Item 15. The antibacterial resin composition according to any one of Items 14 to 14. (16) The antibacterial resin composition according to any one of the above (13) or (14), wherein the dispersant is at least one dispersant selected from metal salts of fatty acids. (17) The above (13) or (14), wherein the dispersant is at least one dispersant selected from hydrocarbon compounds.
Item 14. The antibacterial resin composition according to any one of the above items. (18) The above (13) or (14), wherein the dispersant is at least one dispersant selected from amide compounds.
Item 14. The antibacterial resin composition according to any one of the above items. (19) The above (13) or (14), wherein the dispersant is at least one dispersant selected from ester compounds.
Item 14. The antibacterial resin composition according to any one of the above items. (20) The antibacterial resin composition according to any one of the above (13) or (14), wherein the dispersant is at least one dispersant selected from higher alcohols. (21) The dispersant according to any one of (13) and (14), wherein the dispersant is at least two or more dispersants selected from the dispersants according to any one of (16) to (20). 2. The antibacterial resin composition according to claim 1. (22) A molded article obtained by using the antibacterial resin composition according to any one of the above items 13 to 21.

(23) An ε-polylysine or an ε-polylysine salt, one or more surfactants according to any one of the above-mentioned items 5 to 8, and the above-mentioned items 16 to An antibacterial resin composition containing at least one of the dispersants according to any one of items 20 to 20. (24) The ε-polylysine or the ε-polylysine salt is added to the thermoplastic resin in an amount of 0.001 to 10% by weight based on the composition, and the composition according to any one of items 5 to 8 above. One or more surfactants may be present in the composition at 0.0001% to 50% by weight.
21. The composition according to any one of items 16 to 20, wherein the at least one dispersant is at least 0.0001% by weight based on the composition.
An antimicrobial resin composition added in a range of 50% by weight. (25) A molded article obtained by using the antibacterial resin composition according to any one of the above items 23 and 24.

Hereinafter, the present invention will be described in detail. The antimicrobial agent ε-polylysine or a salt thereof used in the present invention is:
For example, an ε-polylysine-producing bacterium described in JP-B-59-20359, Streptomyces alplus subsp. Lysinopolymeras belonging to the genus Streptomyces, is cultured in a medium, and ε is obtained from the resulting culture.
-Obtained by separating and collecting polylysine.
The ε-polylysine or a salt thereof is a substance described in the list of existing additives of the Ministry of Health and Welfare, and is used for food preservatives and the like.

In the present invention, ε-polylysine may be in a free form or may be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like, or acetic acid, propionic acid, fumaric acid, malic acid, citric acid, maleic acid, adipic acid, It can also be used in the form of a salt of an organic acid such as gluconic acid. Also, depending on the use and purpose of use, salts of medium- and long-chain saturated fatty acids such as caproic acid, lauric acid and stearic acid, and medium- and long-chain unsaturated fatty acids such as oleic acid, linoleic acid and arachidonic acid Can also be used. ε-polylysine, whether in free form or in the form of a salt with the above-mentioned inorganic or organic acids, has essentially no difference in its antibacterial effect.

The surfactants used in the present invention include polyhydric alcohol type nonionic surfactants such as fatty acid esters of glycerin, fatty acid esters of sorbitol, fatty acid esters of sorbitan, and alkyl glucosides, and polyethylene glycol type nonionic surfactants. , Betaine-type amphoteric surfactants and quaternary ammonium salt-type cationic surfactants are particularly excellent in terms of compatibility of ε-polylysine with resin, improvement of dispersibility, and manifestation of antibacterial effect. Can also be used according to the application and intended purpose without impairing the antibacterial effect of ε-polylysine. The form of the surfactant used in the present invention may be any of solid, powder, liquid, and paste.

The form of the mixture of the antibacterial agent and the surfactant used in the present invention may be any of powder, liquid and paste.

The mixture of the powdered antibacterial agent and the surfactant may be produced by uniformly mixing the finely pulverized antibacterial agent and the finely pulverized surfactant. After uniformly dispersing the agent and surfactant in an appropriate solvent, for example, water, drying under reduced pressure, vacuum freeze drying, spray drying, or the like, the resulting mixture is pulverized using a pulverizing device. It may be manufactured. In the case of a drying method involving heating, the drying temperature is preferably set to 60 ° C. or lower in order to prevent decomposition of the antibacterial agent and the surfactant.

The liquid or paste mixture of the antimicrobial agent and the surfactant may be prepared by uniformly dispersing the antimicrobial agent and the surfactant in a suitable solvent, for example, water.
The mixture may be concentrated and produced by a suitable method such as concentration under reduced pressure and heat concentration. In the case of a concentration method involving heating,
In order to prevent the decomposition of the antibacterial agent and the surfactant, the concentration temperature is preferably set to 60 ° C. or lower.

The mixed weight ratio of the antimicrobial agent and the surfactant used in the present invention, that is, the weight ratio of the antimicrobial agent to the surfactant is preferably in the range of 9: 1 to 1: 9 depending on the purpose and application.

In the present invention, the dispersant improves the microdispersion properties of the antimicrobial agent in the thermoplastic resin when added to the thermoplastic resin in combination with the antimicrobial agent, compared to when the antimicrobial agent is added alone. Such a dispersing agent is a metal soap which is a salt of a metal such as lithium, magnesium, calcium and zinc with a fatty acid such as stearic acid, lauric acid and oleic acid, polyethylene wax, polypropylene wax and the like. Hydrocarbon compounds, amide compounds such as stearic acid amide and ethylene bisoleic acid amide, ester compounds such as glycerol tristearate and dioctyl phthalate, higher alcohols such as hexyl alcohol, heptyl alcohol, octyl alcohol and decyl alcohol But compatible with the antibacterial agent and the resin used, dispersion It is particularly excellent in terms of improvement effect and antibacterial effect expression. The other dispersants are not particularly limited as long as they have the above-mentioned effects.

The antimicrobial agent and the dispersant may be mixed in advance in a proper ratio and uniformly, and the resulting formulation may be added to the thermoplastic resin, or each may be added separately to the resin.

The mixing ratio of the antimicrobial agent and the dispersant used in the present invention, that is, the ratio of the antimicrobial agent to the dispersant is in the range of 100: 1 to 1: 100, more preferably 10: 1, by weight depending on the purpose and application. １ ： 1: 10.

In the present invention, any of ε-polylysine and a salt of ε-polylysine may be used.
For applications that are processed at a processing temperature of 230 ° C or higher, ε
-The use of ε-polylysine salt is preferred because the ε-polylysine salt has better thermal stability than the free polylysine.

