JPH0733613A - Antimicrobial resin composition - Google Patents

Abstract

PURPOSE:To provide the composition excellent in antimicrobial capability and high in its sustainability, highly adhesive to various kinds of material surfaces, comprising a combination of a biguanidyl group-bearing organopolysiloxane compound and a curing agent therefor. CONSTITUTION:This composition comprising (A) an organopolysiloxane compound having at least one biguanidyl group and reactive functional group, respectively, and (B) a curing agent for the component A. The component A is, e.g. a compound of formula I (R is of formula II, III or IV; m is >=1). The component B is, e.g. an organosilicon compound of formula V. This composition can impart various kinds of materials with highly sustainable, favorable antimicrobial capability through surface treatment therewith, causing no toxic chemical ingredients to be leached. This composition can also be made into a high-strength film; therefore, being usable as an antimicrobial sheet or film by itself, or as an antimicrobial sealant or adhesive.

Description

Detailed Description of the Invention

[0001]

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 and concrete, glass, metals and other inorganic substances, synthetic and natural resins, and the like. By this surface treatment, a film exhibiting antimicrobial properties such as antibacterial properties and antifungal properties is formed on the surface of the material, and the antimicrobial property can be continuously imparted to the material. The resin composition of the present invention can also be used as a sheet or film having antimicrobial properties by itself, 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 lasting antimicrobial properties to materials. However, in the method by kneading, the drug enters inside the material, the antibacterial effect is reduced relative to the amount of the antibacterial agent used, the efficiency is poor, the materials that can be kneaded are limited, and natural fibers are used. Is not applicable. Further, since silver ions are said to be harmful to the human body, it is not preferable that the silver ions be eluted to exhibit an antibacterial effect.

On the other hand, if the material surface is given antibacterial properties by surface treatment such as coating, the utilization efficiency of the antibacterial drug is increased, but conventional organic antibacterial drugs are soluble or bound to the material surface. Due to its weak strength, it was lost from the surface at an early stage, and the effect was poor in sustainability, and its application was limited in terms of toxicity.

[0004]

The object of the present invention is to impart a preferable antimicrobial property to a variety of materials by surface treatment, have a long-lasting effect, and prevent harmful drug components from eluting. 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 form a high strength film, which can be used alone as an antimicrobial sheet or film, and also as an antimicrobial sealant or adhesive. Another object of the present invention is to provide the silicone-based resin composition.

[0006]

In order to achieve the above-mentioned object, a material which is excellent in antimicrobial properties and which can bind to various material surfaces well and form an antimicrobial film having high film strength is provided. I wish I had it. As a result of repeated research to develop such a material, the present inventors have arrived at the present invention, knowing that the combination of an organopolysiloxane compound containing a biguanidyl group and a curing agent for curing the same is optimal.

Here, the present invention provides (a) an organopolysiloxane compound containing at least one biguanidyl group and at least one reactive functional group, and (b) an anti-curing agent comprising a curing agent reactive with the organopolysiloxane. The subject matter is a microbial resin composition.

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

The main component of the resin composition of the present invention is (a) an organopolysiloxane compound containing at least one biguanidyl group and at least one reactive functional group. In this compound, the biguanidyl group is a structural unit represented by the general formula: —XYSiO— (wherein, X is a C _{1 to} C ₅ alkyl group, and Y is a monovalent group containing a biguanidyl group). Present in the polysiloxane molecule, this biguanidyl group imparts antimicrobial properties to the compound. The number of the biguanidyl group-containing constitutional unit is not particularly limited and may be one or two or more, but generally one or two is sufficient antimicrobial property. Further, the bonding position of the above-mentioned biguanidyl group-containing constitutional unit may be either terminal, non-terminal, or both.

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

The organopolysiloxane compound as 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 preferred 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. Specific examples of the organopolysiloxane compound useful as the component (a) are shown below.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4]

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

The organopolysiloxane compound as the component (a) is generally a liquid at room temperature, and has a viscosity at 25 ° C. of 100 to 1,000,000 cSt from the viewpoint of strength and workability of the formed film.
Particularly preferred is 500 to 100,000 cSt.

The component (b) alone imparts a temporary antimicrobial property to the surface of the material by the surface treatment, but the formed film merely adheres to the surface and is not immobilized, and Since the strength is weak, the antimicrobial effect is lost early. Therefore, in the present invention, as the component (b), a curing agent reactive with the component (a) is further used.

