JP3178546B2 - Antimicrobial agent for polymer material and antimicrobial polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to an antibacterial agent for polymer materials and
Relates and antimicrobial polymer composition, the antimicrobial comprising more particularly from antimicrobial polymer containing at least vinylbenzyl phosphonium salts or / and salts as a monomer component
The present invention relates to an antibacterial polymer composition containing an agent .

[0002]

2. Description of the Related Art In an environment surrounding us, for example, various kinds of antibacterial agents are used in fields such as industrial use, agricultural use and food additive use. Most of the antibacterial agents currently used are synthetic antibacterial agents having a rather high toxicity. However, in recent years, research aimed at reducing the toxicity of antibacterial agents has been progressing, and immobilized antibacterial agents which are insoluble and show little toxicity have been developed.

As a polymer-type antibacterial agent as an immobilized antibacterial agent, there has been reported a pendant-type bactericide fixed to a polymer chain such as polyvinyl, polyacrylate, polymethacrylate, polyester and polyamide. For example, an alkylpyridinium salt and an alkyldimethylbenzylammonium salt are fixed on a polyvinyl chain, biguanites are fixed on a polyacrylate chain and a polymethacrylate chain, and an alkylpyridinium salt is fixed on a polyester chain and a polyamide chain. Have been. Among these, most of the immobilized antibacterial agents that are being put into practical use or under study are quaternary ammonium salts.

On the other hand, phosphonium salt compounds, like various nitrogen-containing compounds, are known as biologically active chemicals, and have a broad activity spectrum against bacteria, fungi and algae. As regards these, for example, JP-A-63-60903 and JP-A-1-9359
No. 6, JP-B-2-58998 and the like.

[0005]

However, although the quaternary ammonium salt-based immobilized antibacterial agent has a broad antibacterial spectrum, the bactericidal effect of acting on microorganisms by short-time contact is still insufficient. Similarly, the phosphonium salt compounds also do not have sufficient antibacterial activity.

In view of the above facts, the inventors of the present invention have conducted intensive studies and have found that an antibacterial agent comprising a vinylbenzylphosphonium salt and / or an antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component is used as a polymer material. The present inventors have found that a polymer composition obtained by adding and blending with a polymer exhibits excellent antibacterial activity, and have completed the present invention.

[0007]

Means for Solving the Problems That is, the first aspect of the present invention
The invention of the following general formula (1)

Embedded image (Wherein R ₁ , R ₂ and R ₃ are a hydrogen atom, hydroxy
Group, linear or branched alkyl having 1 to 18 carbon atoms
Represents an alkyl group, an aryl group or an aralkyl group;
Groups, aryl groups and aralkyl groups are hydroxy or
May be substituted with an alkoxy group. X ^- is Anio
To indicate Vinylbenzylphosphonium represented by)
It is an antibacterial agent for polymer materials consisting of salt.

[0008] The second invention of the present invention provides the following general
Equation (1)

Embedded image (Wherein R ₁ , R ₂ , R ₃ and X ⁻ are the same as defined above)
You. The vinylbenzylphosphonium salt represented by
Antibacterial polymer containing at least as a nomer component
It is an antimicrobial agent for polymer materials.

Further, a third invention of the present invention provides the following general formula (1)

Embedded image (Wherein, R ₁ , R ₂ , R ₃ and X ⁻ are the same as described above) by adding an antibacterial agent comprising a vinylbenzylphosphonium salt represented by the following formula to a thermoplastic resin, a thermosetting resin, a synthetic rubber and a thermosetting resin. An antimicrobial polymer composition characterized by being added to and blended with a polymer material selected from plastic elastomers. Further, a fourth invention of the present invention provides the following general formula (1)

Embedded image (Wherein R ₁ , R ₂ , R ₃ and X ⁻ are the same as described above). An antibacterial agent comprising an antibacterial polymer containing at least a vinylbenzylphosphonium salt represented by the following formula: An antibacterial polymer composition for molding characterized by being added to and blended with a polymer material selected from a thermosetting resin, a synthetic rubber and a thermoplastic elastomer. Further, the fifth invention of the present invention provides the following general formula (1)

Embedded image (Wherein, R ₁ , R ₂ , R ₃ and X ⁻ are the same as described above), and an antibacterial agent comprising an antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component. Agent
An antibacterial polymer composition for molding characterized by being added to and blended with a polymer material selected from a thermoplastic resin, a thermosetting resin, a synthetic rubber, and a thermoplastic elastomer.