Examples of the synthetic resin used in the present invention include polyolefin resins such as polypropylene and binary or ternary copolymers of propylene with other α-olefins, low-density polyethylene, linear low-density polyethylene and high-density polyethylene. Thermoplastic resins such as polyethylene terephthalate, polybutylene terephthalate, and copolyester; polyamide resins such as nylon 6 and nylon 66; polystyrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer; and polyvinyl chloride. , Thermoplastic resins such as vinylidene chloride resin,
Thermoplastic elastomers such as ethylene-propylene-rubber copolymers, styrene-butadiene-rubber copolymers and mixtures thereof, and heats of unsaturated polyester resins, diallyl phthalate resins, phenol resins, epoxy resins, melamine-formaldehyde resins, etc. Curable resins can be mentioned.

The method for producing the antibacterial resin composition of the present invention will be described below. In the antibacterial resin composition using a mixture of an antibacterial agent and a surfactant, a powder obtained by uniformly mixing a finely crushed antibacterial agent and a finely crushed surfactant with respect to the synthetic resin described above. Mixture, an antimicrobial agent and a surfactant or a powdery mixture of an antimicrobial agent and a surfactant or a dispersant obtained by uniformly dispersing an antimicrobial agent and a surfactant in an appropriate solvent, followed by drying and pulverization, and an antimicrobial agent and a surfactant. A liquid or paste-like mixture in which the agent and the agent are uniformly dispersed in an appropriate solvent, or a mixture obtained by concentrating the above-mentioned liquid or paste-like mixture, preferably 0.001 to 10% by weight,
More preferably, it is added to the synthetic resin so as to have a weight percentage of 0.01 to 5% by weight, and furthermore, heat stability for preventing heat deterioration, heat resistance, and heat resistance commonly used in general synthetic resins. Stabilizers, weathering agents for adding weather resistance, light stabilizers for adding light resistance, various stabilizers for adding functions, additives, surfactants, organic or inorganic pigments and products It can be obtained by stirring and mixing an organic or inorganic filler for improving the mechanical strength, an antibacterial promoting substance to increase the antibacterial property of ε-polylysine or a salt thereof for imparting functionality, and a thermoplastic resin. Can be obtained in the form of pellets by heating and kneading the stirred and mixed mixture with a heating and kneading apparatus, for example, an extruder or a roll, and then pelletizing. Further, in the case of a composition using a thermosetting resin, a mixture of the above antibacterial agent and surfactant is added to the prepolymer before curing, mixed, put into a mold having a desired shape, and molded. You can also. When the concentration of ε-polylysine or its salt in the resin is less than 0.001% by weight, it is difficult to obtain a sufficient antibacterial effect.
There is no point in increasing the content because the antibacterial property is almost saturated, and the cost is increased, and further, the appearance and mechanical properties of the product may be reduced.

Further, in the antibacterial resin composition to which the antibacterial agent and the dispersant are added, the above thermoplastic resin is
A mixture in which the antibacterial agent and the dispersant are uniformly mixed so as to have an appropriate ratio, or each of the antibacterial agent and the dispersant is added so as to have an appropriate ratio in the resin. At this time, the antimicrobial agent concentration in the resin composition is preferably added to the resin so that the weight percentage is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, and furthermore, usually a thermoplastic resin is added. Widely used in heat stability, heat deterioration prevention, heat stabilizer for adding heat resistance, weathering agent for adding weather resistance, light stabilizer for adding light resistance, and various for adding functionality Stabilizer,
To improve the mechanical strength of additives, surfactants, organic or inorganic pigments, etc. and products, and to increase the antibacterial properties of organic or inorganic fillers and ε-polylysine or salts thereof for imparting functionality. An antibacterial promoting substance can be obtained by stirring and mixing, and also, the stirred and mixed mixture can be obtained in the form of pellets by heating and kneading with a heating and kneading apparatus, for example, a screw extruder, a roll, or the like, and then pelletizing. it can. If the concentration of ε-polylysine or a salt thereof in the resin is significantly lower than 0.001% by weight, it is difficult to obtain a sufficient antibacterial effect.
If the content is more than 10% by weight, the antibacterial property reaches a substantially saturated state, and there is no point in increasing the content, which leads to an increase in cost and a reduction in the appearance and mechanical properties of the product.

In the antibacterial resin composition of the present invention, which comprises a thermoplastic resin and an antibacterial agent, a surfactant and a dispersant, the mixture of the above antibacterial agent and surfactant, A masterbatch in which a mixture of a dispersant or a mixture of an antibacterial agent and a surfactant and a dispersant is added to a thermoplastic resin at a high concentration is prepared in advance, and these masterbatches are prepared at a predetermined antibacterial agent concentration, a dispersant concentration and a It can be manufactured by adding and mixing to a resin so as to obtain the agent concentration.

In order to obtain a desired molded article from the antibacterial resin composition using the thermoplastic resin of the present invention, the resin composition obtained by the above-mentioned method is converted into a desired molded article by using various ordinary molding machines. Obtained by molding.

Further, by using a surfactant, a dispersant or a mixture of both, the dispersibility of the antibacterial agent in the thermoplastic resin is improved, the antibacterial effect is improved, and the surfactant or the dispersant is used. Functions of the dispersant, such as radical scavenging action, improvement of mechanical properties by nucleation effect, improvement of surface gloss of molded article, improvement of smoothness, provision of service lubricity, provision of antistatic function, provision of wet performance, etc. Additional effects are also expected. When a surfactant or dispersant having an antibacterial effect is used, the antibacterial agent and the surfactant act synergistically and synergistically to obtain a resin composition having more excellent antibacterial properties.

[0032]

The details of the present invention will be described below with reference to Test Examples and Examples of the present invention. Note that the present embodiment does not limit the present invention at all.

Examples 1 to 6 Polypropylene (MFR 10 g / 10 min, 230 ° C., 2
1.18N), a mixture of ε-polylysine described in Table 1 described below and a surfactant was added so that the concentration of ε-polylysine in the resin composition became 1% by weight, and then 50 ×
200 ° C, 19.61MP in a 50x0.5mm mold
Heat compression molding was performed for 1 minute under the condition of a to prepare a polypropylene sheet.

[0034]

[Table 1]

Comparative Example 1 A polypropylene sheet was prepared according to Examples 1 to 6, except that ε-polylysine powder was added so that the concentration of ε-polylysine in the resin composition was 1% by weight.

