WO2020013033A1

WO2020013033A1 - Antiviral resin composition

Info

Publication number: WO2020013033A1
Application number: PCT/JP2019/026321
Authority: WO
Inventors: 素美夏目; 英雄竹内; 靖弘井戸田; 掛樋　浩司
Original assignee: 株式会社Ｌｉｘｉｌ
Priority date: 2018-07-09
Filing date: 2019-07-02
Publication date: 2020-01-16
Also published as: JP2020007265A; JP7198601B2

Abstract

An antiviral resin composition comprising a polyamide-based resin and an antiviral agent that is soluble in water and has a decomposition temperature higher than the melting temperature of the polyamide-based resin. Due to moisture absorbed in the polyamide-based resin, the water-soluble antiviral agent existing inside the antiviral resin composition is gradually eluted toward the surface of the resin composition. As a result, the antiviral agent can sustainably exert the antiviral effect over a long period of time on the surface of the antiviral resin composition.

Description

Antiviral resin composition

The present disclosure relates to an antiviral resin composition.

JP-A-2000-302615 discloses various functional resin compositions in which a functional material such as an antiviral agent is added to impart functionalities to the surface.

In this functional resin composition, the functional material existing near the surface exerts its effect, whereas the functional material buried inside the resin cannot exert its effect, so it is important to arrange the functional material on the surface. is there. The functional resin composition is required to have abrasion resistance and water resistance. When the surface of the functional resin composition disappears due to abrasion, the functional material buried inside the functional resin composition is exposed to the surface, so that the functionality can be maintained. On the other hand, when the functional material on the surface of the functional resin composition is eluted by water, the resin on the surface remains without being lost, and the functionality is reduced. In other words, there is a problem that the functional material is lost at an early stage due to the elution of the functional material upon contact with water during use.

機能 By the way, when the functional material buried inside the resin is a low-molecular-weight and easily movable substance of less than the order of submicron, it may move (bleed) inside the resin and move to the surface. That is, by increasing the fluidity of the functional material inside the resin, the functional material buried inside the resin can function on the surface.

The present disclosure uses a water-soluble antiviral agent and, by using a resin having water absorbability, transfers a functional material buried in the resin to the resin surface, and can exhibit a function for a long period of time. The purpose is to provide.

An antiviral resin composition of the present disclosure is an antiviral resin composition, comprising a polyamide resin and an antiviral agent that exhibits water solubility and has a decomposition temperature higher than the melting temperature of the polyamide resin. .

FIG. 1 shows bleeding of an antiviral agent in an antiviral resin composition according to an embodiment, FIG. 2 shows bleeding of an antiviral agent in an antiviral resin composition containing glass fibers according to the embodiment, FIG. 3 shows the relationship between the amount of antiviral agent added and the amount of calcium ion (Ca ²⁺ ) eluted in water in the antiviral resin composition according to the embodiment, FIG. 4 shows the relationship between the amount of calcium ion eluted in water and the antiviral property of each virus in the antiviral resin composition according to the embodiment.

The antiviral resin composition 1 according to the present embodiment includes a polyamide base resin 2 and an antiviral agent 3 that exhibits water solubility and has a decomposition temperature higher than the melting temperature of the base resin 2. You. The antiviral resin composition 1 exerts an antiviral effect on its surface by the antiviral agent 3 existing near the surface. Antiviral agent 3 also exerts an antibacterial effect. Other raw materials can be blended with the antiviral resin composition 1 as long as the effects of the present disclosure are not impaired. Examples include polymerization inhibitors, curing agents, curing accelerators, dyes, plasticizers, ultraviolet absorbers, thixotropic agents, fillers, defoamers, stabilizers, leveling agents, and the like.