Hereinafter, the present invention will be described in more detail.
As described above, the antibacterial polymer composition according to the present invention comprises, as an active ingredient having an antibacterial activity, a vinylbenzylphosphonium salt or / and an antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component. The composition comprises the following three embodiments.

A mixture in which the vinylbenzylphosphonium salt is mixed with a polymer material as an antibacterial agent A mixture in which an antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component is mixed with a polymer material as an antibacterial agent Mixture of an antimicrobial polymer containing at least a vinylbenzylphosphonium salt as a monomer component mixed with a polymer material as an antimicrobial agent

In the present invention, the vinylbenzylphosphonium salt is represented by the following general formula (1):

[0013]

Embedded image

In the formula, specific examples of R _{1 to} R ₃ include:
Hydrogen atom; hydroxy group; linear or branched alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, octyl, dodecyl, isopropyl; phenyl, tolyl, xylyl, etc. An aralkyl group such as benzyl and phenyl; the alkyl group, the aryl group and the aralkyl group may be substituted with a hydroxy group or an alkoxy group. Among them, preferred are an alkyl group, an aryl group and an aralkyl group, and more preferred are an alkyl group and an aryl group. Also,
R ₁ , R ₂ and R ₃ may be the same or different groups.

Further, the anion (X ^-) include, for example fluorine, chlorine, bromine or a halogen such as iodine ions,
Carboxyl ion such as formic acid, acetic acid, oxalic acid, sulfate ion, phosphate ion, methyl or dimethyl phosphate ion, ethyl or diethyl phosphate ion, antimony fluoride ion, phosphorus fluoride ion, arsenic fluoride ion, boron fluoride ion , Perchlorate ion and the like, and among them, a halogen ion is preferable.

When X ^- is an antimony fluoride ion, a phosphorus fluoride ion, an arsenic fluoride ion, a boron fluoride ion, or a perchlorate ion, it becomes water-insoluble and the solubility is determined by R ₁ to R _1. It also changes by changing ₃ .

Therefore, the vinylbenzylphosphonium salt and the antibacterial polymer can be designed with the solubility according to the use by changing R _{1 to} R ₃ and X ⁻ in the general formula (1).

The antibacterial effect of the vinylbenzylphosphonium salt represented by the general formula (1) is affected by the length of R _{1 to} R ₃ of the phosphonium salt in the formula when R _{1 to} R ₃ are alkyl groups. , Ethyl, butyl, octyl, the longer the antibacterial effect increases.

Next, the vinylbenzylphosphonium salt represented by the general formula (1) will be described more specifically. For example, triethyl-3-vinylbenzylphosphonium chloride, triethyl-4-vinylbenzylphosphonium chloride, tributyl-3-vinyl Benzylphosphonium chloride and tributyl-4-vinylbenzylphosphonium chloride, triphenyl-3-vinylbenzylphosphonium chloride and triphenyl-4-vinylbenzylphosphonium chloride, trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4
-Vinylbenzylphosphonium chloride, triethyl-3-vinylbenzylphosphonium bromide and triethyl-4-vinylbenzylphosphonium bromide, triethyl-3-vinylbenzylphosphonium tetrafluoroborate and triethyl-4-vinylbenzylphosphonium tetrafluoroborate. You can,
It is not limited to these.

Next, as the antibacterial polymer used as the antibacterial agent, a polymer containing at least the vinylbenzylphosphonium salt as a monomer component is used.

Specifically, the following general formula (2)

[0022]

Embedded image

(Wherein, R _{1 to} R ₃ , X ⁻ are the same as above, and n is an integer of 2 or more), and a vinylbenzylphosphonium salt represented by the above general formula (1) And / or a copolymer of the above-mentioned vinylbenzylphosphonium salt and a compound having an unsaturated double bond copolymerizable with the salt.