The appearance of the polypropylene sheets obtained in Examples 1 to 6 and Comparative Example 1 was visually observed. Table 2 shows the results.

[0037]

[Table 2]

As is clear from Table 2, the polypropylene sheet obtained from the resin composition to which ε-polylysine and the surfactant mixture of Examples 1 to 6 of the present invention were added was the same as the ε-polylysine of Comparative Example 1. It can be seen that the dispersibility of ε-polylysine in the synthetic resin is excellent and the compatibility with the synthetic resin is better than the polypropylene sheet obtained from the resin composition to which only the powder is added.

Examples 7 to 12 For the same polypropylene used in Example 1,
A mixture of ε-polylysine and a surfactant described in Table 3 described below was used as a ε-polylysine concentration in the resin composition of 0.1.
A polypropylene sheet was prepared in accordance with Examples 1 to 6, except that it was added so as to be 1% by weight.

[0040]

[Table 3]

Comparative Example 2 For the same polypropylene as used in Example 1,
Except that ε-polylysine powder is added so that the ε-polylysine concentration in the resin composition is 0.1% by weight,
A polypropylene sheet was prepared according to Examples 1 to 6.

Examples 13 to 18 For the same polypropylene used in Example 1,
According to Examples 1 to 6, except that a mixture of ε-polylysine and a surfactant described in Table 4 below is added so that the concentration of ε-polylysine in the resin composition becomes 5% by weight. A polypropylene sheet was made.

[0043]

[Table 4]

Comparative Example 3 For the same polypropylene as used in Example 1,
A polypropylene sheet was prepared according to Examples 1 to 6, except that ε-polylysine powder was added so that the concentration of ε-polylysine in the resin composition was 5% by weight.

Comparative Example 4 For the same polypropylene used in Example 1,
A polypropylene sheet was prepared according to Examples 1 to 6, except that neither ε-polylysine powder nor a mixture of ε-polylysine and a surfactant was used.

Comparative Examples 5 to 10 Polypropylene sheets prepared according to Comparative Example 4
After spray-coating a 2% by weight aqueous solution of a mixture of ε-polylysine and a surfactant described in Table 5 below by spraying, the mixture was dried in a hot-air dryer at 50 ° C. for 30 minutes, and dried.
A polypropylene sheet coated with a mixture of polylysine and a surfactant was prepared.

[0047]

[Table 5]

Comparative Example 11 A polypropylene sheet prepared in accordance with Comparative Example 4
A polypropylene sheet coated with ε-polylysine was prepared according to Comparative Examples 5 to 10 except that a 1% by weight aqueous solution of ε-polylysine was applied.

Antibacterial Test 1 Test pieces (50 × 50 ×) prepared from the polypropylene sheets obtained in Examples 1 to 18 and Comparative Examples 1 to 11 described above.
0.5 mm) was washed with running water for 30 to 60 minutes under a flow rate of 2 L / min for 30 to 60 minutes, and then an antibacterial effect test was performed by the following antibacterial test method. Antibacterial Test Method (SEK Shake Flask Method) An antibacterial test was carried out by the following method in accordance with the “Steel Product Sanitation Processing Council Antibacterial and Deodorizing Processed Product Evaluation Test Manual / SEK Shake Flask Method”. After adding 29.7 mL of pH 7.2 phosphate buffer solution to a 100 mL Erlenmeyer flask with a screw cap, after capping,
After being subjected to wet heat sterilization in an autoclave at 121 ° C. and 0.10 MPa for 15 minutes, the mixture was cooled at room temperature. Then, with a sterile pipette, Staphylococ
cus aureus, IFO12732) was inoculated with 0.3 mL of the bacterial suspension, and the number of viable bacteria in the flask was 3.
It was adjusted to 5 × 10 ⁴ cells / mL. A test piece was immersed in this test bacterial solution, shaken at a test temperature of 37 ° C. for 1 to 3 hours, and the number of viable bacteria after shaking was measured by a standard agar medium method. In addition, as a control, the same operation was performed using only the test bacterial solution as a blank test. After the test was completed, the difference between the increase and decrease values was calculated by the following formula, and the results are shown in Tables 6 to 11. Unprocessed sample [A]: Viable bacterial count immediately after inoculation [B]: Viable bacterial count after fixed-time shaking operation Antibacterial processed sample [C]: Viable bacterial count after fixed-time shaking operation Increase / decrease value difference = log ( B / A)-log (C /
A)

[0050]

[Table 6]

[0051]

[Table 7]

[0052]

[Table 8]

[0053]

[Table 9]

[0054]

[Table 10]

[0055]

[Table 11]

As is clear from Tables 6 to 11, the antibacterial effects of the sheets obtained in Examples 1 to 18 of the present invention on Staphylococcus aureus were superior to those of Comparative Examples 1 to 11. You can see that there is. In addition, as compared with the antibacterial effects of Comparative Examples 1 to 3 and Comparative Examples 5 to 11, the antibacterial effects after the cleaning treatment for 30 to 60 minutes are excellent although the unwashed test pieces have the same antibacterial effect. In addition, the same antibacterial effect as in Examples 1 to 18 can be obtained in Comparative Example 3, but ε
-The appearance of the sheet is extremely poor due to the large amount of polylysine added, and the physical properties of the sheet are significantly reduced. There are also problems in productivity and cost.

Antibacterial Test 2 Test pieces (50 × 50 ×) made from the polypropylene sheets obtained in Examples 1 to 18 and Comparative Examples 1 to 11 described above.
0.5 mm) with tap water at a flow rate of 2 L / min for 30 to 60 minutes under running water, and the test bacteria were transformed into E. coli (E. coli) by the same method as the antibacterial test method described in Antibacterial Test 1.
scherichia coli, IFO12734)
An antibacterial test was performed. The results are shown in Tables 12 to 17.

