JP6125965B2 - Method for producing p-hydroxybenzoic acid allyl polymer - Google Patents

Description

  The present invention relates to a method for producing an allyl p-hydroxybenzoate polymer having high antibacterial properties.

  In recent years, there has been a demand for maintaining a high level of safety in the living environment, and plastics having antibacterial and antifungal properties are used in various applications. For example, kitchenware (chopping board, knife pattern, sponge, detergent bottle, etc.), bathware (shower hose, shower head, shower curtain, bathtub, shampoo bottle, etc.), textile products (synthetic fiber, natural fiber, clothing, carpet, curtain) , Leather, etc.), household appliances (refrigerators, air conditioner parts, air conditioners, humidifiers, vacuum cleaners, etc.), rubber products, containers, polystyrene foam, food packaging materials, footwear, stationery, toys, automobile interior materials, etc. In addition, plastics having anti-rust properties are used.

  Conventionally, such antibacterial and antifungal products have been manufactured by using a physical method such as kneading the antibacterial agent into plastic, or coating the surface of the product with a paint dispersed with the antibacterial agent. Chemical methods such as introduction into plastic by modification or polymerization of antibacterial monomers are used. In particular, the chemical method provides a plastic that has a low elution of antibacterial components and is safe and has a low decrease in antibacterial activity over time.

  Paraoxybenzoates are conventionally known as antibacterial agents. For example, Patent Document 1 describes an antibacterial resin composition containing paraoxybenzoates. The antibacterial resin composition of Patent Document 1 is obtained by adding and mixing paraoxybenzoates in a resin, and elution of antibacterial components is inevitable.

  On the other hand, when paraoxybenzoates are used as polymer raw materials, the efficiency of the polymerization reaction is low, and it may be difficult to produce a resin.

Japanese Patent Laid-Open No. 10-237317

  An object of the present invention is to provide a method for efficiently producing an allyl p-hydroxybenzoate polymer having high antibacterial properties.

  As a result of intensive studies on the polymerization of allyl p-hydroxybenzoate, the present inventors have been able to efficiently obtain a polymer having antibacterial properties by polymerizing allyl p-acetoxybenzoate and then deacetylating it. As a result, the present invention has been completed.

  Further, the present inventors converted p-acetoxybenzoic acid into an acid chloride, reacted with allyl alcohol, and further acetylated allyl p-hydroxybenzoate as a by-product, whereby allyl p-acetoxybenzoate was obtained. It was found that a high yield was obtained.

式（Ｉ）

［式中、Ａｃはアセチル基を表す］。
That is, the present invention includes (A) a step of acidifying p-acetoxybenzoic acid, (B) a step of reacting the product obtained in step (A) with allyl alcohol, and (C) step (B). Provided is a method for producing allyl p-acetoxybenzoate represented by the formula (I), comprising the step of acetylating allyl p-hydroxybenzoate contained in the obtained product:

Formula (I)

[In the formula, Ac represents an acetyl group].

式（ＩＩ）

［式中、ｎは、ｎ≧５を満たす整数である］。
Further, the present invention is represented by the formula (II) including (D) a step of polymerizing allyl p-acetoxybenzoate and (E) a step of deacetylating the polymer obtained in step (D). Provided is a method for preparing an allyl p-hydroxybenzoate polymer:

Formula (II)

[Wherein n is an integer satisfying n ≧ 5].

  The present invention also provides an antibacterial resin composition containing the allyl p-hydroxybenzoate polymer obtained by the above production method, and a molding obtained by molding the allyl p-hydroxybenzoate polymer or the antibacterial resin composition. Provide goods.

  In the method for producing an allyl polymer of p-hydroxybenzoate of the present invention, by using allyl p-acetoxybenzoate as a monomer, radical polymerization caused by a hydroxyl group-containing monomer does not occur and p- has high antibacterial properties. An allyl hydroxybenzoate polymer can be produced efficiently. Further, the production efficiency of allyl p-hydroxybenzoate polymer is further increased by producing allyl p-acetoxybenzoate used as a monomer in the method by using the method for producing allyl p-acetoxybenzoate of the present invention. Can do.

