JP2016175956A - Bacteria-repellent material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bacteria-repellent material where, even if microorganisms are deposited thereon, the microorganisms can be easily removed with aqueous solution.SOLUTION: A bacteria-repellent material comprises polyacetal resin (A) comprising an ester terminal group represented by the following formula, where the ester terminal group is contained at the rate of 20 μmol or less in the polyacetal resin (A) 1 g. RCOO- (where R is a hydrogen atom or an alkyl group).SELECTED DRAWING: None

Description

  The present invention relates to a bacteria repellent material.

  Resin products are often used for wallpaper in medical facilities and nursing care facilities, shower heads, toilet seats, water facilities such as washbasins, and nursing care products. Regarding these resin products, it has been pointed out that the propagation of microorganisms attached to the surface of the resin products has an adverse effect on the human body. For this reason, various proposals have been made with the idea of suppressing the growth of microorganisms in order to reduce the adverse effects on the human body.

  For example, Patent Document 1 below proposes an antibacterial composition containing zeolite substituted with silver ions, and this antibacterial composition is shown to have excellent antibacterial properties.

JP 2007-091501 A

  However, the antibacterial composition described in Patent Document 1 has the following problems.

  That is, microorganisms such as bacteria are attached to the antibacterial composition described in Patent Document 1 above. In the antibacterial composition, the growth of the attached microorganism is only suppressed. For this reason, the antibacterial composition described in Patent Document 1 has room for further improvement from the viewpoint of reducing adverse effects on the human body.

  In this respect, the microorganism low-adhesive material (hereinafter referred to as “bacterial repellent”) that does not suppress the growth of attached microorganisms but can remove microorganisms more easily with an aqueous solution even if the microorganisms adhere. Such a material is very useful in medical facilities, nursing homes, and water facilities. Therefore, development of such a bactericidal material has been demanded. In addition, since the water repellent material makes it difficult to attach microorganisms such as bacteria, the water repellent material is named in this way.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a bactericidal material capable of easily removing microorganisms with an aqueous solution even if the microorganisms adhere.

  As a result of intensive studies to solve the above problems, the present inventors have found that a material containing a polyacetal resin containing an ester end group amount in a specific range can solve the above problems, and the completion of the present invention. It came to.

That is, the present invention includes a polyacetal resin (A) containing an ester end group represented by the following formula, and 1 g of the polyacetal resin (A) contains the ester end group in a proportion of 20 μmol or less. It is a material.
RCOO-
(Wherein R represents a hydrogen atom or an alkyl group)

  According to the antibacterial material of the present invention, even if microorganisms adhere, the microorganisms can be easily removed with an aqueous solution. The aqueous solution includes not only a mixture of water and solute but also mere water.

  The present inventors infer the reason why the above-described effect can be obtained by the antimicrobial material of the present invention as follows. That is, the oxygen atom in the polyacetal resin (A) relatively reduces the proportion of carbon atoms that are likely to adhere to proteins in the microorganism, and the charge amount of the polyacetal resin (A) decreases, so that the polyacetal resin (A ) And the intermolecular force between microorganisms is reduced. As a result, the present inventors presume that even if microorganisms adhere, the microorganisms can be easily removed with an aqueous solution.

  In the above-mentioned bactericidal material, the polyacetal resin (A) includes an oxymethylene group and an oxyalkylene group having 2 or more carbon atoms, and the oxyalkylene group is greater than 0 mol and less than or equal to 10 mol per 100 mol of the oxymethylene group. It is preferably included.

  In this case, even if microorganisms adhere, the microorganisms can be more easily removed with an aqueous solution than the repellant material in which the proportion of oxyalkylene groups exceeds 10 mol per 100 mol of oxymethylene groups. In addition, superior thermal stability can be obtained as compared with a fungicide having a ratio of oxyalkylene groups of 0 mol per 100 mol of oxymethylene groups.

  The bactericidal material preferably further contains a lubricant (B).

  According to this antibacterial material, even when microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution than the antibacterial material not containing the lubricant (B).

  In the said antimicrobial material, it is preferable that the said lubricating material (B) is mix | blended in the ratio of 1-3 mass parts with respect to 100 mass parts of said polyacetal resins (A).

  In this case, more excellent measurement stability and mechanical properties at the time of molding can be obtained as compared with the antibacterial material in which the blending ratio of the lubricant (B) exceeds 3 parts by mass. Moreover, even if microorganisms adhere, compared with the case where the blending ratio of the lubricant (B) is less than 1 part by mass, the microorganisms can be more easily removed by the aqueous solution.

  In the said antimicrobial material, it is preferable that the said lubricating material (B) is an olefin type lubricating material.

  In this case, compared to the case where the lubricant (B) is a lubricant other than the olefin-based lubricant, even if microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution.

In the said antimicrobial material, it is preferable that the density of the said olefin type lubricant is 950-1000 kg / m < ³ >.

In this case, compared to the case where the density of the olefin-based lubricant is less than 950 kg / m ³ , even if microorganisms adhere, the microorganisms tend to be more easily removed by the aqueous solution. The density of the olefinic lubricant is generally 1000 kg / m ³ or less.