[0058]

[Table 12]

[0059]

[Table 13]

[0060]

[Table 14]

[0061]

[Table 15]

[0062]

[Table 16]

[0063]

[Table 17]

Examples 19 to 24 A 1 L four-necked flask was equipped with a stirring rod, a condenser, a nitrogen gas inlet tube, and a thermometer.
66 g and 228 g of neopentyl glycol are added and heated with stirring. One hour later, the reaction temperature reached 180 ° C, the temperature was gradually raised, and the reaction was carried out for 8 hours.
When the reaction reached −KOH / g, the first-stage reaction was completed and 1
Cool to 00 ° C. After cooling, 116 g of fumaric acid was added, and the mixture was heated and stirred again.
When the acid value reached 25 ° C and the acid value reached 25, the reaction was terminated. The obtained alkyd resin was cooled to 100 ° C., and 200 ppm of hydroquinone was added to 420 g of the resin as a polymerization inhibitor, and a styrene monomer was added as a crosslinking agent to obtain a 65% solution to obtain a liquid unsaturated polyester resin. Was. To this resin composition, 1.2% by weight of a curing agent Permec N (manufactured by NOF Corporation), 5% by weight of cobalt naphthenate as an accelerator, and ε-polylysine and a surfactant described in Table 18 below were used. Was added so that the concentration of ε-polylysine in the composition was 1% by weight, and was uniformly dissolved.
After dispersing, it is poured into a 50 × 50 × 0.5 mm mold and
After holding at 5 ° C for 12 hours, further increase to 80 ° C for 1 hour at 100 ° C
For 2 hours to produce an unsaturated polyester sheet.

[0065]

[Table 18]

Comparative Example 12 Unsaturated polyester sheets were prepared according to Examples 19 to 24, except that ε-polylysine powder was added so that the concentration of ε-polylysine in the resin composition was 1% by weight. .

The appearance of the unsaturated polyester sheets obtained in Examples 19 to 24 and Comparative Example 1 was visually observed. Table 19 shows the results.
It was shown to.

[0068]

[Table 19]

As is clear from Table 19, the unsaturated polyester sheet obtained from the resin composition to which the mixture of ε-polylysine and the surfactant was added in Examples 19 to 24 of the present invention, -It can be seen that, compared to the unsaturated polyester sheet obtained from the resin composition to which only the polylysine powder was added, the dispersibility of ε-polylysine in the synthetic resin was excellent, and the compatibility with the synthetic resin was good.

Examples 25 to 30 Except that a mixture of ε-polylysine and a surfactant described in Table 20 below was added so that the concentration of ε-polylysine in the resin composition was 0.1% by weight. Example 19
Unsaturated polyester sheet was prepared according to.

[0071]

[Table 20]

Comparative Example 13 The procedure of Example 1 was repeated except that ε-polylysine powder was added so that the concentration of ε-polylysine in the resin composition was 0.1% by weight.
Unsaturated polyester sheets were prepared according to Examples 19 to 24.

Examples 31 to 36 A mixture of ε-polylysine and a surfactant described in Table 21 below was used as a ε-polylysine concentration in the resin composition.
Examples 19 to 24, except that they are added so as to be in a% by weight.
An unsaturated polyester sheet was prepared according to the standard.

[0074]

[Table 21]

Comparative Example 14 Unsaturated polyester sheets were prepared according to Examples 19 to 24, except that ε-polylysine powder was added so that the concentration of ε-polylysine in the resin composition was 5% by weight. .

Comparative Example 15 Unsaturated polyester sheets were prepared according to Examples 19 to 24, except that neither ε-polylysine powder nor a mixture of ε-polylysine and a surfactant was used.

Comparative Examples 16 to 21 A 2% by weight aqueous solution of a mixture of ε-polylysine and a surfactant described in Table 22 below was sprayed on an unsaturated polyester sheet prepared in accordance with Comparative Example 15 by spraying. After spray coating, the mixture was dried in a hot air drier at 50 ° C. for 30 minutes to prepare an unsaturated polyester sheet coated with a mixture of ε-polylysine and a surfactant.

[0078]

[Table 22]

Comparative Example 22 An unsaturated polyester sheet prepared in accordance with Comparative Example 15 was coated with ε-polylysine in accordance with Comparative Examples 16 to 21 except that a 1% by weight aqueous solution of ε-polylysine was coated. A saturated polyester sheet was made.

Antibacterial Test 3 Test pieces (50) made from the unsaturated polyester sheets obtained in Examples 19 to 36 and Comparative Examples 12 to 22 described above.
(× 50 × 0.5 mm) was washed with running water for 30 to 60 minutes at a flow rate of 2 L / min for 30 to 60 minutes, and then subjected to the antibacterial test in the same manner as the antibacterial test method described in the antibacterial test 1. . The results are shown in Tables 23 to 28.

[0081]

[Table 23]

[0082]

[Table 24]

[0083]

[Table 25]

[0084]

[Table 26]

[0085]

[Table 27]

[0086]

[Table 28]

As is clear from Tables 23 to 28, the antibacterial effects of the sheets obtained in Examples 19 to 36 of the present invention on Staphylococcus aureus were superior to those of Comparative Examples 12 to 22. You can see that there is. Comparative Example 12
As compared with the antibacterial effects of Comparative Examples 16 to 21 and Comparative Examples 16 to 21, 30 to 6
The antibacterial effect after the 0 minute washing treatment is excellent. In Comparative Example 14, the same antibacterial effect as in Examples 19 to 36 was obtained, but the appearance of the sheet was extremely poor due to the large amount of ε-polylysine, and the physical properties of the sheet were significantly reduced. There are also problems in productivity and cost.

Antibacterial Test 4 Test pieces (50) prepared from the unsaturated polyester sheets obtained in Examples 19 to 36 and Comparative Examples 12 to 22 described above.
× 50 × 0.5 mm) was washed with running water for 30 to 60 minutes at a flow rate of 2 L / min for 30 to 60 minutes, and then subjected to the antibacterial test in the same manner as the antibacterial test method described in Antibacterial Test 2. . The results are shown in Tables 29 to 34.

[0089]

[Table 29]

[0090]

[Table 30]

[0091]

[Table 31]

[0092]

[Table 32]

[0093]

[Table 33]

[0094]

[Table 34]

As is clear from Tables 29 to 34, the antibacterial effect of the sheets obtained in Examples 19 to 36 of the present invention on Escherichia coli was superior to that of Comparative Examples 12 to 22. I understand. Further, as compared with the antibacterial effects of Comparative Examples 12 to 14 and Comparative Examples 16 to 21, the antibacterial effects after the cleaning treatment for 30 to 60 minutes are excellent, although the unwashed test pieces have the same antibacterial effect. In Comparative Example 14, the same antibacterial effect as in Examples 19 to 36 was obtained, but the appearance of the sheet was extremely poor due to the large amount of ε-polylysine, and the physical properties of the sheet were significantly reduced. There are also problems in productivity and cost.

Examples 37 to 41 Polypropylene (MFR 10 g / 10 min, 230 ° C., 2
1.18N), 0.1% by weight of ε-polylysine and 0.3% by weight of a dispersant described in Table 35 described below were added thereto, and then 200 μm in a 50 × 50 × 0.5 mm mold.
Heat compression molding was performed for 1 minute at a temperature of 19.61 MPa to produce a polypropylene sheet.