The antibacterial effect of the homopolymer of the vinylbenzylphosphonium salt represented by the general formula (2) is similar to that of the vinylbenzylphosphonium salt, when R _{1 to} R ₃ of the phosphonium salt in the formula are alkyl groups. Although affected by its length, its antimicrobial effect is several orders of magnitude better for homopolymers than the vinylbenzylphosphonium salts.

The degree of polymerization of the polymer represented by the general formula (2) is not particularly limited, but is 2 or more, and in many cases, 5 or more, preferably 40 to 200.

Next, as the compound having an unsaturated double bond copolymerizable with the vinylbenzylphosphonium salt represented by the general formula (1), for example, ethylene, propylene, butylene, isobutylene, diisobutylene, vinyl chloride, chloride Vinylidene, vinyl bromide, (meth) acrylic acid, alkyl (meth) acrylate, (meth) acrylamide, vinyl alcohol, vinyl acetic acid, acrylonitrile, vinyl sulfonate, N-vinyl-2-pyrrolidone, maleic acid, fumaral Acid, styrene, vinyltoluene, cinnamic acid, vinylthiophene, vinylpyridine or vinylimidazole.
Species or two or more species may be used.

The proportion of the structural unit of the vinylbenzylphosphonium salt in the copolymer of the compound having an unsaturated double bond and the vinylbenzylphosphonium salt is usually 1 to 99 mol%, preferably 5 to 50 mol. % Is desirable. The ratio of the structural unit of the compound having an unsaturated double bond is usually 99 to 1 mol%, preferably 95 to 50 mol%.

The polymerization form of each structural unit in the copolymer is various, and may be any of random, block and graft.

The degree of polymerization of such a copolymer is not particularly limited, but in most cases, the antibacterial activity is 5 or more, preferably 40 to 200.

The antibacterial polymer composition according to the present invention can be adjusted from the water-soluble to the water-insoluble one according to the design of the compound. When blended with the polymer material of the base material, it does not matter if it is used in combination with another antibacterial agent, for example, an inorganic antibacterial agent such as antibacterial zeolite or antibacterial apatite, or a quaternary ammonium salt-based organic antibacterial agent. Absent.

Further, silica, talc, diatomaceous earth, silicate clay, metal silicate, alumina, magnesia, titanium oxide, zinc white, zeolite, hydrotalcite,
It may be used by being supported on an inorganic carrier such as hydrocalcite.

The polymer material in which the antibacterial agent according to the present invention is blended is not particularly limited, and may be not only a thermoplastic or thermosetting resin but also an elastic resin such as a synthetic rubber depending on the purpose of use. What is necessary is just to select suitably.

Representative examples of the thermoplastic resin include chlorine resins such as polyvinyl chloride, polyvinylidene chloride and chlorinated polyolefin, polyolefin resins such as polyethylene and polypropylene, polystyrene, polyvinyl acetate, and (meth) acrylic. Resin, other vinyl resins such as polyacetal resin, polyester resin, polysulfone resin, fluorine resin, polyamide resin, polyimide resin, polyphenylene sulfide resin, polycarbonate resin, ionomer resin, silicon resin, fluorine resin or AAS resin, AES resin, AS Resins, ABS resins, copolymer resins such as EVA resins, etc., may be one or more composite resins such as polymer alloys.

Examples of the thermosetting resin include phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, urethane resin, diallyl phthalate resin, silicon resin and the like.
There may be more than one species.

Examples of the synthetic rubber include SBR, BR, I
Elastic resins such as R, NBR, urethane rubber, silicone, and thermoplastic elastomer are exemplified.

According to the present invention, the amount of the vinylbenzylphosphonium salt represented by the above general formula (1) and / or the antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component, which is added to the polymer material, is as follows: Although it varies depending on the use of the synthetic resin composition, it is often in the range of 0.001 to 50% by weight, preferably 0.01 to 20% by weight based on the total weight of the antibacterial polymer resin composition. In the resin composition constituted as above, it can be blended up to 50% by weight. If the amount is less than 0.001% by weight, the antibacterial action of the antibacterial polymer composition cannot be substantially obtained, and the upper limit is often limited for economic reasons. Is set.