  In the said antimicrobial material, it is preferable that the viscosity of the said olefin type lubricant is 500-10000 mPa * s.

  In this case, even if microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution than the repellency of the olefin-based lubricant having a viscosity of less than 500 mPa · s. Further, when the viscosity of the olefin-based lubricant (B) is within the above range, the dispersibility of the lubricant (B) is further improved as compared with the case where it exceeds 10,000 mPa · s.

  In the above-mentioned bactericidal material, it is preferable that the acid value of the olefin-based lubricant is greater than 0 mgKOH / g and not more than 20 mgKOH / g.

  In this case, even if microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution than the antimicrobial material having an acid value of the olefin-based lubricant outside the above range.

In the repellent fungus material, said polyacetal 190 ° C. of resin (A), the melt volume rate measured at 2.16 kg (hereinafter, referred to herein as "MVR") is 2~50cm ^3/10 min Is preferred.

In this case, MVR as compared to the repellent fungus material is less than ^{2 cm} 3/10 min, becomes what moldability repellent fungus material is excellent, as compared with the case where MVR exceeds 50 cm ^3/10 min, microorganisms Even if it adheres, the microorganisms can be more easily removed by the aqueous solution, and the mechanical strength of the molded article increases.

  The bactericidal material preferably further contains a formaldehyde scavenger (C).

  In this case, generation of formaldehyde during the production of the polyacetal resin can be sufficiently suppressed, and contamination of the mold during the molding process can be sufficiently suppressed.

In the bacteriostatic material, the formaldehyde scavenger (C) is at least one selected from the group consisting of a dihydrazone compound represented by the following general formula (1) and a dihydrazone compound represented by the following general formula (2). It is preferable that the dihydrazone compound (C1) is included and 0.02 to 5 parts by mass of the dihydrazone compound (C1) is blended with respect to 100 parts by mass of the polyacetal resin.
(In the above formula, R ¹ represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ² to R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, at least one of R ² and R ³ represents an alkyl group having 1 or 2 carbon atoms, and among R ⁴ and R ⁵ At least one represents an alkyl group having 1 or 2 carbon atoms.)
(In the above formula, R ⁸ represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ⁶ and R < ⁷ > shows a C3-C12 alicyclic hydrocarbon group each independently.)

  In this case, generation of formaldehyde can be sufficiently suppressed, contamination of the mold during the molding process can be sufficiently suppressed, and excellent mechanical properties can be imparted to the molded product.

In the general formula (1), it is preferred that R ¹ is an aliphatic hydrocarbon group having 6 to 12 carbon atoms.

  In this case, the reactivity between the dihydrazone compound (C1) and formaldehyde becomes higher, and the generation of formaldehyde is more effectively suppressed. Further, contamination of the mold during molding can be more sufficiently suppressed.

In the general formula (1), when R ² and R ⁴ are ethyl groups, R ³ and R ⁵ are hydrogen atoms, and when R ² and R ⁴ are methyl groups, R ³ and R ⁵ is preferably a hydrogen atom or a methyl group.

  In this case, the reactivity between the dihydrazone compound (C1) and formaldehyde becomes higher, and the generation of formaldehyde is more effectively suppressed. Further, contamination of the mold during molding can be more sufficiently suppressed.

  It is preferable that 0.05-3 mass parts of said dihydrazone compound (C1) is mix | blended with respect to 100 mass parts of said polyacetal resins (A).

  In this case, compared with the case where the compounding quantity of the said dihydrazone compound (C1) is less than 0.05 mass part, generation | occurrence | production of formaldehyde can be suppressed more fully. Moreover, compared with the case where the compounding quantity of the said dihydrazone compound (C1) exceeds 3 mass parts, the more excellent mechanical characteristic can be provided with respect to the molded article obtained by shape | molding a polyacetal resin composition.

  In the said antimicrobial material, the said formaldehyde scavenger (C) contains a hydrazide compound (C2), and the said hydrazide compound (C2) is a ratio of 0.01-1 mass part with respect to 100 mass parts of polyacetal resin (A). It is preferable that it is blended.

  In this case, compared with the case where the compounding quantity of the hydrazide compound (C2) with respect to 100 mass parts of polyacetal resin (A) is less than 0.01 mass part, generation | occurrence | production of formaldehyde can be suppressed more fully. Moreover, compared with the case where the compounding quantity of the hydrazide compound (C2) with respect to 100 mass parts of polyacetal resin (A) exceeds 1 mass part, the contamination of the metal mold | die at the time of a molding process can fully be suppressed, and a polyacetal resin composition is molded. Thus, more excellent mechanical properties can be imparted to the molded product obtained.

  The hydrazide compound (C2) is preferably composed of at least one selected from the group consisting of a monohydrazide compound and a dihydrazide compound.

  In this case, the hydrazide group (C2) can be more efficiently dispersed in the polyacetal resin (A) than the case where the hydrazide compound (C2) is composed of a hydrazide compound having three or more hydrazide groups in the molecule. The amount of C2) added can be more sufficiently suppressed.