The component (b) may be any crosslinkable compound containing at least one functional group reactive with the component (a).
Preferred as the curing agent for the component (b) is an organosilicon compound containing at least one functional group reactive with the component (b) and at least two hydrolyzable groups. Such an organosilicon compound is reactive with the component (a) and has crosslinkability due to the presence of two or more hydrolyzable groups.
It is possible to form a cured resin film while incorporating the component organopolysiloxane in the crosslinked structure. Also,
The component (b) also forms a siloxane bond by hydrolysis and crosslinks, so that a film having an overall siloxane bond skeleton, excellent heat resistance, and substantially retaining the desired 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. Further, the reactive functional group for bonding with the component (a) may be any one capable of reacting with the functional group contained in the component (a) to form a bond. Specifically, if the reactive functional group in the component (a) is an amino group, an epoxy group or the like is preferable, and conversely, if the component (a) contains an epoxy group, an amino group or the like is preferable. Further, if the component (a) contains a hydroxyl group, the 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 which can be used as the component (b), various compounds are commercially available as a silane coupling agent. Some specific examples of such a silane coupling agent will be given below, but the present invention is not limited thereto.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

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

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

The blending ratio of the component (b) to the component (a) is
(B) Component (b) Component (b) 0.1 to 1000 parts by weight, especially 1 to 200 parts by weight is preferable, and if it is less than this, curing may be insufficient, or curing may take a long time. If the amount is larger than this, there arises a problem that the physical properties such as flexibility of the obtained resin deteriorate. However, since an appropriate compounding ratio differs depending on the types of the component (a) and the component (b), it 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, addition of a curing accelerator (eg, organic tin compound, organic lead compound, etc.) accelerates 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 application. Suitable solvents include
Examples include ethers such as diethyl ether, hydrocarbons such as hexane, cyclohexane, toluene, xylene, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.

In the resin composition of the present invention, the curing agent of the component (b) and other additives, if necessary, are mixed with the organopolysiloxane of the component (a) which is generally liquid at room temperature, and further it is necessary. For example, it can be prepared by diluting with an organic solvent.
When the component (b) is the above organosilicon compound, hydrolysis starts due to moisture in the air and crosslinking occurs, so if the component (a) and the component (b) are kept in a sealed state after mixing, crosslinking will occur. It can be stored while maintaining a fluid state without causing a reaction. After use, if left at room temperature, the moisture in the air gradually starts to cure and becomes a cured resin. It is also possible to cure under heating or humidification in order to accelerate the curing. If the reaction between the component (b) and the component (b) or the crosslinking of the component (b) begins even in a closed state, use a two-component type resin composition and prepare the two components (a) and (b). The mixing may be performed just before use.

The cured resin obtained from the resin composition of the present invention exhibits flexibility similar to that of so-called silicone rubber, and has high antimicrobial property and high transparency. Therefore, the resin composition of the present invention can be used in the same applications as silicone rubber, and thereby impart antimicrobial properties to the product.

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 film or sheet can be produced by a method of forming a film on a peelable substrate and then peeling 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 sealing material or an adhesive as in the case of silicone rubber. Sealing materials and adhesives have conventionally been problematic in the generation of microbes such as mold, and the use of the resin composition of the present invention for this purpose is extremely advantageous because the generation and reproduction of microbes can be prevented. When the composition of the present invention is used as a sealing material 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 treatment agent, the mixture of the component (a) and the component (b) retains fluidity if kept in a sealed state, so that it is not diluted. It can be used as it is for application to materials. of course,
You may dilute if necessary. When the material is surface-treated by dipping or spraying, it is preferably diluted with a suitable solvent before use.

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

As the material to which the surface treatment with the antimicrobial resin composition of the present invention is applied, various materials including glass, metal, resin moldings, fibers and fabrics, paper, concrete, tile and other building materials are possible. Since the insoluble film is firmly bound to the material by hardening the film when left at room temperature, the antimicrobial effect is highly durable, and the harmful component does not elute. is there.

[0037]

EXAMPLES Examples will be shown below, but these do not limit the present invention. In Examples and Comparative Examples, parts are parts by weight unless otherwise specified.

Example 1 Polysiloxane compound in which R is a p-chlorophenyl group in the formula (1) (amino group equivalent: 1880 g / mol, biguanidyl group equivalent: 1880 g / mol) was added to 100 parts 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 it was as a surface treatment solution without dilution, and it was 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 investigate the durability of the antibacterial property, the surface-treated glass plate was immersed in water at room temperature for 1 week, and then the antibacterial property was evaluated by the following antibacterial test. Put the glass plate in a sterilized container, and put the bacterial suspension (test bacteria: Staphylococcus aureus> ATCC 6
538 strains) was inoculated with 0.1 ml (the number of bacteria: about 2.0 × 10 ⁷ / ml) and statically cultured at 35 ° C. for 18 hours in a constant temperature incubator. Sterile water in a container
When 10 ml was added and shaken to measure the number of viable bacteria dispersed in water, no viable bacteria were observed.

Example 2 The procedure of Example 2 was repeated except that the polysiloxane compound was changed to 100 parts of a compound in which R was a phenyl group in the formula (1) (amino group equivalent: 1840 g / mol, biguanidyl group equivalent: 1840 g / mol). A surface treatment solution was prepared and a glass plate was surface-treated in the same manner as in Example 1. 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 observed.