[0097]

[Table 35]

The appearance of the polypropylene sheets obtained in Examples 37 to 41 and Comparative Example 2 was visually observed and evaluated according to the following criteria. The results are shown in Table 36 below. ：: The sheet appearance was extremely excellent, and it was determined that the sheet could be used without problems in a wide range of applications. ：: The sheet appearance is excellent, and it is determined that the sheet can be used in a wide range of applications without any problem. X: It is determined that the sheet cannot be used because of poor sheet appearance and poor appearance.

[0099]

[Table 36]

As is clear from Table 36, the sheets obtained from the resin compositions of Examples 37 to 41 of the present invention in which ε-polylysine as an antibacterial agent and a dispersant are used in combination are the same as those of Comparative Example 2. -It can be seen that the dispersibility of ε-polylysine in the resin is excellent as compared with the sheet obtained from the resin composition to which only polylysine was added.

Examples 42 to 46 Based on the same polypropylene used in Examples 37 to 41, 0.05% by weight of ε-polylysine and Table 37 to be described later were used.
A polypropylene sheet was prepared according to Examples 37 to 41, except that the dispersant described in above was added so as to be 0.3% by weight.

Comparative Example 23 A polypropylene sheet was prepared according to Examples 42 to 46 except that no dispersant was used.

[0103]

[Table 37]

Examples 47 to 51 Based on the same polypropylene used in Examples 37 to 41, 0.5% by weight of ε-polylysine and 0.3% by weight of a dispersant described in Table 38 below were used. , A polypropylene sheet was prepared according to Examples 37 to 41.

Comparative Example 24 A polypropylene sheet was prepared according to Examples 47 to 51 except that no dispersant was used.

[0106]

[Table 38]

Antibacterial Test 5 Examples 37 to 51 and Comparative Examples 2, 4, 23 to 24
(50 × 50 ×)
0.5 mm) was washed with running water at a flow rate of 2 L / min for 0 to 30 minutes using a tap water, and an antibacterial effect test was performed by the following antibacterial test method.

Antibacterial Test Method (Film Adhesion Method) The “film adhesion method” which is a synthetic resin antibacterial test method specified in the “Studies on the Study of Silver and Other Inorganic Antibacterial Agents (1995)” The antibacterial test was performed according to the above.

Preparation of Test Bacterial Solution Normal broth medium was diluted 500-fold with sterile purified water.
E. coli (Escherichia coli) was added to a 1/500 medium in which H was adjusted to 7.0 ± 0.2 using a sterilized pipette.
li, IFO3972), the viable cell count in the medium was 3.0 ×
And adjusted to a concentration of 10 ⁵ cells / mL.

Preparation of Test Pieces The resin pieces to be subjected to the antibacterial test were gently wiped twice or three times with a local gauze soaked in ethanol, and dried again at room temperature to obtain test pieces.

Antimicrobial test Each test piece was placed in a sterile petri dish, and the test surface was inoculated with 0.5 mL of the inoculum bacterial solution, covered with a sterilized polyethylene coating film, and capped. Culture was performed for 24 hours under the conditions of a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more. After the cultivation, the bacteria adhering to each test piece and the clothing film were sufficiently washed out in a sterilized petri dish using SCDLP medium (10 mL), and the washed liquid 1
The number of viable bacteria in mL was measured by a standard agar medium method. After the test was completed, the difference between the increase and decrease values was calculated by the following formula, and the results are shown in Table 39 below.

Antibacterial unprocessed sample [A]: Viable bacterial count immediately after inoculation [B]: Viable bacterial count after fixed-time culture operation Antibacterial processed sample [C]: Viable bacterial count after fixed-time culture operation Increase / decrease value difference = log (B / A)-log (C /
A)

[0113]

[Table 39]

As is clear from Table 39, the antibacterial effects of the sheets obtained from the resin compositions using the ε-polylysine of Examples 37 to 51 of the present invention in combination with the dispersant against Escherichia coli were compared with those of Comparative Examples 2, 23 and It can be seen that both the unwashed test piece and the washed test piece have an excellent antibacterial effect as compared with those obtained from the resin composition to which only ε-polylysine was added.

Antibacterial Test 6 Examples 37 to 51 and Comparative Examples 2, 4, 23 to 24
(50 × 50 ×)
0.5 mm) was washed with running water at a flow rate of 2 L / min for 0 to 30 minutes using tap water, and the test bacterium was tested for yellow grape by the same method as the antibacterial test method described in Antibacterial Test 1. Staphylococcus aur
eus, IFO12732). The results are shown in Table 40 below.

[0116]

[Table 40]

As is clear from Table 40, the antibacterial effect of the sheet obtained from the resin composition in which ε-polylysine of Examples 37 to 51 of the present invention was used in combination with a dispersant against Staphylococcus aureus was compared with Comparative Example 2, It can be seen that both the unwashed test piece and the washed test piece have an excellent antibacterial effect as compared with those obtained from the resin compositions to which only ε-polylysine of Nos. 23 and 24 were added.

Examples 52 to 55 Polypropylene (MFR 10 g / 10 min, 230 ° C., 2
1.18N), a mixture of ε-polylysine and a surfactant described in Table 41 described below was added so that the concentration of ε-polylysine in the resin composition was 1% by weight, and then 50%.
200 ° C, 19.61M in a × 50 × 0.5mm mold
Heat compression molding was performed for 1 minute under the condition of Pa to prepare a polypropylene sheet.

[0119]

[Table 41]

The appearance of the polypropylene sheets obtained in Examples 52 to 55 and Comparative Example 1 was visually observed. The results are shown in Table 42.

[0121]

[Table 42]

As is apparent from Table 42, the polypropylene sheet obtained from the resin composition of Examples 52 to 55 of the present invention to which the ε-polylysine and the surfactant mixture were added was the same as the ε-polylysine of Comparative Example 1. It can be seen that the dispersibility of ε-polylysine in the synthetic resin is excellent and the compatibility with the synthetic resin is better than the polypropylene sheet obtained from the resin composition to which only the powder is added.

Examples 56 to 59 The same polypropylene as that used in Examples 52 to 55 was mixed with a mixture of ε-polylysine and a surfactant described in Table 43 below to obtain ε-polylysine in the resin composition. A polypropylene sheet was prepared in accordance with Examples 52 to 55 except that the concentration was 0.1% by weight.