  More preferably, the hydrazide compound (C2) is composed of only a dihydrazide compound.

  In this case, generation of formaldehyde can be more sufficiently suppressed as compared with the case where the hydrazide compound (C2) is composed of only the monohydrazide compound or the case of being composed of the monohydrazide compound and the dihydrazide compound.

  The dihydrazide compound (C2) is selected from adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, 1,18-octadecanedicarbohydrazide, terephthalic acid dihydrazide, 1,8-naphthalenedicarbohydrate and 2,6-naphthalenedicarbohydrazide. It is preferably composed of at least one selected from the group consisting of

  In this case, formaldehyde can be captured more efficiently and mold deposits during molding can be reduced.

In the present invention, the antibacterial material is a material containing a polyacetal resin, and when the number of microorganisms attached per unit area (1 mm 2) is A, the following formula:
Number of attached microorganisms = log ₁₀ [A / number per unit area (1 mm 2) of microorganisms attached to the surface of the polyethylene pellet]
A material having a ratio of attached microorganisms calculated on the basis of −1 is −1 or less.

  Here, the “polyethylene pellet” refers to a polyethylene resin specified by a trade name “Novatech HD HJ360” manufactured by Nippon Polyethylene.

Further, “the number of microorganisms attached per unit area A to a material containing a polyacetal resin” refers to a value obtained according to the following procedures (1) to (8).
(1) First, a material containing the polyacetal resin is molded to obtain a molded piece having dimensions of 13 mm × 123 mm × 0.4 mmt. And the test piece cut into 13 mm square is obtained from this shaping | molding piece.
(2) After washing the cultured microorganisms, the microorganism concentration is adjusted to 1 × 10 ⁶ cells / ml in phosphate buffered saline (hereinafter referred to as “PBS”) to obtain a microorganism solution. .
(3) Three test pieces are placed in each well of a 24-well plate, and then the above microorganism solution is added to the well plate.
(4) After leaving still at 37 degreeC for 1 hour, a test piece is taken out from a well and it wash | cleans 10 times lightly with PBS.
(5) Dry the test piece and deposit gold on the surface.
(6) Using a tabletop scanning electron microscope (product name “Miniscope TM-1000”, manufactured by Hitachi, Ltd.), the surface of the test piece was observed at a magnification of 2000 times and randomly selected 10 fields of view. Import images.
(7) The number of attached microorganisms in the visual field is measured using image analysis software (product name “Win Roof”, manufactured by Mitani Corporation).
(8) Calculate the total number of attached microorganisms in 10 fields of view and divide this total by the total area of 10 fields of view. Thus, the number A of attached microorganisms per square mm is calculated.

  ADVANTAGE OF THE INVENTION According to this invention, even if microorganisms adhere, the antimicrobial material which can remove the microorganisms easily with aqueous solution is provided.

It is a figure which shows the observation image by the microscope of the surface of the test piece of Example 1 at the time of making Staphylococcus aureus adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of Example 2 at the time of making Staphylococcus aureus adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of Example 3 at the time of making Staphylococcus aureus adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of the comparative example 1 at the time of making Staphylococcus aureus adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of the comparative example 2 at the time of making Staphylococcus aureus adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of Example 1 at the time of adhere | attaching Escherichia coli as microorganisms. It is a figure which shows the observation image by the microscope of the surface of the test piece of Example 2 at the time of adhere | attaching Escherichia coli as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of Example 3 at the time of making colon_bacillus | E._coli adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of the comparative example 1 at the time of making colon_bacillus | E._coli adhere as a microorganism. It is a figure which shows the observation image by the microscope of the surface of the test piece of the comparative example 2 at the time of making colon_bacillus | E._coli adhere as a microorganism.

The antibacterial material according to the present invention includes a polyacetal resin (A) containing an ester end group represented by the following formula, and the ester end group is contained in 1 g of the polyacetal resin (A) at a ratio of 20 μmol or less. It is a repellent material.
RCOO-
(Wherein R represents a hydrogen atom or an alkyl group)

  According to the above-mentioned bactericidal material, even if microorganisms adhere, the microorganisms can be easily removed with an aqueous solution. Here, the microorganism is not particularly limited, and specific examples of such a microorganism include, for example, Staphylococcus aureus, Escherichia coli, Candida and Pseudomonas aeruginosa.

  Hereinafter, the antibacterial material of the present invention will be described in detail.

(A) Polyacetal resin Polyacetal resin (A) should just contain the ester terminal group represented by the said formula in the ratio of 20 micromol or less in 1g of polyacetal resin (A).

  The ester terminal group amount in 1 g of the polyacetal resin (A) may be 20 μmol or less. Therefore, the amount of ester end groups in 1 g of polyacetal resin (A) may be 0 μmol. The amount of ester end groups in 1 g of the polyacetal resin (A) is preferably 0 to 18 μmol. In this case, compared with the case where the ester terminal group amount in polyacetal resin (A) remove | deviates from the said range, it is excellent in thermal stability.