  The allyl p-hydroxybenzoate polymer obtained by the production method of the present invention has a high antibacterial effect. Moreover, the elution of antibacterial components is less than that of the structure, and the antibacterial activity is less likely to decrease with time.

  The present invention relates to a process for producing allyl p-acetoxybenzoate and a process for producing an allyl p-hydroxybenzoate polymer. Hereafter, each process in this manufacturing method is demonstrated in detail.

(Synthesis of allyl p-acetoxybenzoate)
Step (A) in the method for producing allyl p-acetoxybenzoate of the present invention is a step of acidifying p-acetoxybenzoic acid. The p-acetoxybenzoic acid used in this step may be commercially available or may be produced using a method known to those skilled in the art. Examples of such a method include a method in which acetoxybenzoic acid is obtained by acetylating p-hydroxybenzoic acid with an acetylating agent such as acetic anhydride, acetyl chloride, methyl acetate, N, N-methylacetamide and the like.

  The acidification in the step (A) can be performed by a method in which p-acetoxybenzoic acid is reacted with a chlorinating agent such as thionyl chloride, oxalyl chloride, phosphorus trichloride, or phosphorus pentachloride. The molar ratio of p-acetoxybenzoic acid and chlorinating agent to be subjected to such a reaction is preferably 1: 1 to 1:10.

  In this reaction, an organic base such as N, N-dimethylformamide (DMF) or pyridine can be used as a catalyst. Moreover, although a solvent is not necessarily required, organic solvents, such as toluene and xylene, can be used.

  The reaction conditions are not particularly limited as long as acidification proceeds, but the reaction is preferably performed under a nitrogen stream or under nitrogen bubbling, the reaction temperature is 50 to 100 ° C., and the reaction time is 1 to 10 hours. Is preferred.

  After completion of the acid chloride step, the solvent and by-products are distilled off under reduced pressure, and the resulting acid chloride is subjected to the reaction with allyl alcohol in step (B).

  Step (B) in the method for producing allyl p-acetoxybenzoate of the present invention comprises reacting the product obtained in step (A) (p-acetoxybenzoic acid chloride) with allyl alcohol to form p-acetoxybenzoic acid. This is a process for producing allyl.

  The molar ratio of p-acetoxybenzoic acid chloride and allyl alcohol used in the reaction of step (B) is preferably 1: 1 to 1:10.

  A solvent is not always necessary, but an organic solvent such as N-methyl-2-pyrrolidone (NMP), DMF, dimethyl sulfoxide (DMSO) can be used. The reaction conditions are not particularly limited as long as the reaction between p-acetoxybenzoic acid chloride and allyl alcohol proceeds, but it is preferably performed under a nitrogen stream or under nitrogen bubbling, and the reaction temperature is 0 to 50 ° C. The reaction time is preferably 1 to 10 hours.

  After completion of the reaction, an extraction solvent is added to the reaction product, and a solvent layer containing allyl p-acetoxybenzoate can be recovered by a normal liquid separation operation. A common organic solvent can be used as the extraction solvent, but it is preferable to use ethyl acetate, diethyl ether, or the like.

  A small amount of allyl p-hydroxybenzoate is by-produced together with allyl p-acetoxybenzoate by the reaction of p-acetoxybenzoic acid chloride with allyl alcohol. Therefore, the product obtained in the step (B) may contain allyl p-acetoxybenzoate and a small amount of allyl p-hydroxybenzoate.

  In step (C) in the method for producing allyl p-acetoxybenzoate of the present invention, allyl p-hydroxybenzoate contained in the product obtained in step (B) is acetylated to form allyl p-acetoxybenzoate. It is the process of converting. Allyl p-hydroxybenzoate can be acetylated by reacting with acetic anhydride in the presence of a base such as pyridine or triethylamine and a solvent to give allyl p-acetoxybenzoate.

