JP3060786B2 - Antimicrobial resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone resin composition capable of forming an antimicrobial film on the surface of various materials. The resin composition of the present invention can be used for surface treatment of various materials such as fibers, fabrics, paper, building materials, concrete, glass, metals and other inorganic materials, synthetic and natural resins. By this surface treatment, a film having antimicrobial properties such as antibacterial property and antifungal property is formed on the surface of the material, and the material can be continuously provided with antimicrobial property. The resin composition of the present invention can also be used alone as a sheet or film having antimicrobial properties, and is also useful as an antimicrobial sealing material or adhesive.

[0002]

2. Description of the Related Art By kneading or applying a powder carrying an inorganic substance such as silver or an organic antibacterial agent to a material,
Attempts have been made to impart sustained antimicrobial properties to the material. However, in the method by kneading, the drug enters the inside of the material, the antibacterial effect is reduced depending on the amount of the antibacterial agent used, the efficiency is poor, the material that can be kneaded is limited, and natural fibers are used. Is not applicable. Further, since silver ions are considered to be harmful to the human body, it is not preferable that silver ions elute and exhibit an antibacterial effect.

On the other hand, when antibacterial properties are imparted to the material surface by surface treatment such as coating, the use efficiency of the antibacterial drug increases, but the conventional organic antibacterial drug is soluble or binds to the material surface. Because of its weak power, it was lost from the surface early, and its effect was not long lasting and its use was limited in terms of toxicity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a variety of materials with surface treatments to impart favorable antimicrobial properties, and have a long-lasting effect, so that no harmful drug components are eluted. An object of the present invention is to provide a resin composition capable of forming an antimicrobial film.

Another object of the present invention is to provide an antimicrobial film which can form a high-strength film and can be used alone as an antimicrobial sheet or film, and also as an antimicrobial sealing material or adhesive. Is to provide a silicone resin composition of the invention.

[0006]

In order to achieve the above-mentioned object, a material which has excellent antimicrobial properties and which can form a high-strength antimicrobial film that is well bonded to various material surfaces and has high film strength is required. I just need. As a result of repeated studies for developing such a material, the present inventors have found that the combination of an organopolysiloxane compound containing a biguanidyl group and a curing agent for curing the same are optimal, and have reached the present invention.

Here, the present invention relates to (a) an organopolysiloxane compound containing at least one biguanidyl group and at least one reactive functional group, and (b) an antioxidant comprising a curing agent reactive with the organopolysiloxane. The gist is a microbial resin composition.

According to the present invention, there are also provided an antimicrobial resin film, film and sheet formed by curing the above resin composition, and an antimicrobial surface treating agent, sealing material and adhesive comprising the above resin composition. Is done.

The main component of the resin composition of the present invention is an organopolysiloxane compound containing at least one biguanidyl group and at least one reactive functional group of (a). In this compound, Biguanijiru group of the general formula: -XYSiO- (wherein, X is an alkyl group of C ₁ -C _5, Y is a is a monovalent group containing a Biguanijiru group) as a constituent unit represented by Present in the polysiloxane molecule, the biguanidyl group imparts antimicrobial properties to the compound. The number of the biguanidyl group-containing structural units is not particularly limited, and may be one or two or more. Generally, one or two provides sufficient antimicrobial properties. In addition, the binding position of the above-mentioned biguanidyl group-containing structural unit may be terminal, non-terminal, or both.

The monovalent group Y containing a biguanidyl group is preferably represented by the following general formula. -R ¹ -NHC (= NH) NH-C (= NH) NH-R ^{2 wherein} R ¹ is an intervening group such as an oxy group, an azo group, a thio group, a hydroxymethylene group, an oxycarbonyl group, a phenylene group Means a C _{1 to} C ₃₀ alkylene group which may be contained in the chain, and R ² is hydrogen, a C _{1 to} C ₂₀ alkyl group, or a phenyl group, and the phenyl group is a group such as fluorine, chlorine, or bromine. It may be substituted with one or more substituents such as a halogen, a trifluoromethyl group and an alkoxyl group.