  The amount of ester end groups in 1 g of the polyacetal resin (A) is more preferably 0 to 15 μmol.

  In the ester terminal group, R represents a hydrogen atom or an alkyl group, but the polyacetal resin (A) may be composed only of a polyacetal resin in which R is a hydrogen atom, or a polyacetal resin in which R is a hydrogen atom. And a polyacetal resin in which R is an alkyl group.

  When R is an alkyl group in the ester terminal group, the alkyl group is preferably a methyl group.

  Polyacetal resin (A) should just contain a bivalent oxymethylene group as a structural unit. Therefore, the polyacetal resin (A) may be a homopolymer containing only an oxymethylene group as a constituent unit, or a copolymer containing an oxymethylene group and an oxyalkylene group having 2 or more carbon atoms as constituent units. Also good. Among these, from the viewpoint of obtaining excellent long-term stability, a copolymer containing an oxymethylene group and an oxyalkylene group having 2 or more carbon atoms as constituent units is preferable.

  Examples of the oxyalkylene group having 2 or more carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group. These may be used alone or in combination of two or more. Among the specific examples described above, an oxyethylene group is preferable because the characteristics of the polyacetal resin (A) are more sufficiently suppressed.

  In the polyacetal resin (A), as described above, the proportion of oxyalkylene groups having 2 or more carbon atoms is preferably contained in a proportion of more than 0 mol and not more than 10 mol per 100 mol of oxymethylene groups.

  In this case, even if microorganisms adhere, the microorganisms can be more easily removed with an aqueous solution than the repellant material in which the proportion of oxyalkylene groups exceeds 10 mol per 100 mol of oxymethylene groups. In addition, superior thermal stability can be obtained as compared with a fungicide having a ratio of oxyalkylene groups of 0 mol per 100 mol of oxymethylene groups.

  The ratio of the oxyalkylene group is more preferably more than 0 mol and not more than 5 mol per 100 mol of the oxymethylene group.

  In order to produce the polyacetal resin (A), trioxane is usually used as a main raw material. In order to introduce an oxyalkylene group having 2 or more carbon atoms into the polyacetal resin (A), for example, cyclic formal or cyclic ether can be used. Specific examples of cyclic formal include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3-dioxocane, 1,3,5-trioxepane, 1,3,6-trioxocane and the like. Can be mentioned. Specific examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide and the like. In order to introduce an oxyethylene group into the polyacetal resin (A), for example, 1,3-dioxolane may be used, and in order to introduce an oxypropylene group, 1,3-dioxane may be used. For introduction, 1,3-dioxepane may be introduced.

  In addition, polyacetal resin (A) is, for example, a catalyst deactivation treatment, unreacted monomer of a raw material obtained by polymerizing the above raw material in the presence of a catalyst and a molecular weight modifier for a predetermined residence time. After performing removal, washing, drying, stabilization treatment of the unstable terminal portion, and the like, it can be obtained by further performing stabilization treatment by blending various stabilizers.

  In the case where the polyacetal resin (A) is a copolymer, as a method for producing the polyacetal resin (A), cationic polymerization using trioxane as a main monomer and a cyclic ether or cyclic formal having an adjacent carbon atom as a comonomer is known, As the catalyst used for these polymerizations, a cation active catalyst is used. Cationic active catalysts include Lewis acids, especially boron, tin, titanium, phosphorus, arsenic and antimony halides such as boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentachloride, phosphorus pentafluoride, pentafluoride. Compounds such as arsenic fluoride and antimony pentafluoride, and complex compounds or salts thereof are known. Among them, boron trifluoride, or a coordination compound of boron trifluoride and an organic compound such as ethers, is mainly composed of trioxane. It is the most common polymerization catalyst used as a monomer.

  On the other hand, protic acids such as heteropolyacids such as silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, phosphotungstic acid, isopolyacids such as isopolytungstic acid, perfluoroalkylsulfonic acids, perchloric acid, or esters of these protic acids In particular, esters of perchloric acid and lower aliphatic alcohols, protonic acid anhydrides, mixed anhydrides of perchloric acid and lower aliphatic carboxylic acids, and the like can also be used as the cationically active catalyst.

  When the polyacetal resin (A) is a copolymer, the amount of ester terminal groups in the polyacetal resin (A) adjusts, for example, the type of catalyst, the amount of catalyst, the temperature in the system during the reaction, the residence time, the reaction rate, and the like. Can be adjusted. For example, it can be reduced by reducing the amount of catalyst or shortening the stay time, and can be increased by increasing the amount of catalyst or lengthening the stay time.