  The molar ratio of allyl p-hydroxybenzoate and acetic anhydride used in the acetylation reaction in step (C) is preferably 1: 2 to 1:50. The reaction conditions are not particularly limited as long as acetylation proceeds, but the reaction is preferably performed under a nitrogen stream or nitrogen bubbling, the reaction temperature is 50 to 150 ° C., and the reaction time is 1 to 10 hours. Is preferred.

  After completion of the acetylation reaction, allyl p-acetoxybenzoate can be recovered by a liquid separation operation similar to the above.

  When allyl p-hydroxybenzoate is subjected to a polymerization reaction, the hydroxy group may act as a radical scavenger and inhibit the polymerization reaction. On the other hand, since the product obtained through the above steps (A) to (C) is substantially free of allyl p-hydroxybenzoate, it requires an operation for separating and recovering all p-acetoxybenzoate. It can use for the below-mentioned polymerization reaction, without.

(Polymerization process)
Step (D) in the method for producing an allyl p-hydroxybenzoate polymer of the present invention is a step of subjecting allyl p-acetoxybenzoate to a polymerization reaction. The allyl p-acetoxybenzoate used as a monomer in step (D) is either a commercially available product, one obtained by the production method of the present invention described above, or one obtained by a production method known to those skilled in the art. Also good. In order to obtain an allyl p-hydroxybenzoate polymer in high yield, it is preferable to use allyl p-acetoxybenzoate produced by the production method of the present invention described above.

  The polymerization step in the step (D) can be performed by a known method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., but is particularly preferably performed by bulk polymerization and solution polymerization.

  Bulk polymerization can be performed by polymerizing a monomer without using a solvent in the presence of a polymerization initiator in a nitrogen stream or under nitrogen bubbling. Polymerization initiators include peroxides such as benzoyl peroxide and acetyl peroxide, and azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis-2,4-dimethylvaleronitrile. Can be used.

  Solution polymerization can be carried out in the same manner as bulk polymerization except that a solvent such as toluene or 1,4-dioxane is used.

  In any polymerization, the reaction temperature is preferably 50 to 150 ° C. and the reaction time is preferably 1 to 50 hours.

  After completion of the polymerization, a solvent in which the polymer is insoluble and the monomer is soluble can be added to precipitate the allyl p-acetoxybenzoate polymer, and the polymerized product can be recovered. Examples of the solvent that can be used for polymer precipitation include chloroform and methylene chloride. Alternatively, the p-acetoxybenzoic acid allyl polymer can be recovered by a method in which an organic solvent is added and a polymer is extracted into the organic layer by a liquid separation operation. Examples of the solvent that can be used for such extraction include ethyl acetate and diethyl ether.

(Deacetylation process)
Step (E) in the method for producing a p-hydroxybenzoic acid allyl polymer of the present invention is a step of obtaining a p-hydroxybenzoic acid allyl polymer by deacetylating the polymer obtained in step (D). The deacetylation in the step (E) can be performed, for example, by hydrolysis using a base, but is not limited to such a method.

  Deacetylation using a base can be carried out by adding 1 to 10 moles of a base such as sodium hydroxide or potassium hydroxide to the monomer unit of the p-acetoxybenzoic acid allyl polymer and reacting them.

  In the reaction, if necessary, a solvent such as acetone or methanol may be used. The reaction conditions are not particularly limited as long as deacetylation proceeds, but the reaction temperature is preferably 0 to 100 ° C. and the reaction time is preferably 0.5 to 5 hours.

  After completion of the deacetylation step, an acid such as hydrochloric acid is added to recover the p-hydroxybenzoic acid allyl polymer by precipitation. Moreover, when the unreacted monomer remains, it can be removed by a known purification means such as reprecipitation or dialysis.