ポリアミド As the base resin 2, a polyamide resin is used. Since the polyamide resin has high water absorption, bleeding occurs when the water-soluble antiviral agent 3 dissolves in the absorbed water, and the antiviral agent 3 inside the base resin 2 is applied to the surface of the antiviral resin composition 1. As a result, the antibacterial and antiviral actions are exerted continuously (see FIG. 1). Specific examples of the polyamide resin include 6-nylon and 6,6-nylon. Bleeding is more likely to occur as the water absorption is higher, and an antiviral effect is more likely to be obtained. Preferably, a polyamide resin having a water absorption of 1% by mass or more is used as the base resin 2. The method of measuring the water absorption will be described in detail later.

The antiviral agent 3 is added to the base resin 2. The base resin 2 is formed by either injection molding or extrusion molding. For this reason, the decomposition temperature of the antiviral agent 3 is required to be higher than the melting temperature (molding temperature) of the base resin 2. Furthermore, from the viewpoint of easiness of bleeding in the antiviral resin composition 1, it is necessary to be water-soluble. Substances exhibiting antibacterial and antiviral properties include quaternary ammonium salts, calcium hydroxide (slaked lime), TiO ₂ supported on copper, and copper iodide. In view of the above, slaked lime is more preferably used. This is because slaked lime is water-soluble and its decomposition temperature is as high as 400 ° C. or higher, which is higher than the melting temperature of various polyamide resins (for example, 250 ° C. to 320 ° C.).

(4) The antiviral agent 3 has an antibacterial activity against bacteria such as Escherichia coli and Staphylococcus aureus, and has an antiviral activity against enveloped viruses and non-enveloped viruses. Regarding the above antiviral properties, it is possible to evaluate the antiviral properties by measuring the infectious titer of the influenza A virus as an enveloped virus and the feline calicivirus as a non-enveloped virus by the TCID50 method. is there.

Further, it is preferable that the antiviral resin composition 1 contains the filler 4. When the antiviral agent 3 dissolves in the absorbed water and bleeds inside the antiviral resin composition 1, compared to when the antiviral agent 3 passes through the infinite number of complicated crosslinked structures in the base resin 2, This is because the inclusion of No. 4 results in formation of a path that easily passes through the boundary between the filler 4 and the base resin 2, thereby promoting bleeding of the antiviral agent 3 (see FIG. 2).

The filler 4 is preferably one that can be kneaded with a resin, for example, glass fiber or the like is more preferably used. This is because, along with the improvement of the strength, the long fiber shape well forms a route for transferring the antiviral agent 3 to the surface of the antibacterial / antiviral antiviral resin composition 1.

Next, a method for producing the antiviral resin composition 1 of the present embodiment will be described.

製造 Examples of the method for producing the antiviral resin composition 1 include a pelletizing method, a direct addition method, a master batch method, and the like.

In the pelletizing method, the base resin 2 and the antiviral agent 3 are kneaded using a kneader to produce a pellet of the target antiviral resin composition 1. At the time of kneading, the temperature of the base resin 2 is raised to a melting temperature or higher to melt the base resin 2. The antiviral agent 3 according to the target content is added to the melted base resin 2 and kneaded well, and when it becomes uniform, it is molded into a pellet. Using the pellets, a member is manufactured by molding into a desired shape.

In the direct addition method, when the base resin 2 is injection-molded, the antiviral / antiviral agent is directly added, whereby the antiviral resin composition 1 molded into a desired shape can be obtained. The antiviral resin composition 1 can be obtained by putting the base resin 2 and the antiviral agent 3 mixed in advance into an injection molding machine. The temperature during injection molding is equal to or higher than the melting temperature of the base resin 2 as in the pelletizing method.

In the masterbatch method, pellets having a large content of the antiviral agent 3 in the pelletizing method are prepared, and the pellets are added to the injection molding machine together with the base resin 2, whereby the antiviral resin composition 1 having the desired composition is obtained. can get.

実施 The following examples and comparative examples are examples produced using either the pelletizing method or the master batch method. The effects of the present disclosure are similarly exerted regardless of the above-mentioned manufacturing method.