The organopolysiloxane compound of the component (A) contains at least one reactive functional group in addition to the biguanidyl group so that it can react with the component (B) to form a cured resin film. Need to be. As the reactive functional group, those containing an amino group are particularly preferable because they are easily available, but in addition, an epoxy group, a carboxyl group, a hydroxyl group,
It may be an isocyanate group or the like. The number of reactive functional groups and the bonding position in the organopolysiloxane compound are not particularly limited.

Such a compound can be produced by the method described in Japanese Patent Application No. 3-359590 previously proposed by the present inventors. (A) Specific examples of the organopolysiloxane compound useful as a component are shown below.

[0013]

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[0014]

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[0015]

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[0016]

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In the formulas (2) to (4), R may be the same as in the formula (1), and l, m and n are each an integer of 1 or more.

The organopolysiloxane compound of component (a) is generally liquid at room temperature, and has a viscosity at 25 ° C. of 100 to 1,000,000 cSt in view of the strength and workability of the resulting film.
Particularly, those having a cSt of 500 to 100,000 cSt are preferable.

[0019] Even if only the component (a) is used, the surface treatment temporarily imparts antimicrobial properties to the material surface. However, the formed film is merely adhered to the surface and is not immobilized. Due to its low strength, the antimicrobial effect is lost early. Therefore, in the present invention, a curing agent reactive with the component (a) is further used as the component (b).

The component (b) may be any crosslinkable compound containing at least one functional group reactive with the component (a).
Preferred as the curing agent of the component (b) are organosilicon compounds containing at least one functional group reactive with the component (a) and at least two hydrolyzable groups. Such an organosilicon compound is reactive with the component (a) and has a crosslinking property due to the presence of two or more hydrolyzable groups.
A cured resin film can be formed while incorporating the organopolysiloxane component into the crosslinked structure. Also,
Since the component (b) also forms a siloxane bond by hydrolysis and crosslinks, a film having a siloxane bond skeleton as a whole, having excellent heat resistance, and substantially retaining desirable properties as silicone is formed. .

As the hydrolyzable group in the organosilicon compound suitable as the component (b), an alkoxy group such as a methoxy group and an ethoxy group and a halogen such as chlorine can be used. The reactive functional group for bonding to the component (a) may be any reactive functional group capable of forming a bond by reacting with the functional group contained in the component (a). Specifically, if the reactive functional group in the component (a) is an amino group, an epoxy group is preferred, and if the reactive functional group in the component (a) contains an epoxy group, an amino group is preferred. Further, if component (a) contains a hydroxyl group, component (b) preferably contains a functional group such as an epoxy group or a carboxy group, and vice versa.

As the organosilicon compound containing a reactive functional group that can be used as the component (b), various compounds are commercially available as silane coupling agents. Some specific examples of such a silane coupling agent are described below, but are not limited thereto.

[0023]

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[0024]

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[0025]

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From the viewpoint of curing reactivity, film properties, and availability, the component (A) having an amino group and the epoxy group
It is most preferred to combine the components (b), and both of these components may be a mixture of two or more different compounds.

The preferred (ii) component is the above-mentioned organosilicon compound, but a usual carbon-based organic compound can also be used as a curing agent for the (ii) component. For example, when the component (a) contains an epoxy group as a reactive functional group, various compounds (e.g., acid anhydride, polyamine, polyamide resin, etc.) that can be used as an epoxy curing agent may be used as the component (b). Can be used. Those skilled in the art will be able to select an appropriate (ii) component that is reactive with the (ii) component.

The mixing ratio of the component (b) to the component (a) is as follows:
The component (b) is preferably 0.1 to 1000 parts by weight, particularly 1 to 200 parts by weight, based on 100 parts by weight of the component (A). If the amount is larger than this, there arises a problem that physical properties such as flexibility of the obtained resin are deteriorated. However, an appropriate compounding ratio varies depending on the types of the component (a) and the component (b), and may be selected experimentally within the above range.