  In the p-hydroxybenzoic acid allyl polymer obtained by the production method of the present invention, all monomer units constituting the polymer have a structure of p-hydroxybenzoic acid ester. That is, the polymer has a high antibacterial effect because p-hydroxybenzoic acid, which is an antibacterial component, is uniformly covalently bonded to the allyl polymer chain, thereby making contact with bacteria more effective. In addition, since the allyl p-hydroxybenzoate polymer has an antibacterial component introduced by a covalent bond, the antibacterial component is hardly eluted out of the system and the antibacterial property is less deteriorated over time. Furthermore, the polymer is highly safe because it has very little environmental pollution and no influence on the human body and is not decomposed in vivo.

  The allyl p-hydroxybenzoate polymer obtained by the production method of the present invention may be mixed with another resin as an antibacterial component to obtain an antibacterial resin composition. Other resins that can be mixed with the allyl p-hydroxybenzoate polymer are not particularly limited. For example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, polyacrylonitrile, polycarbonate, polyethylene terephthalate, ABS resin, nylon, Polyacetal, polytetrafluoroethylene, unsaturated polyester resin, polyvinylidene chloride, polyurethane, melamine resin, urea resin, epoxy resin, phenol resin, silicone resin, natural rubber, styrene butadiene rubber, chloroprene rubber, nitrile rubber, butadiene rubber, acrylic Rubber or the like can be used. The blending amount of the other resin is preferably 5 to 300 parts by weight, more preferably 10 to 250 parts by weight, based on 100 parts by weight of the p-hydroxybenzoic acid allyl polymer obtained by the production method of the present invention. Is more preferable.

  The present invention also provides a molded article obtained by molding the allyl p-hydroxybenzoate polymer obtained by the above production method. The allyl p-hydroxybenzoate polymer obtained by the production method of the present invention can be used as a molding resin as it is and can be formed into a molded product by known molding means such as injection molding, but the effect of the present invention is not impaired. It may be mixed with other moldable resins within the range and used for molding. In this case, as the other moldable resin, those described above can be used as other resins that can be mixed with the p-hydroxybenzoic acid allyl polymer in order to obtain an antibacterial resin composition. It is preferable to mix 1 to 100 parts by weight of the allyl p-hydroxybenzoate polymer obtained by the production method of the present invention with respect to parts by weight, and more preferably 5 to 50 parts by weight.

  The allyl p-hydroxybenzoate polymer obtained by the production method of the present invention can be used in various industrial applications, such as adhesives, cosmetics, ceramics, films, leathers, cloths, fibers, coatings, and coating agents. , Oil resistant paper, polymerization stabilizers and synthetic sponges can be used as main components. According to each of these applications, if necessary, filler, plasticizer, colorant, foaming agent, lubricant, ultraviolet absorber, antioxidant, processing stabilizer, weathering stabilizer, antistatic agent, flame retardant, Additives such as mold release agents and reinforcing materials may be added.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