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) was added to 100 parts 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 with this surface treatment solution in the same manner as in Example 1, and the viable cell count was measured. As a result, no viable cell was observed.

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

Example 5 A polysiloxane compound in which R is a p-chlorophenyl group in the formula (4) (epoxy group equivalent: 1000 g / mol, biguanidyl group equivalent: 1000 g / mol) was added to 100 parts by the formula (7). A surface treatment liquid 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 with this surface treatment solution in the same manner as in Example 1, and the viable cell count was measured. As a result, no viable cell was observed.

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 added with 0.1 part of a known antibacterial agent chlorhexidine hydrochloride and the formula (5).
The resin composition prepared by mixing with 10 parts of the epoxy group-containing silane compound represented by is used as a surface treatment liquid, and the surface treatment and antibacterial test of the glass plate are performed with this surface treatment liquid in the same manner as in Example 1 to produce live cells. As a result of measuring the number, 3.4 × 10 ⁷ (pieces
/ ml).

Example 6 5 g of the surface treatment solution prepared in Example 1 was treated with 20 ml of ethyl ether.
g, and this diluted solution was repeatedly sprayed twice on a 50 × 50 × 2 mm acrylic plate twice (spraying amount of 1.5 ml each time) and allowed to stand at room temperature for one day 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 viable cell count was measured. As a result, viable cells were not found.

Example 7 The diluted solution prepared in Example 6 was repeatedly sprayed twice on a slate plate of 50 × 50 × 5 mm (spraying amount is the same as in Example 6), and the mixture was allowed to stand at room temperature for one day and night to complete the surface. The film was cured. The slate plate thus surface-treated is immersed in water at room temperature for 1 week, and then placed on potato dextrose agar medium to spore the mold.
(Test bacteria: Aspergillus niger
>) And culturing at 30 ° C. for 2 weeks and observing the growth state of the mold, the mold did not grow on the slate plate and the original appearance was maintained.

Comparative Example 2 5 g of the surface treatment solution prepared in Comparative Example 1 was mixed with ethyl ether 20
When the surface treatment of the slate plate by spraying was carried out in the same manner as in Example 7 using this diluted solution and the antifungal test after immersion in water was carried out, the entire surface of the slate plate was found to mold after 2 weeks. Development was recognized.

Example 8 The resin composition prepared in Example 1 was used without dilution and had a diameter of 40 m.
m, cast in 1mm thick mold, let cure at room temperature for 1 week,
A silicone rubber-like transparent sheet having a thickness of 1 mm was obtained. Using the obtained sheet, an antibacterial test was conducted after immersion in water in the same manner as in Example 1, and the viable cell count was measured. As a result, viable cells were not recognized.

Comparative Example 3 A sheet was prepared in the same manner as in Example 8 using the resin composition prepared in Comparative Example 1. Using the obtained sheet, an antibacterial test was conducted after immersion in water in the same manner as in Example 1, and the viable cell count was measured to be 5.1 × 10 ⁷ (cells / ml).

Example 9 In order to evaluate the characteristics of the resin composition of the present invention as an adhesive, the composition (treatment liquid) prepared in Example 1 was used to examine the adhesiveness to various materials. The adhesive strength was measured after the materials were adhered and then cured 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 mortar and cured at 20 ° C. and 65% RH for 3 days. From this, water was dropped on the coated surface to evaluate the waterproofness. As a result, the dropped water was repelled even after 1 hour and was not absorbed at all.

[0053]

The resin composition of the present invention gives an antimicrobial transparent cured product having properties similar to those of silicone rubber. Therefore, it can be used alone as an antimicrobial film or sheet, or can be used as an antimicrobial sealing material or adhesive, and can prevent the growth of fungi and bacteria, which have been a problem in this type of application, It can keep a good appearance.

The resin composition of the present invention can impart antibacterial and antifungal properties to various materials as a surface treatment agent,
Since it has a reactive functional group in its component, it has excellent binding properties to the surface of the material, and it is possible to impart favorable antibacterial and antifungal properties to materials such as plastics and metals that were difficult to surface-treat in the past. It is possible.

Further, since the resin composition of the present invention is a cured product in which the whole is integrally bonded by curing, the drug component does not elute, the safety is high, and the antimicrobial effect is excellent in sustainability. . Further, since it retains the properties of silicone, it is possible to impart the effects such as heat resistance, weather resistance, water repellency, gloss, surface protection, and electrical properties, which are unique to silicone, in addition to antimicrobial properties.

Claims (5)

[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. object. 2. An antimicrobial resin film, film and sheet formed by curing the composition according to claim 1. 3. An antimicrobial surface treatment agent comprising the composition according to claim 1. 4. An antimicrobial sealant comprising the composition of claim 1. 5. An antimicrobial adhesive comprising the composition according to claim 1.