[0124]

[Table 43]

Examples 60 to 63 A mixture of ε-polylysine and a surfactant described in Table 44 below was used for the same polypropylene as that used in Examples 52 to 55, and ε-polylysine in the resin composition was used. Example 52 was repeated except that the concentration was adjusted to 5% by weight.
A polypropylene sheet was prepared according to No.-55.

[0126]

[Table 44]

Comparative Examples 25 to 28 Polypropylene sheets prepared according to Comparative Example 4
A 2% by weight aqueous solution of a mixture of ε-polylysine and a surfactant described in Table 45 described below is spray-coated using a spray, and then dried in a hot-air dryer at 50 ° C. for 30 minutes.
-A polypropylene sheet coated with a mixture of polylysine and surfactant was prepared.

[0128]

[Table 45]

Antibacterial Test 7 Examples 52-63 and Comparative Examples 1-4, 25-28
A test piece (50 × 50 × 0.5 mm) prepared from the polypropylene sheet obtained in the above was used at a flow rate of 2 L using tap water.
After washing with running water for 30 to 60 minutes under the conditions of / min, an antibacterial test was performed in the same manner as the antibacterial test method described in the antibacterial test 1. The results are shown in Tables 46 to 49.

[0130]

[Table 46]

[0131]

[Table 47]

[0132]

[Table 48]

[0133]

[Table 49]

As is clear from Tables 46 to 49, the antibacterial effects of the sheets obtained in Examples 52 to 63 of the present invention on Staphylococcus aureus are different from those of Comparative Examples 1-4 and 25-28. It turns out that it is superior. In addition, as compared with the antibacterial effects of Comparative Examples 1 to 3 and Comparative Examples 25 to 28, although the unwashed test pieces have the same antibacterial effect,
The antibacterial effect after the washing treatment for 0 to 60 minutes is excellent. In addition,
Also in Comparative Example 3, the same antibacterial effect as in Examples 56 to 63 is obtained, but the appearance of the sheet is extremely poor due to the large amount of ε-polylysine, and the physical properties of the sheet are significantly reduced.
There are also problems in productivity and cost.

Antibacterial Test 8 Examples 52-63 and Comparative Examples 1-4, 25-28
A test piece (50 × 50 × 0.5 mm) prepared from the polypropylene sheet obtained in the above was used at a flow rate of 2 L using tap water.
After washing with running water for 30 to 60 minutes under the condition of / min, an antibacterial test was performed by the same method as the antibacterial test method described in the antibacterial test 2. The results are shown in Tables 50 to 53.

[0136]

[Table 50]

[0137]

[Table 51]

[0138]

[Table 52]

[0139]

[Table 53]

As is clear from Tables 50 to 53, the antibacterial effects of the sheets obtained in Examples 52 to 63 of the present invention on Staphylococcus aureus were lower than those of Comparative Examples 1 to 4, 25 to 28. It turns out that it is superior. In addition, as compared with the antibacterial effects of Comparative Examples 1 to 3 and Comparative Examples 25 to 28, although the unwashed test pieces have the same antibacterial effect,
The antibacterial effect after the washing treatment for 0 to 60 minutes is excellent. In addition,
Also in Comparative Example 3, the same antibacterial effect as in Examples 56 to 63 is obtained, but the appearance of the sheet is extremely poor due to the large amount of ε-polylysine, and the physical properties of the sheet are significantly reduced.
There are also problems in productivity and cost.

Examples 64 to 67 To the same unsaturated polyester resin as used in Examples 19 to 24, a mixture of ε-polylysine and a surface active substance shown in Table 54 below was added to a resin composition. Unsaturated polyester sheets were prepared according to Examples 19 to 24, except that ε-polylysine was added so as to have a concentration of 1.0% by weight.

[0142]

[Table 54] With respect to the unsaturated polyester sheets obtained in Examples 64 to 67 and Comparative Example 12, the appearance of the sheet was visually observed. The results are shown in Table 55.

[0143]

[Table 55]

As is clear from Table 55, the unsaturated polyester sheet obtained from the resin composition to which the ε-polylysine and the surfactant mixture of Examples 64 to 67 of the present invention were added was different from the ε of Comparative Example 12 -It can be seen that, compared to the unsaturated polyester sheet obtained from the resin composition to which only the polylysine powder was added, the dispersibility of ε-polylysine in the synthetic resin was excellent, and the compatibility with the synthetic resin was good.

Examples 68 to 71 Except that a mixture of ε-polylysine and a surfactant described in Table 56 below was added so that the concentration of ε-polylysine in the resin composition was 0.1% by weight. Example 19
Unsaturated polyester sheet was prepared according to.

[0146]

[Table 56]

Examples 72 to 75 A mixture of ε-polylysine and a surfactant described in Table 57 below was used as the ε-polylysine concentration in the resin composition.
Examples 19 to 24, except that they are added so as to be in a% by weight.
An unsaturated polyester sheet was prepared according to the standard.

[0148]

[Table 57]

Comparative Examples 25 to 28 A 2% by weight aqueous solution of a mixture of ε-polylysine and a surfactant described in Table 58 described below was sprayed on an unsaturated polyester sheet prepared in accordance with Comparative Example 15. After spray coating, the mixture was dried in a hot air drier at 50 ° C. for 30 minutes to prepare an unsaturated polyester sheet coated with a mixture of ε-polylysine and a surfactant.

[0150]

[Table 58]

Antibacterial Test 9 Examples 64-75 and Comparative Examples 12-15, 25-
After washing a test piece (50 × 50 × 0.5 mm) prepared from the unsaturated polyester sheet obtained in No. 28 with tap water at a flow rate of 2 L / min for 30 to 60 minutes, an antibacterial test 1 The antibacterial test was performed by the same method as the antibacterial test method described above. The results are shown in Tables 59 to 62.

[0152]

[Table 59]

[0153]

[Table 60]

[0154]

[Table 61]

[0155]

[Table 62]

As is clear from Tables 59 to 62, the antibacterial effects of the sheets obtained in Examples 64 to 75 of the present invention on Staphylococcus aureus are shown in Comparative Examples 12 to 15, 25 to 28,
It can be seen that the antibacterial effect is excellent in comparison with that of No. In addition, as compared with the antibacterial effects of Comparative Examples 12 to 14 and Comparative Examples 25 to 28, the antibacterial effects after the cleaning treatment for 30 to 60 minutes are excellent although the unwashed test pieces have the same antibacterial effect. In Comparative Example 14, the same antibacterial effect as in Examples 19 to 36 was obtained, but the appearance of the sheet was extremely poor due to the large amount of ε-polylysine, and the physical properties of the sheet were significantly reduced. There are also problems in productivity and cost.