Example 1 (Synthesis of p-hydroxybenzoic acid allyl polymer)
Reaction of p-acetoxybenzoic acid chloride and allyl alcohol A 1000-ml four-necked flask purged with nitrogen was charged with 225 g of toluene, 3 drops of DMF and 90.0 g of p-acetoxybenzoic acid (AcPOB), and dissolved by stirring. Next, 89.2 g of thionyl chloride was added and stirred at 60 ° C. for 120 minutes, and then toluene was distilled off under reduced pressure to obtain p-acetoxybenzoic acid chloride. To this p-acetoxybenzoic acid chloride, 68 ml of allyl alcohol previously dissolved in 100 ml of N-methyl-2-pyrrolidone was added dropwise at 0 ° C. and stirred at room temperature for 1 hour, and then the reaction solution was mixed with ethyl acetate. Transfer to a liquid funnel. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution for liquid separation, and then a saturated aqueous sodium chloride solution was added for liquid separation, and the aqueous layer was discarded to remove unreacted carboxylic acid, raw materials and inorganic components. The resulting ethyl acetate layer was dehydrated by adding sodium sulfate and stirring. After filtration, the filtrate was concentrated under reduced pressure to obtain 107.2 g of a yellow liquid.
^{By 1} H NMR (400 MHz, DMSO-d ₆ ) analysis, 1.99 (s, 3H), 4.80-4.82 (d, J = 3.9 Hz, 2H), 5.26-5.29 ( dd, J = 1.2 Hz, 7.8 Hz, 1H), 5.38-5.43 (dd, J = 1.2 Hz, 12.9 Hz, 1H), 6.01-6.04 (m, 1H) 7.29-7.32 (d, J = 6.6 Hz, 2H), 7.42-7.45 (dd, J = 4.7 Hz, 10.4 Hz, 1H), 8.03-8.05 ( d, 6.6 Hz, 2H) was confirmed, and it was confirmed to be allyl p-acetoxybenzoate.
Further, as a by-product, 13 mol% of allyl p-hydroxybenzoate was confirmed by ¹ H NMR proton ratio.

Acetic anhydride 100 ml, pyridine 50 ml and the yellow liquid 107.2 g obtained above were placed in a 500 ml four-necked flask in which allyl p-hydroxybenzoate was substituted with acetylated nitrogen and stirred. Subsequently, after heating up to 80 degreeC and making it react for 4 hours, the reaction liquid was moved to the separating funnel which put ethyl acetate. To this reaction solution, 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, saturated aqueous copper sulfate solution, deionized water and saturated aqueous sodium chloride solution were added, and the mixture was separated in sequence, and the aqueous layer was discarded to remove unreacted raw materials. . The resulting ethyl acetate layer was dehydrated by adding sodium sulfate and stirring, and after filtration, the filtrate was concentrated under reduced pressure to obtain 104.4 g of a yellow liquid.
^{By 1} H NMR (400 MHz, DMSO-d ₆ ) analysis, 2.30 (s, 3H), 4.80-4.82 (d, J = 3.9 Hz, 2H), 5.26-5.29 ( dd, J = 1.2 Hz, 7.8 Hz, 1H), 5.38-5.43 (dd, J = 1.2 Hz, 12.9 Hz, 1H), 6.01-6.04 (m, 1H) , 7.29-7.32 (d, J = 6.6 Hz, 2H), 8.03-8.05 (d, J = 6.6 Hz, 2H), and allyl p-acetoxybenzoate was confirmed. It was confirmed that.

Polymerization of allyl p-acetoxybenzoate 104.4 g of allyl p-acetoxybenzoate synthesized above was placed in a 1000 ml four-necked flask and stirred at 100 ° C. for 1 hour under nitrogen bubbling. Next, 8 g of azobisisobutyronitrile (AIBN) was added and reacted at 100 ° C. for 4 hours under nitrogen bubbling. Then, 4 g of AIBN was added again and reacted for 5 hours, and the reaction solution was separated into ethyl acetate. Moved to the funnel. After deionized water was added to the reaction solution for liquid separation, a saturated aqueous sodium chloride solution was further added for liquid separation, and the aqueous layer was discarded to recover the reaction product in the ethyl acetate layer. The reaction product was dehydrated by adding sodium sulfate and stirring. After filtration, the filtrate was concentrated under reduced pressure to obtain 28.2 g of a tan solid.