Next, the present invention will be described in more detail based on embodiments. The present disclosure is not limited to this. Detailed mixing ratios of the examples are described later in Table 1 together with the evaluation results.

<Examples and Comparative Examples>
Polyamide resin was used as the base resin, and slaked lime (Kanto Chemical Reagents) was used as the antibacterial and antiviral agent. The feed amount of the feeder was controlled so that the content of the antibacterial / antiviral agent in the resin composition was 5% by mass. Antibacterial and antiviral agents were kneaded into each resin by a kneader to produce pellets. The kneading conditions were a screw diameter of φ25 mm, L / D = 41, the number of kneading chambers was eight, and the kneading temperature was set in consideration of the melting temperature of the resin. For the example containing glass fiber as a filler, a required amount of glass fiber was put together during kneading to produce a pellet. In each of Examples and Comparative Examples, the following base resins were used.
(Examples 1 to 4, Comparative Examples 1 and 8)
PA66 resin Amilan CM3007 (Toray)
(Comparative Examples 2 to 4 and 9 to 11)
ABS resin Toyolac 700-314 (Toray)
(Comparative Examples 5 to 7 and 12 to 14)
PP resin Novatec MA3UD (Nippon Polypro)
(Examples 5 to 16, Comparative Example 15)
PA66 resin Leona 90G50 (Asahi Kasei)
(Examples 17 to 23, Comparative Example 16)
PAMXD resin Reny 1022F (Mitsubishi Engineering Plastics)
Leona 90G50 (Asahi Kasei) and Reny 1022F (Mitsubishi Engineering Plastics) are resin products in which 50% by mass of glass fiber is mixed in advance in a commercially available base resin.

(4) Using the obtained pellets, a molded product of a resin composition having a length and width of 150 mm × 150 mm and a thickness of 3 mm was produced with an injection molding machine (ROBOSHOT S-2000i100B FANUC). The cylinder temperature was 270 ° C. for the polyamide resin, 200 ° C. for the PP resin, and 200 ° C. for the ABS resin.

The above molded article was subjected to an antibacterial test, an antiviral test, an abrasion test, a water resistance test, and a dissolution test to evaluate antibacterial performance, antiviral performance, and its durability. The test results are shown in Tables 1 to 5 below. The water absorption of the resin composition after molding was calculated by multiplying the weight composition ratio based on the water absorption of the base resin.
[test]

<Antibacterial test>
With respect to the antibacterial property of the resin, an antibacterial property evaluation test was performed in accordance with JIS Z2801. When the infectious titer log reduction value was 2.0 or more, it was judged as effective.

<Antiviral test>
With respect to the antiviral properties of the resin, an evaluation test of the antiviral properties was carried out using influenza A virus as an enveloped virus and feline calicivirus as a non-enveloped virus with a contact time of 24 hours with reference to JIS Z 2801. Was. When the infectious titer log reduction value was 2.0 or more, it was judged as effective.

<Water resistance test>
At a rate of ultrapure water 50ml of the surface area 25 cm ² of the test specimen, subjected to antibacterial and antiviral test described above was immersed for 16 hours in ultrapure water, the antibacterial and antiviral resin surface after water immersion evaluated.

<Wear test>
Using a base cloth width as a contact, a load of 9.8 N was applied to the test piece per 10 cm × 10 cm area, and friction was applied 7,300 times by a sliding wear tester. Thereafter, the antibacterial and antiviral tests described above were performed to evaluate the antibacterial and antiviral properties of the resin surface after abrasion.