  When the polyacetal resin (A) is a copolymer, in order to make the amount of ester terminal groups in 1 g of the polyacetal resin (A) 20 μmol or less, when the catalyst used is a Lewis acid, it is usually the main monomer trioxane. The catalyst amount may be 0.01 to 0.06 mmol with respect to 1 mol. When the catalyst to be used is a proton acid composed of a very active heteropolyacid, perfluoroalkylsulfonic acid and derivatives thereof, the catalyst amount is usually 0.05 to 50 ppm with respect to the main monomer trioxane. Good. Furthermore, in order to reduce the ester end group amount in 1 g of the polyacetal resin (A) to 20 μmol or less, the specific residence time depends on the amount of the catalyst, so it cannot be generally stated. For example, the amount of the catalyst is the main monomer. If it is 0.04 mmol with respect to 1 mol of a certain trioxane, what is necessary is just 3-20 minutes.

  When the polyacetal resin (A) is a homopolymer, the amount of ester terminal groups in the polyacetal resin (A) can be reduced by reducing the amount of the molecular weight modifier, and the amount of the molecular weight modifier is increased. Can be enlarged.

  As the molecular weight regulator, for example, acetic anhydride can be used.

  In order to make the ester terminal group amount in 1 g of the polyacetal resin (A) 20 μmol or less, the amount of the molecular weight regulator may be, for example, 0.01 to 0.05 mol with respect to 1 mol of trioxane as the main monomer.

  Examples of the stabilizer include hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, and carboxylates.

(B) Lubricant It is preferable that the antibacterial material of the present invention further includes a lubricant (B). In this case, even if microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution than the antibacterial material not containing the lubricant (B).

  Examples of the lubricant (B) include silicon-based lubricants, olefin-based lubricants, fatty acid salts, fatty acid esters, and polyalkylene glycol (PAG). These can be used alone or in combination of two or more.

  Examples of the silicon-based lubricant include dimethyl silicone. These can be used alone or in combination of two or more.

  Examples of the olefin-based lubricant include polyethylene wax and liquid paraffin. These can be used alone or in combination of two or more.

  The fatty acid salt is a salt of a fatty acid and an alkali. Here, examples of the fatty acid include stearic acid. Examples of the alkali include calcium hydroxide. Specific examples of the fatty acid salt include calcium stearate. These can be used alone or in combination of two or more.

  The fatty acid ester is an ester of a fatty acid and an alcohol. Here, as the fatty acid, the same fatty acid as that described above can be used. Examples of the alcohol include glycerin. Specific examples of the fatty acid ester include stearic acid monoglyceride. These can be used alone or in combination of two or more.

  Among the above-mentioned lubricants (B), olefin-based lubricants are particularly preferable. In this case, compared to the case where the lubricant (B) is a lubricant other than the olefin-based lubricant, even if microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution.

The density of the olefin-based lubricant is not particularly limited, but is preferably 950 to 1000 kg / m ³ . In this case, compared to the case where the density of the olefin-based lubricant is less than 950 kg / m ³ , even if microorganisms adhere, the microorganisms tend to be more easily removed by the aqueous solution. The density of the olefin-based lubricant is more preferably 960 to 1000 kg / m ³ , and further preferably 970 to 1000 kg / m ³ . The density is a density measured by a density gradient tube method.

  The viscosity of the olefin-based lubricant is not particularly limited, but is preferably 500 to 10,000 mPa · s. In this case, even if microorganisms adhere, the microorganisms can be more easily removed by the aqueous solution than the repellency of the olefin-based lubricant having a viscosity of less than 500 mPa · s. Further, when the viscosity of the olefin-based lubricant is within the above range, the dispersibility of the lubricant (B) is further improved as compared with the case where it exceeds 10,000 mPa · s. The viscosity of the olefin-based lubricant is more preferably 1000 to 10,000 mPa · s, and further preferably 5,000 to 10,000 mPa · s. Here, the viscosity means a viscosity measured at 140 ° C. using a B-type viscometer.

  The acid value of the olefin-based lubricant is not particularly limited, but is preferably greater than 0 mgKOH / g and not greater than 20 mgKOH / g. In this case, even if microorganisms are attached, the microorganisms can be more easily removed by the aqueous solution than the anti-bacterial material having an acid value of the olefinic lubricant outside the above range. The acid value of the olefin-based lubricant is more preferably greater than 0 mgKOH / g and not greater than 15 mgKOH / g, and still more preferably greater than 0 mgKOH / g and not greater than 3 mgKOH. Here, the acid value refers to an acid value measured by a neutralization titration method.

  The blending ratio of the lubricant (B) with respect to 100 parts by mass of the polyacetal resin (A) is not particularly limited, but is preferably 1 to 3 parts by mass.

  In this case, more excellent measurement stability and mechanical properties at the time of molding can be obtained as compared with the antibacterial material in which the blending ratio of the lubricant (B) exceeds 3 parts by mass. Moreover, even if microorganisms adhere, compared with the case where the blending ratio of the lubricant (B) is less than 1 part by mass, the microorganisms can be more easily removed by the aqueous solution. The blending ratio of the lubricant (B) to 100 parts by mass of the polyacetal resin (A) is more preferably 1 to 2 parts by mass.

Although MVR is not particularly limited in the polyacetal resin (A), the it is preferably 2~50cm ^3/10 min. Here, MVR shall mean the value measured according to ASTM-D1238 standard on the conditions of 190 degreeC and 2.16 kg.