The content of the polymer material in the antibacterial polymer composition of the present invention is 99.999 to 50% by weight, preferably 9% by weight, based on the total weight of the antibacterial polymer resin composition.
A range of 9.99 to 80% by weight is desirable.

In preparing the antimicrobial polymer composition, various polymer additives such as extender pigments such as titanium oxide, calcium carbonate and silica, organic or inorganic coloring materials, plasticizers, heat-resistant agents, antioxidants It is possible to use a heat stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, and the like in combination, and if necessary, it can be used as a mixture as a so-called one-pack type additive in advance. These additives are appropriately selected according to the physical properties and use of the resin or its composition, and the amount of the additive does not need to be particularly limited.

Next, the antibacterial polymer composition according to the present invention can be formed into a film, sheet, plate, pellet, or the like by a usual molding method such as extrusion molding, casting, vacuum molding, low pressure molding and the like. .

[0040]

The present invention will be further described below with reference to examples.

Examples 1 to 22 (1) Synthesis of antibacterial agent of vinylbenzylphosphonium salt 9.85 parts by weight of chloromethylstyrene and trioctylphosphine were placed in a flask sufficiently purged with nitrogen.
88 parts by weight were added and then 20 parts by volume of n-hexane were added. The liquid temperature in the flask was set to 25 ° C., and the reaction was carried out for 24 hours to obtain a product of white crystals. The crystals are filtered and n
-Washed thoroughly with hexane. The obtained product was dried under reduced pressure and room temperature to obtain 8.84 parts by weight of a mixture of trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride (referred to as sample A).

(2) Synthesis of antibacterial polymer (i) 2.00 parts by weight of a mixture of trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride was dissolved in 20 parts by volume of water. 0.0367 parts by weight of -azobis- (2-aminodipropane) hydrochloride was added, followed by degassing and sealing.
This was left to polymerize at 60 ° C. for 6 hours, then poured into a large excess of tetrahydrofuran, and the precipitated precipitate was collected by filtration. 0.97 parts by weight of a mixture of polytrioctyl-3-vinylbenzylphosphonium chloride and polytrioctyl-4-vinylbenzylphosphonium chloride (hereinafter referred to as sample B) was obtained. The weight average molecular weight of the polymer was 76,200.

(Ii) 1.5 parts by weight of a mixture of trioctyl-3-vinylbenzylphosphonium chloride and trioctyl-4-vinylbenzylphosphonium chloride and 0.31 part by weight of acrylamide were dissolved in 10 parts by weight of dimethylformamide. 0.0181 parts by weight of butyronitrile was added and the tube was degassed and sealed. This is 6
After polymerizing by allowing to stand at 0 ° C. for 6 hours, the mixture was poured into a large excess of acetone, and the resulting precipitate was collected by filtration to obtain polytrioctyl-3-vinylbenzylphosphonium chloride and polytrioctyl-4-vinylbenzyl. 1.11 parts by weight of a phosphonium chloride: acrylamide copolymer (referred to as sample C) was obtained. The weight average molecular weight of the copolymer was 10,500.

(Preparation of antibacterial polymer composition) To a variety of resins shown in Table 1, samples A, B and C of various antibacterial agents were added in predetermined amounts shown in Tables 2 and 3 and kneaded. By injection molding, each 180mm x width 50
A test piece having a size of 1 mm × 1 mm was obtained.

(Antibacterial activity test) (1) Staphylococcus aureu, a representative of Gram-positive bacteria
s) Escherichia coli (Escherichia col) as a representative of IFO 12732 and Gram-negative bacteria
i) The antibacterial resin material obtained in each example was allowed to act on IFO 3806 at the action time shown in Tables 2 and 3. Tables 2 and 3 show the results of the obtained bactericidal activity. The evaluation of the bactericidal activity was performed by a solution dilution method.