The resin composition of the present invention may further contain other additives in addition to the components (A) and (B). For example, the addition of a curing accelerator (eg, an organic tin compound, an organic lead compound, etc.) accelerates the curing. Other additives that can be used include pigments and ultraviolet absorbers. Further, the resin composition of the present invention may be used after being diluted with a solvent depending on the use. Suitable solvents include
Examples include ethers such as diethyl ether, hydrocarbons such as hexane, cyclohexane, toluene, and xylene, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.

The resin composition of the present invention is generally obtained by mixing a curing agent of component (b) with other additives, if necessary, in an organopolysiloxane of component (a) which is liquid at room temperature. For example, it can be prepared by diluting with an organic solvent.
When the component (b) is the above-mentioned organosilicon compound, hydrolysis starts due to moisture in the air and cross-linking occurs.If the components (a) and (b) are kept in a sealed state after mixing, the cross-linking can be performed. It can be stored in a fluid state without causing a reaction. When left at room temperature after use, curing gradually starts due to moisture in the atmosphere, and a cured resin is obtained. It is also possible to cure under heating or humidification in order to promote curing. If the reaction between component (a) and component (b) or the cross-linking of component (b) starts even in a closed state, a two-pack resin composition is used. The mixing may be performed immediately before use.

The cured resin obtained from the resin composition of the present invention has the same flexibility properties as a so-called silicone rubber, and has high transparency as well as strong antimicrobial properties. Therefore, the resin composition of the present invention can be used for the same applications as silicone rubber, and can impart antimicrobial properties to products.

For example, the resin composition of the present invention can be used alone as an antimicrobial film or sheet in various packaging materials and medical instruments. The production of a film or sheet can be carried out by a method of forming a film on a peelable substrate and peeling it after curing, or by using a molding method such as casting, extrusion or press molding.

Further, the resin composition of the present invention can be used as a sealant or an adhesive, similarly to silicone rubber. Conventionally, generation of microorganisms such as mold has been a problem for sealing materials and adhesives, and the use of the resin composition of the present invention for this purpose is very advantageous since the generation and propagation of microorganisms can be prevented. When the composition of the present invention is used as a sealant or an adhesive, it can be diluted with an organic solvent, if necessary.

When the resin composition of the present invention is used as a surface treating agent, the mixture of the component (a) and the component (b) retains fluidity if kept in a sealed state, so that the mixture is not diluted. Can be used as it is for application to materials. of course,
It may be diluted if necessary. When the material is subjected to surface treatment by dipping or spraying, it is preferable to use the material after diluting it with an appropriate solvent.

The film formed on the material surface by the surface treatment using the resin composition of the present invention has high transparency in addition to antimicrobial properties, and is also suitable for applications requiring transparency. . In addition, since this film has desirable characteristics unique to silicone resin, it is necessary to simultaneously impart high functionality such as heat resistance, weather resistance, water repellency, glazing effect, surface protection, and electrical characteristics to the material surface. Is possible.

As a material to which the surface treatment with the antimicrobial resin composition of the present invention is applied, various materials including building materials such as glass, metal, resin molded product, fiber and woven fabric, paper, concrete, and tile can be used. The advantage is that the insoluble film is firmly bonded to the material by leaving the film hardened at room temperature, so the durability of the antimicrobial effect is high, and the safety is high because no harmful components are eluted. is there.

[0037]

EXAMPLES The following examples are given, but do not limit the present invention. In the examples and comparative examples, parts are parts by weight unless otherwise specified.

Example 1 In the formula (1), 100 parts of a polysiloxane compound in which R is a p-chlorophenyl group (amino equivalent: 1880 g / mol, biguanidyl equivalent: 1880 g / mol) was used as a silane coupling agent. A resin composition was prepared by mixing 10 parts of a commercially available epoxy group-containing silane compound represented by the formula (5). This composition was used as a surface treatment solution without dilution, applied to a 25 × 65 × 2 mm glass plate with a bar coater to a thickness of 10 μm, and allowed to stand at room temperature for one day to cure the film.