Deacetylation of p-acetoxybenzoic acid allyl polymer A 200 ml acetone flask was charged with 200 g of acetone and 28.2 g of the tan solid obtained above, and dissolved by stirring. Subsequently, 200 g of a 30 wt% aqueous sodium hydroxide solution was added dropwise at 0 ° C., and the mixture was returned to room temperature and stirred for 1 hour. Further, 100 g of deionized water was added, and acetone was distilled off under reduced pressure. While maintaining the reaction solution at 0 ° C., 15% by weight hydrochloric acid was added until pH 3 and acidified, and then transferred to a separatory funnel containing ethyl acetate. To this reaction solution, a saturated sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride aqueous solution were sequentially added and separated, and the aqueous layer was discarded to remove unreacted raw materials and inorganic components. The resulting ethyl acetate layer was dehydrated by adding sodium sulfate and stirring. After filtration, ethyl acetate was distilled off from the filtrate under reduced pressure to obtain a tan solid. The obtained tan solid was dissolved in 20 ml of acetone and dialyzed for 24 hours (using Spectra / Por ^{(registered trademark)} Dialysis Membrane MWCO 6-8,000 manufactured by SPECTRUM LABORATORIES) three times. After completion of dialysis, acetone was distilled off under reduced pressure, followed by vacuum drying to obtain 24.4 g (yield 29%) of a tan solid.
^{By 1} H NMR (400 MHz, DMSO-d ₆ ) analysis, 0.50-2.38 (br, 4H), 3.78-4.35 (br, 1H), 6.54-6.91 (br, 2H), 7.53-7.90 (br, 2H), 10.08-10.48 (br, 1H), and the formation of p-hydroxybenzoic acid allyl polymer was confirmed.

Comparative Example 1 (Synthesis of p-hydroxybenzoic acid allyl polymer)
In a 50 ml Erlenmeyer flask, 1.1 g of allyl p-acetoxybenzoate synthesized in the same manner as in Example 1 and 10 g of acetone were added and stirred. Next, 2 g of a 30 wt% aqueous sodium hydroxide solution was added dropwise at 0 ° C., and the mixture was returned to room temperature and stirred for 1 hour. Further, 10 g of deionized water was added, and acetone was distilled off under reduced pressure. While maintaining the reaction solution at 0 ° C., 15% by weight hydrochloric acid was added until pH 3 and acidified, and then transferred to a separatory funnel containing ethyl acetate. To this reaction solution, a saturated sodium hydrogen carbonate aqueous solution, deionized water and a saturated sodium chloride aqueous solution were sequentially added and separated, and the aqueous layer was discarded to remove unreacted raw materials and inorganic components. The resulting ethyl acetate layer was dehydrated by adding sodium sulfate and stirring. After filtration, ethyl acetate was distilled off from the filtrate under reduced pressure to obtain 0.89 g of a yellowish white solid (allyl p-hydroxybenzoate). Obtained.
A 50 ml two-necked flask was charged with 10 ml of toluene and 0.89 g of the above yellowish white solid, and stirred at 100 ° C. for 1 hour under nitrogen bubbling. Next, 0.08 g of AIBN was added and reacted at 100 ° C. for 4 hours under nitrogen bubbling. After 0.04 g of AIBN was added and reacted again for 5 hours, the reaction solution was transferred to a separatory funnel containing ethyl acetate. After deionized water was added to the reaction solution for liquid separation, a saturated aqueous sodium chloride solution was further added for liquid separation, and the aqueous layer was discarded to recover the reaction product in the ethyl acetate layer. The obtained ethyl acetate layer was concentrated under reduced pressure, and 0.88 g of the obtained solid was subjected to NMR analysis. As a result, no peak broadening was observed, and quantitative recovery of the raw material (allyl p-hydroxybenzoate) was confirmed. It was. Such a result means that an allyl p-hydroxybenzoate polymer was not obtained.