Antibacterial Test 10 Examples 64 to 75 and Comparative Examples 12 to 15, 25 to 25
A test piece (50 × 50 × 0.5 mm) prepared from the unsaturated polyester sheet obtained in step 28 was washed with running tap water for 30 to 60 minutes at a flow rate of 2 L / min. The antibacterial test was performed by the same method as the antibacterial test method described above. The results are shown in Tables 63 to 66.

[0158]

[Table 63]

[0159]

[Table 64]

[0160]

[Table 65]

[0161]

[Table 66]

As is clear from Tables 63 to 66, the antibacterial effect of the sheets obtained in Examples 64 to 75 of the present invention on Escherichia coli was smaller than that of Comparative Examples 12 to 15, 25 to 28. It is understood that it is excellent. Further, as compared with the antibacterial effects of Comparative Examples 12 to 14 and Comparative Examples 25 to 28, although the same antibacterial effect was obtained with the unwashed test piece, 3
The antibacterial effect after the washing treatment for 0 to 60 minutes is excellent. In addition,
In Comparative Example 14, the same antibacterial effect as in Examples 19 to 36 was obtained, but the appearance of the sheet was extremely poor due to the large amount of ε-polylysine, and the physical properties of the sheet were significantly reduced. There are also problems in productivity and cost.

Examples 76 to 77 Polypropylene (MFR 10 g / 10 min, 230 ° C., 2
1.18N), 0.1% by weight of ε-polylysine and 0.3% by weight of a dispersant described in Table 67 described below were added thereto, and then 200 μm in a 50 × 50 × 0.5 mm mold.
Heat compression molding was performed for 1 minute at a temperature of 19.61 MPa to produce a polypropylene sheet.

[0164]

[Table 67]

The appearance of the polypropylene sheets obtained in Examples 76 to 77 and Comparative Example 2 was visually observed, and the results are shown in Table 68 below.

[0166]

[Table 68]

As is clear from Table 68, the sheets obtained from the resin compositions of Examples 76 to 77 of the present invention in which ε-polylysine as an antibacterial agent and a dispersant are used in combination are the same as those of Comparative Example 2. -It can be seen that the dispersibility of ε-polylysine in the resin is excellent as compared with the sheet obtained from the resin composition to which only polylysine was added.

Examples 78 to 79 Based on the same polypropylene used in Examples 76 to 77, 0.05% by weight of ε-polylysine and Table 69 to be described later were used.
The polypropylene sheet was prepared according to Examples 76 to 77 except that the dispersant described in (1) was added so as to be 0.3% by weight.

[0169]

[Table 69]

Examples 80 to 81 Based on the same polypropylene as used in Examples 76 to 77, 0.5% by weight of ε-polylysine and 0.3% by weight of a dispersant described in Table 70 described below were used. , A polypropylene sheet was prepared in accordance with Examples 76 to 77.

[0171]

[Table 70]

Antibacterial Test 11 Examples 76 to 77 and Comparative Examples 2, 4, 23 to 24
(50 × 50 ×)
0.5 mm) was washed with running water at a flow rate of 2 L / min for 0 to 30 minutes using tap water, and an antibacterial test was performed in the same manner as the antibacterial test method described in Antibacterial Test 5. The results are shown in Table 71 below.

[0173]

[Table 71]

As is clear from Table 71, the antibacterial effect of the sheet obtained from the resin composition using the ε-polylysine of Examples 76 to 81 of the present invention and the dispersant in combination against Escherichia coli was compared with Comparative Examples 2, 23 and It can be seen that both the unwashed test piece and the washed test piece have an excellent antibacterial effect as compared with those obtained from the resin composition to which only ε-polylysine was added.

Antibacterial Test 12 Examples 76 to 77 and Comparative Examples 2, 4, 23 to 24
(50 × 50 ×)
(0.5 mm) was washed with running water at a flow rate of 2 L / min for 0 to 30 minutes using the same method as the antibacterial test described in Antibacterial Test 6. The results are shown in Table 72 below.

[0176]

[Table 72]

As is clear from Table 72, the antibacterial effect of the sheet obtained from the resin composition using the ε-polylysine of Examples 76 to 81 of the present invention in combination with the dispersant against Staphylococcus aureus was compared with Comparative Example 2, It can be seen that both the unwashed test piece and the washed test piece have an excellent antibacterial effect as compared with those obtained from the resin compositions to which only ε-polylysine of Nos. 23 and 24 were added.

Examples 82 to 84 Polypropylene (MFR 10 g / 10 min, 230 ° C., 2
1.18N), 0.1% by weight of ε-polylysine, 0.1% by weight of a surfactant described in Table 73 below, and 0.1% by weight of a dispersant.
After adding to 1% by weight, 50 × 50 × 0.
Heat compression molding was performed in a 5 mm mold at 200 ° C. and 19.61 MPa for 1 minute to prepare a polypropylene sheet.

[0179]

[Table 73]

The appearance of the polypropylene sheets obtained in Examples 82 to 84 and Comparative Example 2 was visually observed, and the results are shown in Table 74 below.

[0181]

[Table 74]

As is clear from Table 74, the sheets obtained from the resin compositions of Examples 82 to 84 of the present invention in which ε-polylysine as an antibacterial agent and a surfactant and a dispersant were used in combination were compared. As compared with the sheet obtained from the resin composition to which only the ε-polylysine of Example 2 was added, the ε-
It can be seen that the dispersibility of polylysine is excellent.

Examples 85 to 87 Based on the same polypropylene used in Examples 82 to 84, 0.05% by weight of ε-polylysine and Table 75 described later were used.
The polypropylene sheet was prepared according to Examples 76 to 77 except that the surfactant was added so as to be 0.1% by weight and the dispersing agent was 0.1% by weight described in (1).

[0184]

[Table 75]

Examples 88 to 90 Based on the same polypropylene used in Examples 82 to 84, 0.5% by weight of ε-polylysine, 0.1% by weight of a surfactant described in Table 76 below, and a dispersant Was prepared according to Examples 76 to 77, except that 0.1% by weight was added.

[0186]

[Table 76]

Antibacterial Test 13 Examples 82 to 90 and Comparative Examples 2, 4, 23 to 24
(50 × 50 ×)
0.5 mm) was washed with running water at a flow rate of 2 L / min for 0 to 30 minutes using tap water, and an antibacterial test was performed in the same manner as the antibacterial test method described in Antibacterial Test 5. The results are shown in Table 77 below.