In this case, MVR as compared to the repellent fungus material is less than ^{2 cm} 3/10 min, becomes what moldability repellent fungus material is excellent, as compared with the case where MVR exceeds 50 cm ^3/10 min, microorganisms Even if it adheres, the microorganisms can be more easily removed by the aqueous solution, and the mechanical strength of the molded article increases.

MVR of the polyacetal resin (A) is more preferably 2~30cm ^3/10 min, more preferably from 2 to 10 cm ^3/10 min.

(C) Formaldehyde scavenger The bactericidal material of the present invention preferably further contains a formaldehyde scavenger (C).

  In this case, generation of formaldehyde can be sufficiently suppressed, and contamination of the mold during molding can be sufficiently suppressed.

  The formaldehyde scavenger (C) is not particularly limited as long as it reacts with formaldehyde, and examples thereof include a dihydrazone compound (C1) and a hydrazide compound (C2). You may use these individually or in combination of 2 or more types.

(C1) Dihydrazone Compound Examples of the dihydrazone compound (C1) include a dihydrazone compound represented by the following general formula (1) and a dihydrazone compound represented by the following general formula (2). These may be used alone or in combination.

In the general formula (1), R ¹ represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. R ¹ is preferably an aliphatic hydrocarbon group having 6 to 12 carbon atoms. In this case, the reactivity between the dihydrazone compound (C1) and formaldehyde becomes higher, and generation of formaldehyde is more effectively suppressed. Further, contamination of the mold during molding can be more sufficiently suppressed.

  Specific examples of the aliphatic hydrocarbon group include a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, Examples include an alkylene group such as a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, and an icosylene group.

  The alicyclic hydrocarbon group may be saturated or unsaturated.

  Examples of the alicyclic hydrocarbon group include cycloalkylene groups having 6 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclohexylene group.

  Examples of the aromatic hydrocarbon group include arylene groups such as a phenylene group and a naphthylene group.

  A substituent may be bonded to at least a part of the carbon atoms of the aromatic hydrocarbon group. Examples of the substituent include a halogen group, a nitro group, and an alkyl group having 1 to 20 carbon atoms.

In the general formula (1), R ^{2 to} R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and at least one of R ² and R ³ is an alkyl having 1 or 2 carbon atoms. And at least one of R ⁴ and R ⁵ represents an alkyl group having 1 or 2 carbon atoms.

  Examples of the alkyl group having 1 or 2 carbon atoms include a methyl group and an ethyl group.

In the general formula (1), when R ² and R ⁴ are ethyl groups, R ³ and R ⁵ are hydrogen atoms, and when R ² and R ⁴ are methyl groups, R ³ and R ⁵ is preferably a hydrogen atom or a methyl group.

  In this case, the reactivity between the dihydrazone compound (C1) and formaldehyde becomes higher, and the generation of formaldehyde is more effectively suppressed. Further, contamination of the mold during molding can be more sufficiently suppressed.

  Specific examples of the dihydrazone compound represented by the general formula (1) include, for example, 1,12-bis [2- (1-methylethylidene) hydrazino]]-1,12-dodecanedione, 1,12-bis ( 2-ethylidenehydrazino) -1,12-dodecanedione, 1,12-bis (2-propylidenehydrazino) -1,12-dodecanedione, 1,12-bis [2- (1-methylpropylidene) Hydrazino] -1,12-dodecanedione, 1,12-bis [2- (1-ethylpropylidene) hydrazino] -1,12-dodecanedione, 1,10-bis [2- (1-methylethylidene) hydrazino ]]-1,10-decanedione, 1,10-bis (2-propylidenehydrazino) -1,10-decanedione, 1,10-bis (2-propylidenehydrazino) -1,10 Decanedione, 1,10-bis [2- (1-methylpropylidene) hydrazino] -1,10-decanedione, 1,10-bis [2- (1-ethylpropylidene) hydrazino] -1,10-decanedione 1,6-bis [2- (1-methylethylidene) hydrazino] -1,6-hexanedione, 1,6-bis (2-ethylidenehydrazino) -1,6-hexanedione, 1,6-bis (2-propylidenehydrazino) -1,6-hexanedione, 1,6-bis [2- (1-methylpropylidene) hydrazino] -1,6-hexanedione, 1,6-bis [2- ( 1-ethylpropylidene) hydrazino] -1,6-hexanedione and the like.

  The dihydrazone compound represented by the general formula (1) may be used alone or in combination of two or more.

In the general formula (2), R ⁸ is an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic having 6 to 10 carbon atoms in the same manner as R ^1. Represents a hydrocarbon group. R ⁸ may be the same as or different from R ¹ in the general formula (1).

R ⁶ and R ⁷ each independently represents an alicyclic hydrocarbon group having 3 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cyclohexylene group.