Comparative Example 2 (Synthesis of allyl benzoate polymer)
In a 20 ml two-necked flask, 8.1 g of allyl benzoate was placed and stirred at 100 ° C. for 1 hour under nitrogen bubbling. Next, 0.4 g of AIBN was added and reacted at 100 ° C. for 4 hours under nitrogen bubbling. After 0.4 g of AIBN was added and reacted again for 5 hours, the reaction solution was transferred to a separatory funnel containing ethyl acetate. After deionized water was added to the reaction solution for liquid separation, a saturated aqueous sodium chloride solution was further added for liquid separation, and the aqueous layer was discarded to recover the product in the ethyl acetate layer. The resulting ethyl acetate layer was dehydrated by adding sodium sulfate and stirring. After filtration, the filtrate was concentrated under reduced pressure to obtain a pale yellow solid. This pale yellow solid was dissolved in 20 ml of acetone and dialyzed for 24 hours (using Spectra / Por ^{(registered trademark)} Dialysis Membrane MWCO 6-8,000 manufactured by SPECTRUM LABORATORIES) three times. After completion of dialysis, acetone was distilled off under reduced pressure, followed by vacuum drying to obtain 1.1 g (yield 14%) of a pale yellow solid.
^{According to 1} H NMR (400 MHz, DMSO-d ₆ ) analysis, 0.92-2.22 (br, 3H), 3.82-4.48 (br, 2H), 7.97-8.12 (br, 5H) was confirmed, and the formation of allyl benzoate polymer was confirmed.

  Table 1 shows the yield of allyl p-hydroxybenzoate polymer obtained in Example 1 and Comparative Example 1.

  By the production method of the present invention, an allyl p-hydroxybenzoate polymer could be obtained in a higher yield than the method of polymerizing allyl p-hydroxybenzoate.

Antibacterial test The polymers obtained in Example 1 and Comparative Example 2 were subjected to an antibacterial test in accordance with JIS L 1902: 2008 (bacterial liquid absorption method) as follows.
Escherichia coli NBRC 3972 and Staphylococcus aureus NBRC 12732 were used as strains. The strain was transplanted into a slant medium (ordinary agar medium (manufactured by Nissui Pharmaceutical Co., Ltd.)) and cultured at 35 ° C. for 21 hours. This was suspended in 1/20 normal bouillon medium (Eiken Chemical Co., Ltd.) supplemented with 0.05% Tween 80, OD ₆₀₀ was measured with a spectrophotometer, and the bacterial concentration was 1 × 10 ^{5 to} 3 ×. It adjusted so that it might become 10 < ⁵ > pieces / ml.
0.4 g of the polymer powder obtained in Example 1 and Comparative Example 2 or 0.4 g of unprocessed test powder (granular polyethylene, manufactured by Scientific Polymer Products) was placed in a sterilized vial, and 0.2 ml of the adjusted bacterial solution was added. Added. These were cultured in a 35 ° C. incubator for 21 hours.
Immediately after adding the bacterial solution, or 20 ml of SCDLP medium (manufactured by Eiken Chemical Co., Ltd.) was added to the vial after 21 hours of culturing, and the cap was closed and shaken 30 times or more by hand to wash out the test bacteria. The washing solution was diluted with physiological saline and dispensed into two sterilized petri dishes (1 ml each). A standard agar medium (manufactured by Nissui Pharmaceutical Co., Ltd.) 15 to 20 ml was added to each, and mixed. The culture was performed in triplicate. After the cultivation, the number of colonies was measured, and the bacteriostatic activity value was calculated as follows. The results are shown in Table 2.

Calculation of viable count M = Z × R × C
M: Viable count (individual)
Z: Average number of colonies of two petri dishes (pieces)
R: dilution rate with physiological saline C: amount of SCDLP medium used for washing (ml)

Calculation of activity value (bacteriostatic activity value S is determined to be antibacterial effect when S is 2.0 or more)
S = (M _b −M _a ) − (M _c −M ₀ ) ≈M _b −M _c
S: Bacteriostatic activity value M _a : Average value of logarithm of viable count immediately after adding bacterial solution to unprocessed test powder M _b : After adding bacterial solution to unprocessed test powder and culturing for 21 hours Average value of logarithmic value of viable cell count M ₀ : Average value of logarithmic value of viable cell count immediately after adding the bacterial solution to the polymer powder obtained in Example 1 and Comparative Example 2 M _c : Example 1 and comparison The average value of the logarithmic value of the number of viable bacteria after adding the bacterial solution to the polymer powder obtained in Example 2 and culturing for 21 hours, the growth value F is 1.0 or more in the control test group It is necessary.
F = M _b −M _a ≧ 1.0