[0188]

[Table 77]

As is clear from Table 77, the antibacterial effect of the sheet obtained from the resin composition using ε-polylysine of Examples 82 to 90 of the present invention, a surfactant and a dispersant in combination against Escherichia coli was compared with that of Comparative Example. It can be seen that both the unwashed test piece and the washed test piece have an excellent antibacterial effect as compared with those obtained from the resin compositions to which only 2, 23 and 24 ε-polylysine were added.

Antibacterial Test 14 Examples 82 to 90 and Comparative Examples 2, 4, 23 to 24
(50 × 50 ×)
(0.5 mm) was washed with running water at a flow rate of 2 L / min for 0 to 30 minutes using the same method as the antibacterial test described in Antibacterial Test 6. The results are shown in Table 78 below.

[0191]

[Table 78]

As is clear from Table 78, the antibacterial effect of the sheet obtained from the resin composition in which ε-polylysine of Examples 82 to 90 of the present invention was used in combination with a dispersant against Staphylococcus aureus was compared with Comparative Example 2, It can be seen that both the unwashed test piece and the washed test piece have an excellent antibacterial effect as compared with those obtained from the resin compositions to which only ε-polylysine of Nos. 23 and 24 were added.

[0193]

The antibacterial resin composition of the present invention has excellent antibacterial properties, and uses ε-polylysine or a salt thereof used as a food preservative as an antibacterial agent. It has very low adverse effects on the human body and is safe. In addition, by adding these antibacterial agents and surfactants, dispersants or mixtures thereof in combination to a thermoplastic resin or a thermosetting resin, the dispersibility of the antibacterial agent in the resin is improved. A molded article obtained by molding the resin composition has excellent appearance, and additionally has excellent washing and washing resistance. Therefore, it can be suitably used in a wide range of fields such as various molded articles, films, sheets, fibers and the like which require antibacterial properties. Further, the molded article obtained by using the resin composition of the present invention maintains its antibacterial effect even when used repeatedly, and is suitable for use for long-term use.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 89/00 C08L 89/00 101/00 101/00 // C12P 13/08 C12P 13/08 A (C08L 23/12 77: 02) (C08L 67/06 77:02) (C08L 101/00 77:02) (C08L 101/00 89:00)

Claims (25)

[Claims] An antibacterial resin composition comprising a synthetic resin and ε-polylysine or a mixture of ε-polylysine salt and a surfactant. 2. An antibacterial resin composition wherein 0.001 to 10% by weight of a synthetic resin is added with a mixture of ε-polylysine or ε-polylysine salt and a surfactant. 3. The antibacterial composition according to claim 1, wherein the mixture of ε-polylysine or ε-polylysine salt and the surfactant is a mixture having a mixing ratio of 9: 1 to 1: 9. Resin composition. 4. The ε-polylysine salt is a salt of an inorganic acid or an organic acid of ε-polylysine.
The antibacterial resin composition according to any one of the above. 5. The surfactant is at least one surfactant selected from fatty acid esters of glycerin, fatty acid esters of sorbitol, fatty acid esters of sorbitan, and polyhydric alcohol-type nonionic surfactants of alkyl glucosides. The antibacterial resin composition according to any one of claims 1 to 3. 6. The surfactant according to claim 1, wherein the surfactant is at least one of a polyethylene glycol type nonionic surfactant.
The antibacterial resin composition according to claim 3. 7. The antibacterial resin composition according to claim 1, wherein the surfactant is at least one of betaine-type amphoteric surfactants. 8. The antibacterial resin composition according to claim 1, wherein the surfactant is at least one kind of a quaternary ammonium salt type cationic surfactant. 9. The surfactant according to claim 1, wherein the surfactant is at least two or more surfactants selected from the surfactant according to any one of claims 6 to 8. An antibacterial resin composition according to any one of the preceding claims. 10. The synthetic resin is a thermoplastic resin.
The antibacterial resin composition according to any one of claims 9 to 9. 11. The synthetic resin is a thermosetting resin.
The antibacterial resin composition according to any one of claims 9 to 9. 12. A molded article obtained by using the antibacterial resin composition according to any one of claims 1 to 11. 13. An antibacterial resin composition comprising ε-polylysine or ε-polylysine salt and a dispersant in a thermoplastic resin. 14. An amount of ε-polylysine or ε-polylysine salt relative to the composition of the thermoplastic resin is 0.001 to 0.001.
10% by weight and ε-polylysine or ε-
100: 1 to 1: 100 based on polylysine salt
The antibacterial resin composition contained in the range of. 15. The thermoplastic resin is a polyolefin resin, a thermoplastic polyester resin, a polyamide resin,
The antibacterial resin composition according to claim 13, which is a polystyrene resin, a vinyl chloride resin, a vinylidene chloride resin, a thermoplastic elastomer, or a mixture thereof. 16. The antibacterial resin composition according to claim 13, wherein the dispersant is at least one dispersant selected from metal salts of fatty acids. 17. The antibacterial resin composition according to claim 13, wherein the dispersant is at least one dispersant selected from hydrocarbon compounds. 18. The antibacterial resin composition according to claim 13, wherein the dispersant is at least one dispersant selected from amide compounds. 19. The antibacterial resin composition according to claim 13, wherein the dispersant is at least one dispersant selected from ester compounds. 20. The antibacterial resin composition according to claim 13, wherein the dispersant is at least one dispersant selected from higher alcohols. 21. The dispersant according to claim 13 or 14, wherein the dispersant is at least two or more dispersants selected from the dispersants according to any one of claims 16 to 20.
The antibacterial resin composition according to any one of the above. A molded article obtained by using the antibacterial resin composition according to any one of claims 13 to 21. 23. An ε-polylysine or an ε-polylysine salt, at least one surfactant according to any one of claims 5 to 8, and at least one of a surfactant and a thermoplastic resin.
An antibacterial resin composition containing at least one of the dispersants according to claim 20. 24. An amount of ε-polylysine or ε-polylysine salt relative to the composition of the thermoplastic resin is from 0.001 to 0.001.
10% by weight, and at least one surfactant according to any one of claims 5 to 8 is 0.0001% to 50% by weight, based on the composition. 21. An antimicrobial resin composition comprising at least one dispersant according to any one of 20 to 20% by weight relative to the composition. (25) A molded article obtained by using the antibacterial resin composition according to any one of (23) and (24).