  Specific examples of the dihydrazone compound represented by the general formula (2) include, for example, 1,12-bis (2-cyclohexylidenehydrazino) -1,12-dodecanedione, 1,10-bis (2-cyclohexene). Silidenehydrazino) -1,10-decanedione, 1,6-bis (2-cyclohexylidenehydrazino) -1,6-hexanedione, and the like.

  The dihydrazone compound represented by the general formula (2) may be used alone or in combination of two or more.

  Although the compounding quantity of the said dihydrazone compound (C1) is not specifically limited, It is preferable that it is 0.02-5 mass parts with respect to 100 mass parts of polyacetal resin (A). In this case, compared with the case where the compounding quantity of the said dihydrazone compound (C1) is less than 0.02 mass part, generation | occurrence | production of formaldehyde can be suppressed more fully. Moreover, when the compounding quantity of the said dihydrazone compound (C1) is 0.02-5 mass parts with respect to 100 mass parts of polyacetal resin (A), and the compounding quantity of the said dihydrazone compound (C1) exceeds 5 mass parts. Compared to, it is possible to impart more excellent mechanical properties to the molded product.

  As for the compounding quantity of the said dihydrazone compound (C1), it is more preferable that it is 0.05-3 mass parts with respect to 100 mass parts of polyacetal resin (A). In this case, compared with the case where the compounding quantity of the said dihydrazone compound (C1) is less than 0.05 mass part, generation | occurrence | production of formaldehyde can be suppressed more fully. Moreover, compared with the case where the compounding quantity of the said dihydrazone compound (C1) exceeds 3 mass parts, the more excellent mechanical characteristic can be provided with respect to the molded article obtained by shape | molding a polyacetal resin composition.

  As for the compounding quantity of the said dihydrazone compound (C1), it is more preferable that it is 0.1-1.0 mass part with respect to 100 mass parts of polyacetal resin (A).

The dihydrazone compound can be obtained by reacting a dicarboxylic acid derivative such as dicarboxylic acid halide or dicarboxylic acid ester with hydrazine to produce a dihydrazide compound, and reacting the dihydrazide compound with a ketone or aldehyde. At this time, R ¹ (COX) ₂ or R ⁸ (COX) ₂ is used as the dicarboxylic acid halide, and R ¹ (COOY) ₂ or R ⁸ (COOY) ₂ is used as the dicarboxylic acid ester. Here, Y represents an alkyl group. As the ketone or aldehyde, R ² —C (═O) —R ³ , R ⁴ —C (═O) —R ⁵ , R ⁶ ═O, or R ⁷ ═O is used.

(C2) Hydrazide Compound The hydrazide compound (C2) is preferably blended in a proportion of 0.01 to 1 part by mass with respect to 100 parts by mass of the polyacetal resin (A). In this case, compared with the case where the compounding quantity of the hydrazide compound (C2) with respect to 100 mass parts of polyacetal resin (A) is less than 0.01 mass part, generation | occurrence | production of formaldehyde can be suppressed more fully. Moreover, compared with the case where the compounding quantity of the hydrazide compound (C2) with respect to 100 mass parts of polyacetal resin (A) exceeds 1 mass part, the contamination of the metal mold | die at the time of a molding process can fully be suppressed, and a polyacetal resin composition is shape | molded. Thus, more excellent mechanical properties can be imparted to the molded product obtained.

  As for the compounding quantity of the said hydrazide compound (C2), it is more preferable that it is 0.02-0.08 mass part with respect to 100 mass parts of polyacetal resin (A).

  The hydrazide compound (C2) is preferably composed of at least one selected from the group consisting of a monohydrazide compound and a dihydrazide compound.

  In this case, compared with the case where the hydrazide compound (C2) is composed of a hydrazide compound having three or more hydrazide groups in the molecule, the hydrazide group can be more efficiently dispersed in the antimicrobial material, and the hydrazide compound (C2) Can be more sufficiently suppressed.

  More preferably, the hydrazide compound (C2) is composed of only a dihydrazide compound.

  In this case, generation of formaldehyde can be more sufficiently suppressed as compared with the case where the hydrazide compound (C2) is composed of only the monohydrazide compound or the case of being composed of the monohydrazide compound and the dihydrazide compound.

  Examples of the dihydrazide compound (C2) include adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,18-octadecanedicarbohydrazide, terephthalic acid dihydrazide, 1,8-naphthalenedicarbohydrazide, and 2,6-naphthalene. Dicarbohydrazide is mentioned. These can be used alone or in combination of two or more.

  In this case, formaldehyde can be captured more efficiently and mold deposits during molding can be reduced.

  The antibacterial material of the present invention is an antioxidant, a heat stabilizer, a coloring agent, a nucleating agent, a plasticizer, a fluorescent brightening agent, a sliding agent, an ultraviolet absorber such as a benzotriazole-based compound or a benzophenone-based compound, or If necessary, an additive such as a light stabilizer such as a hindered amine may be further included.

  Even if microorganisms adhere, the microorganism-repellent material of the present invention can be easily removed with an aqueous solution. For this reason, the bactericidal material of the present invention can be suitably used for articles for which adhesion of microorganisms is desirable, such as wallpaper for medical facilities or nursing care facilities, watering members (such as shower heads), nursing care products, and the like.