(Antibacterial Test) In order to examine the persistence of the antibacterial activity, the surface-treated glass plate was immersed in water at room temperature for one week, and the antibacterial activity was evaluated by the following antibacterial test. Place the glass plate in a sterilized container and place the bacterial suspension (test bacterium: Staphylococcus aureus> ATCC 6
538 strains) was inoculated with 0.1 ml (the number of bacteria: about 2.0 × 10 ⁷ / ml) and allowed to stand still at 18 ° C. for 18 hours in a thermostat. Sterile water in container
10 ml was added, the mixture was shaken, and the number of viable cells dispersed in water was measured. As a result, no viable cells were found.

Example 2 The procedure was carried out except that the polysiloxane compound was changed to 100 parts of the compound of the formula (1) wherein R is a phenyl group (amino equivalent: 1840 g / mol, biguanidyl equivalent: 1840 g / mol). In the same manner as in Example 1, a surface treatment solution was prepared and the surface treatment of the glass plate was performed. As a result of measuring the viable cell count of the surface-treated glass plate by the same test method as in Example 1, no viable cell was found.

Example 3 A polysiloxane compound in which R is a p-chlorophenyl group in the formula (2) (amino group equivalent: 8900 g / mol, biguanidyl group equivalent: 8900 g / mol) 100 parts of the compound represented by the formula (6) A surface treatment liquid was prepared by mixing 20 parts of the indicated silane compound having an epoxy group (commercially available silane coupling agent). The surface treatment of the glass plate and the antibacterial test were performed using this surface treatment solution in the same manner as in Example 1, and the number of viable bacteria was measured.

Example 4 In the formula (3), 100 parts of a polysiloxane compound in which R is a p-chlorophenyl group (hydroxyl equivalent: 1800 g / mol, biguanidyl group equivalent: 1800 g / mol) is represented by the formula (5). The surface treatment liquid was prepared by mixing 10 parts of the silane compound having an epoxy group. The surface treatment of the glass plate and the antibacterial test were performed using this surface treatment solution in the same manner as in Example 1, and the number of viable bacteria was measured. As a result, no viable bacteria were found.

Example 5 In the formula (4), 100 parts of a polysiloxane compound in which R is a p-chlorophenyl group (epoxy group equivalent: 1000 g / mol, biguanidyl group equivalent: 1000 g / mol) A surface treatment solution was prepared by mixing 30 parts of the indicated silane compound having an amino group (commercially available silane coupling agent). The surface treatment of the glass plate and the antibacterial test were performed using this surface treatment solution in the same manner as in Example 1, and the number of viable bacteria was measured.

Comparative Example 1 100 parts of a polysiloxane compound having amino groups at both ends (silicone oil X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 0.1 part of chlorhexidine hydrochloride, a known antibacterial agent, and the compound of the formula (5)
A resin composition prepared by mixing with 10 parts of an epoxy group-containing silane compound represented by the following formula was used as a surface treatment liquid, and the surface treatment of a glass plate and an antibacterial test were performed with this surface treatment liquid in the same manner as in Example 1 to produce live bacteria. 3.4 × 10 ⁷ (pcs
/ ml).

Example 6 5 g of the surface treating solution prepared in Example 1 was added to ethyl ether 20
g, and the diluted solution was repeatedly sprayed twice onto a 50 × 50 × 2 mm acrylic plate (1.5 ml per spray), and allowed to stand at room temperature for 24 hours to cure the surface film. . Using the acrylic plate thus surface-treated, an antibacterial test was performed after immersion in water in the same manner as in Example 1, and the number of viable bacteria was measured. As a result, no viable bacteria were found.