<Dissolution test>
In the resin composition using PA66 resin as the base resin, the test surface of a test piece prepared with the addition amount of the antiviral agent of 0 to 6% by mass for each of those containing glass fiber and those not containing the glass fiber was tested. The side and back surfaces of the test piece processed into a size of 50 mm × 50 mm were sealed with a melt coat so that the antibacterial and antiviral agents were not eluted from other than the test surface. The test surface was immersed in water using 10 ml of ultrapure water with respect to the surface area of 25 cm ^{2 of the} test piece, wrapped so that the water did not evaporate, and allowed to stand at a temperature of 25 ± 1 ° C. for 24 hours.
FIG. 3 is a diagram plotting the amount of the antibacterial / antiviral agent eluted per unit area of the test piece after ionization using ion chromatography and plotting the amount of the antibacterial / antiviral agent added to the test piece. It is. FIG. 4 is a diagram plotting the logarithm of the infectious titer in the antibacterial and antiviral tests described above to clarify the relationship between the amount of calcium ion eluted and the antibacterial and antiviral properties.

<Measurement of water absorption>
With respect to the prepared test piece, the water absorption was measured based on the increase in mass after immersion in water for 24 hours.

The above test results are shown in Tables 1 to 5 below.

[Evaluation]

For antibacterial and antiviral performance, after production, the initial state of the resin composition before conducting a water resistance test, antibacterial test and antiviral test results, in all resin compositions containing antibacterial and antiviral agents, It showed antibacterial and antiviral performance.

(4) Next, regarding the persistence of antibacterial and antiviral performance, antibacterial and antiviral tests were respectively performed on the resin compositions after the abrasion test and the water resistance test. In the present disclosure, “having sustained antibacterial and antiviral properties” requires that at least the antibacterial action is maintained after the water resistance test.

抗菌 The results of the antibacterial and antiviral tests performed after the abrasion test were almost the same as the results of the same test in the initial state. This is considered to be because the resin itself disappears due to abrasion and the antibacterial and antiviral agents inside the resin composition are exposed, so that the surface state which is the same as that of the resin composition in the initial state can be maintained. That is, even if the resin composition is worn, the antibacterial / antiviral agent disappears only in the worn portion, so that the effect on the durability of the antibacterial / antiviral effect is small.

Furthermore, based on the results of antibacterial and antiviral tests performed after the water resistance test, the sustainability of antibacterial and antiviral performance was evaluated.

<Examples 1 to 4, Comparative Examples 1 and 8>
・ PA66 resin Amilan CM3007 (Toray) Water absorption 1.5% by mass
(A) No glass fiber When no glass fiber was contained, in Examples 1 and 2, good antibacterial properties were exhibited even after the water resistance test. Example 2 also showed antiviral properties against only the non-enveloped virus. It is estimated that the antibacterial and antiviral agents inside the resin eluted on the surface.
(B) With Glass Fiber When glass fiber was contained, in Examples 3 and 4, good antibacterial and antiviral properties were exhibited even after the water resistance test. Since the glass fiber is present inside the resin, a path through which moisture easily passes is formed at the interface between the glass fiber and the resin, and as compared with Examples 1 and 2 having no filler, a larger amount of the resin inside is provided. It is estimated that antibacterial and antiviral agents eluted on the surface.

<Comparative Examples 2 to 4 and 9 to 11>
・ ABS resin Toyolac 700-314 (Toray) Water absorption 0.4% by mass
(A) No glass fiber When no glass fiber was contained, no antibacterial and antiviral properties were exhibited in any of the examples. It is estimated that the antimicrobial / antiviral agent on the surface flowed out by immersion in water in the water resistance test, and a sufficient amount of the antibacterial / antiviral agent did not exist on the surface.
(B) With glass fiber When glass fiber was contained, antibacterial and antiviral properties were not shown in Comparative Example 10, and only good antibacterial property was shown in Comparative Example 11 even after the water resistance test. It is presumed that the ABS resin had lower water absorption than the polyamide resin, and a sufficient amount of the antibacterial / antiviral agent could not be eluted on the resin surface.

<Comparative Examples 5 to 7 and 12 to 14>
・ PP resin Novatec MA3UD (Nippon Polypro) water absorption 0.1% by mass
No antibacterial / antiviral properties were observed after the water resistance test, regardless of the presence or absence of glass fibers. It is presumed that the PP resin had even lower water absorption than the ABS resin, and a sufficient amount of the antibacterial / antiviral agent could not be eluted on the resin surface.