式（Ｉ）

［式中、Ａｃはアセチル基を表す］。

〔２〕（Ｄ）ｐ‐アセトキシ安息香酸アリルを重合する工程、および
（Ｅ）工程（Ｄ）で得られた重合物を脱アセチル化する工程
を含む、式（ＩＩ）で表されるｐ‐ヒドロキシ安息香酸アリルポリマーの製造方法：

式（ＩＩ）

［式中、ｎは、ｎ≧５を満たす整数である］。

〔３〕 ｐ‐アセトキシ安息香酸アリルが〔１〕に記載の製造方法によって得られたものである、〔２〕に記載のｐ‐ヒドロキシ安息香酸アリルポリマーの製造方法。
〔４〕 塩基を用いる加水分解によって工程（Ｅ）の脱アセチル化を行う、〔２〕または〔３〕に記載のｐ‐ヒドロキシ安息香酸アリルポリマーの製造方法。
〔５〕 〔２〕〜〔４〕のいずれかに記載の製造方法によって得られたｐ‐ヒドロキシ安息香酸アリルポリマーを含む抗菌性樹脂組成物。
〔６〕 〔２〕〜〔４〕のいずれかに記載の製造方法によって得られたｐ‐ヒドロキシ安息香酸アリルポリマーを成形して得られる成形品。
〔７〕 〔５〕に記載の抗菌性樹脂組成物を成形して得られる成形品。 The polymer obtained by the production method of the present invention showed a high bacteriostatic activity value as compared with the polymer of the comparative example.

Preferred embodiments of the present invention include:
[1] (A) Step of acidifying chloride of p-acetoxybenzoic acid,
(B) reacting the product obtained in step (A) with allyl alcohol; and
(C) A step of acetylating allyl p-hydroxybenzoate contained in the product obtained in step (B).
A process for producing allyl p-acetoxybenzoate represented by the formula (I):

Formula (I)

[In the formula, Ac represents an acetyl group].

[2] (D) a step of polymerizing allyl p-acetoxybenzoate, and
(E) A step of deacetylating the polymer obtained in step (D)
A method for producing an allyl p-hydroxybenzoate polymer represented by formula (II) containing:

Formula (II)

[Wherein n is an integer satisfying n ≧ 5].

[3] The method for producing an allyl p-hydroxybenzoate polymer according to [2], wherein allyl p-acetoxybenzoate is obtained by the production method according to [1].
[4] The method for producing an allyl p-hydroxybenzoate polymer according to [2] or [3], wherein the deacetylation in the step (E) is performed by hydrolysis using a base.
[5] An antibacterial resin composition containing an allyl p-hydroxybenzoate polymer obtained by the production method according to any one of [2] to [4].
[6] A molded product obtained by molding an allyl p-hydroxybenzoate polymer obtained by the production method according to any one of [2] to [4].
[7] A molded product obtained by molding the antibacterial resin composition according to [5].

Claims (3)

(A) a step of acidifying p-acetoxybenzoic acid;
(B) a step of reacting the product obtained in step (A) with allyl alcohol, and (C) a step of acetylating allyl p-hydroxybenzoate contained in the product obtained in step (B). A process for producing allyl p-acetoxybenzoate represented by the formula (I):

Formula (I)

[In the formula, Ac represents an acetyl group].
(D) a method comprising polymerizing allyl p-acetoxybenzoate obtained by the production method according to claim 1 and (E) deacetylating the polymer obtained in step (D). Method for producing p-hydroxybenzoic acid allyl polymer represented by (II):

Formula (II)

[Wherein n is an integer satisfying n ≧ 5].
The method for producing a p-hydroxybenzoic acid allyl polymer according to claim 2 , wherein the deacetylation in the step (E) is performed by hydrolysis using a base.