Example 7 The diluted solution prepared in Example 6 was repeatedly sprayed twice on a slate plate of 50 × 50 × 5 mm (the spraying amount was the same as in Example 6), and allowed to stand at room temperature for one day and night to obtain a surface. Was cured. The slate plate thus surface-treated is immersed in water at room temperature for one week, and then placed on a potato dextrose agar medium, and mold spores are placed.
(Test strain: Aspergillus niger
>) And cultured at 30 ° C. for 2 weeks, and the growth of the mold was observed. As a result, the mold did not grow on the slate plate, and the initial appearance was maintained.

Comparative Example 2 5 g of the surface treatment solution prepared in Comparative Example 1 was
g, and the diluted solution was used to perform surface treatment of the slate plate by spraying and a fungicide test after immersion in water in the same manner as in Example 7. Two weeks later, the mold was completely coated on the entire surface of the slate plate. Was observed.

Example 8 The resin composition prepared in Example 1 was diluted to a diameter of 40 m without dilution.
m, cast into a 1mm thick mold, cured for 1 week at room temperature,
A silicone rubber-like transparent sheet having a thickness of 1 mm was obtained. Using the obtained sheet, an antibacterial test was performed after immersion in water in the same manner as in Example 1, and the number of viable bacteria was measured. As a result, no viable bacteria were observed.

Comparative Example 3 A sheet was prepared in the same manner as in Example 8 using the resin composition prepared in Comparative Example 1. An antibacterial test was performed on the obtained sheet after immersion in water in the same manner as in Example 1, and the number of viable bacteria was measured. As a result, the number was 5.1 × 10 ⁷ (cells / ml).

Example 9 In order to evaluate the properties of the resin composition of the present invention as an adhesive, the composition (treatment liquid) prepared in Example 1 was examined for adhesion to various materials. The adhesive strength was measured after bonding the materials and curing them at 20 ° C. and 65% RH for 3 days. The results are shown in Table 1 below.

[0051]

[Table 1]

Example 10 In order to evaluate the properties of the resin composition of the present invention as a sealing material, the treatment liquid prepared in Example 1 was applied to a mortar and cured at 20 ° C. and 65% RH for 3 days. Then, water was dropped on the coated surface to evaluate waterproofness. As a result, even after one hour, the dropped water was repelled and not absorbed at all.

[0053]

The resin composition of the present invention gives an antimicrobial transparent cured product having the same properties as silicone rubber. Therefore, it can be used alone as an antimicrobial film or sheet, or as an antimicrobial sealant or adhesive, and can prevent the growth of mold and bacteria, which has been a problem in this type of application, A good appearance can be maintained.

Further, the resin composition of the present invention can impart antibacterial and antifungal properties to various materials as a surface treatment agent,
It has a reactive functional group in the component, so it has excellent binding to the material surface, and it can impart favorable antibacterial and fungicidal properties to materials such as plastics and metals, which were conventionally difficult to surface treat. It is possible.

Further, since the resin composition of the present invention becomes a cured product in which the whole is integrally bonded by curing, the drug component is not eluted, the safety is high, and the antimicrobial effect is excellent in persistence. . Further, since the properties of silicone are retained, in addition to antimicrobial properties, effects inherent to silicone such as heat resistance, weather resistance, water repellency, polishing, surface protection, and electrical properties can be imparted.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-26172 (JP, A) JP-A-4-26669 (JP, A) JP-A-3-200793 (JP, A) JP-A 61-261 148285 (JP, A) JP-A-59-196303 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 47/44 C09D 5/14 C09K 3/10

Claims (5)

(57) [Claims] 1. An antimicrobial resin composition comprising (a) an organopolysiloxane compound containing at least one biguanidyl group and at least one reactive functional group, and (b) a curing agent reactive with the organopolysiloxane. Stuff. 2. An antimicrobial resin film, film and sheet formed by curing the composition according to claim 1. 3. An antimicrobial surface treating agent comprising the composition according to claim 1. 4. An antimicrobial sealing material comprising the composition according to claim 1. 5. An antimicrobial adhesive comprising the composition according to claim 1.