Solution dilution method: 1 ml of 18 ml of physiological saline
2 ml of 10 ⁷ bacteria were ingested per ml, and a test piece piece (length 10 × width 10 × thickness 1 mm) was brought into contact, and the number of bacteria was measured thereafter. A significant decrease in the number of bacteria relative to the contact time indicates that the bactericidal property is stronger. The numbers in the table indicate the number of bacteria (cells / ml).

(2) Test piece (vertical 10 × horizontal 1)
(0 × 1 mm) was added to 50 ml of mold dilution water (Note 1) prepared in advance, and the mixture was slowly stirred with a magnetic stirrer for 10 minutes. Next, this liquid was subjected to a culture test (Note 2) using a simple microorganism measuring instrument, San-Ai Bio Checker M (for testing fungi and yeasts: manufactured by San-Ai Oil Co., Ltd.). Table 4 shows the results.

(Note 1) ± 1 g of the black mold occurrence wall was sterilized with 10 parts of sterile water.
Diluted to 0 ml-for fungal test (Note 2) Culture was performed in an incubator at 27 to 30 ° C for 4 days.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

(Note 3) The degree of fungal contamination was evaluated in the following four stages. -: No contamination +: Light contamination +++: Medium contamination +++: Strong contamination (Note 4) When no antibacterial polymer was added.

[0054]

As described above, the antibacterial polymer composition of the present invention contains a vinylbenzylphosphonium salt and / or an antibacterial agent comprising an antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component. Therefore, an effect having excellent antibacterial activity can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 25/00-25/18 C08K 5/50

Claims (8)

(57) [Claims] 1. The following general formula (1): (Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; aralkyl group optionally substituted by a hydroxy group or an alkoxy group .X ^- polymeric materials antibacterial agent comprising a vinylbenzyl phosphonium salt represented by represents an anion).. 2. The antibacterial agent for a polymer material according to claim 1, wherein the polymer material comprises a material selected from a thermoplastic resin, a thermosetting resin, a synthetic rubber, and a thermoplastic elastomer. 3. The following general formula (1): (Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; aralkyl group optionally substituted by a hydroxy group or an alkoxy group .X ^- antibacterial polymer material consisting of antimicrobial polymer containing at least as a monomer component a vinylbenzyl phosphonium salt represented by represents an anion).. 4. The antibacterial agent for a polymer material according to claim 3, wherein the polymer material comprises a material selected from a thermoplastic resin, a thermosetting resin, a synthetic rubber, and a thermoplastic elastomer. 5. The following general formula (1): (Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; aralkyl group optionally substituted by a hydroxy group or an alkoxy group .X ^-. is an antimicrobial agent comprising a vinylbenzyl phosphonium salt represented by indicating the anion), thermoplastic resins, thermosetting resins, synthetic rubbers and thermal An antimicrobial polymer composition characterized by being added to and blended with a polymer material selected from plastic elastomers. 6. The following general formula (1): (Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; aralkyl group optionally substituted by a hydroxy group or an alkoxy group .X ^-. is an antimicrobial agent comprising an antimicrobial polymer containing at least vinylbenzyl phosphonium salt represented by showing the anion) as a monomer component, a thermoplastic resin An antibacterial polymer composition for molding characterized by being added to and blended with a polymer material selected from a thermosetting resin, a synthetic rubber and a thermoplastic elastomer. 7. The following general formula (1): (Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group; aralkyl group optionally substituted by a hydroxy group or an alkoxy group .X ^- antibacterial consisting antimicrobial polymer containing at least vinylbenzyl phosphonium salt and the vinylbenzyl phosphonium salt represented by an anion) as a monomer component. An antibacterial polymer composition for molding , characterized in that an agent is added to and blended with a polymer material selected from thermoplastic resins, thermosetting resins, synthetic rubbers and thermoplastic elastomers. 8. The method according to claim 5, wherein the vinylbenzylphosphonium salt and / or the antibacterial polymer containing at least the vinylbenzylphosphonium salt as a monomer component is contained in an amount of 0.001 to 50% by weight based on the total weight. Item 10. The antibacterial polymer composition for molding according to item 8.