<Examples 5 to 16, Comparative Example 15>
・ PA66 resin Leona 90G50 (Asahi Kasei)
The resin product is a resin product containing glass fiber from the time of marketing. In Example 5, only the antibacterial property was shown. Examples 6 to 16 all exhibited antibacterial and antiviral properties, and particularly, Examples 12 to 16 exhibited antiviral properties for both enveloped and non-enveloped viruses. The addition amount of the antibacterial / antiviral agent is preferably 1.5% by mass or more, and good antiviral properties are exhibited.

<Examples 17 to 23, Comparative Example 16>
・ PAMXD resin Reny 1022F (Mitsubishi Engineering Plastics)
The resin product is a resin product containing glass fiber from the time of marketing. Examples 17 to 23 all exhibited antibacterial and antiviral properties, and particularly Examples 19 to 23 exhibited antiviral properties against any type of virus.

Further, the results of the dissolution test shown in FIG. 3 indicate that the dissolution amount of calcium ions tends to increase with the addition amount of the antibacterial / antiviral agent regardless of the presence or absence of the glass fiber. When glass fibers were used, the amount of calcium ions eluted greatly increased when the amount of the antibacterial / antiviral agent added was 1 to 3% by mass, and gradually increased when the amount was 3% by mass or more. Calcium ions are presumed to be derived from slaked lime, and as shown in FIG. 4, the antiviral performance was improved as the amount of eluted calcium ions increased. In particular, when the amount of eluted calcium ions was 0.06 μmol / cm ² or more, it exhibited antiviral properties against both influenza virus and feline calicivirus.

(4) The resin composition containing glass fiber as a filler significantly increased the amount of calcium ions eluted as compared with the resin composition containing no filler. It is presumed that the glass fiber promotes the dissolution of slaked lime, and the slaked lime inside the resin functions on the resin surface. Therefore, it is presumed that the antiviral effect can be continuously exerted even after dissolution by the water resistance test.

Further, regarding the water absorption of the resin composition and the antibacterial and antiviral properties after the water resistance test, the resin composition containing no glass fiber shows good antibacterial and antiviral properties in the resin composition having a water absorption of 1.5% by mass. It was observed. Although the antibacterial property was observed in the resin composition of 0.4% by mass, the antiviral property was not observed.
On the other hand, in the resin composition containing glass fibers, good antibacterial and antiviral properties were observed in the resin composition having a water absorption of 0.3% by mass or more. That is, by containing glass fibers in the resin composition, the antibacterial and antiviral effects can be increased.

Claims

Polyamide-based resin,
An antiviral resin composition comprising: an antiviral agent that exhibits water solubility and has a decomposition temperature higher than the melting temperature of the polyamide resin.
抗 The antiviral resin composition according to claim 1, wherein the antiviral agent is slaked lime.
The antiviral resin composition according to claim 1 or 2, wherein the antiviral resin composition further has a filler.
The antiviral resin composition according to claim 3, wherein the filler is a glass fiber.
The antiviral resin composition according to any one of claims 1 to 4, wherein the antiviral agent has antibacterial properties.
The antiviral resin composition according to any one of claims 1 to 5, wherein the amount of the antiviral agent added is 1.5% by mass or more.
The antiviral resin composition according to claim 6, wherein the amount of the antiviral agent added is 3% by mass or more.
The antiviral resin composition according to any one of claims 1 to 7, wherein the polyamide resin has a water absorption of 0.3% by mass or more.
The antiviral resin composition according to claim 8, wherein the polyamide resin has a water absorption of 0.4% by mass or more.
The antiviral resin composition according to claim 9, wherein the polyamide resin has a water absorption of 1.5% by mass or more.
The antiviral resin composition according to any one of claims 2 to 10, wherein the elution amount of calcium ions per unit area of the resin composition is 0.06 µmol / cm 2 or more.