  The bactericidal material of the present invention can be used in various forms. For example, the antibacterial material of the present invention can be processed into a sheet and used as it is. Moreover, it is also possible to use the bactericidal material of the present invention in the form of particles and kneaded with other resins. Furthermore, it can also be used by coating the surface of an article that is required to be free of microorganisms. Moreover, it can also be made into a fiber form and used for a filter.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely, the present invention is not limited to the following example.

  The lubricant used in the examples was as follows.

(B) Lubricant (B1) Olefin-based lubricant (hereinafter sometimes abbreviated as “olefin-based”) a
Polyethylene wax, density 960 kg / m ³ , viscosity 650 mPa · s, acid value 1 mg KOH / g (Mitsui Chemicals, trade name “High Wax 405MP”)
(B2) Olefin-based b
Polyethylene wax, density 920 kg / m ³ , viscosity 80 mPa · s, acid value 0 mg KOH / g (trade name “High Wax 220P” manufactured by Mitsui Chemicals, Inc.)
(B3) Olefin-based c
Polyethylene wax, density 920 kg / m ³ , viscosity 6000 mPa · s, acid value 0 mg KOH / g (trade name “High Wax 720P” manufactured by Mitsui Chemicals)
(B4) Olefin-based d
Polyethylene wax, density 930 kg / m ³ , viscosity 650 mPa · s, acid value 0 mgKOH / g (trade name “High Wax 420P” manufactured by Mitsui Chemicals, Inc.)
(B5) Olefin-based e
Polyethylene wax, density 970 kg / m ³ , viscosity 8000 mPa · s, acid value 0 mgKOH / g (trade name “High Wax 800P” manufactured by Mitsui Chemicals, Inc.)
(B6) Olefin-based f
Polyethylene wax, density 970 kg / m ³ , viscosity 80 mPa · s, acid value 0 mg KOH / g (trade name “High Wax 200P” manufactured by Mitsui Chemicals)
(B7) Olefinic g
Polyethylene wax, density 970 kg / m ³ , viscosity 500 mPa · s, acid value 12 mgKOH / g (Mitsui Chemicals, trade name “High Wax 4051E”)
(B8) Olefinic h
Polyethylene wax, density 970 kg / m ³ , viscosity 440 mPa · s, acid value 20 mgKOH / g (Mitsui Chemicals, trade name “High Wax 4052E”)
(B9) Olefin-based i
Polyethylene wax, density 980 kg / m ³ , viscosity 600 mPa · s, acid value 0 mgKOH / g (Mitsui Chemicals, trade name “High Wax 400P”)
(B10) Silicone lubricant (silicone)
Product name "BY27-006B", manufactured by Toray Dow Corning
(B11) Fatty acid salt calcium stearate (manufactured by NOF Corporation, trade name “GF-200”)
(B12) Fatty acid ester stearic acid monoglyceride (manufactured by Riken Vitamin Co., Ltd., trade name “Riquemar S100A”)
(B13) Polyalkylene glycol (PAG)
Polyethylene glycol (made by ADEKA, trade name “PEG20000P”)

The oxyalkylene group content and the ester end group amount in the polyacetal resin were measured as follows.
(1) Oxyalkylene group content 10 g of polyacetal resin was put into 100 ml of 3N-HCl aqueous solution and decomposed by heating at 120 ° C. for 2 hours in a sealed container. After cooling, the amount of alkylene glycol, dialkylene glycol and trialkylene glycol in the aqueous solution is measured by gas chromatography (FID), and the amount of oxyalkylene groups having 2 or more carbon atoms constituting the polyacetal resin is determined by the oxy of the polyacetal resin. It calculated as the mol number with respect to 100 mol of methylene groups.

(2) Ester end group amount The ester end group amount is obtained by dissolving a polyacetal resin in hexafluoroisopropanol (d2) to prepare a measurement sample, and using NMR, which is an analysis technique usually performed for this measurement sample. The NMR spectrum was measured and calculated by performing analysis based on the NMR spectrum. The amount of ester end groups is shown as the number of moles of ester end groups per gram of polyacetal resin (A), and the unit was μmol / g-POM.

Example 1
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket whose temperature is set to 60 ° C., 1.3 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and boron trifluoride diethyl as a catalyst Etherate was continuously added as a benzene solution to 0.025 mmol with respect to 1 mol of all monomers (trioxane and 1,3-dioxolane), and methylal as a molecular weight regulator was continuously added to be 650 ppm with respect to all monomers as a benzene solution, Copolymerization of trioxane and 1,3-dioxolane was carried out so that the residence time was 15 minutes, and 1 mol of boron trifluoride diethyl etherate used as the benzene solution was used for the resulting copolymer. The catalyst is lost by adding 2 mol to After and by pulverizing the resulting copolymer to obtain a crude polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. Part, 0.005 part by mass of a metal-containing compound was added at 60 kg / hour while being added as a stabilizer, the pressure was reduced to 20 kPa at the vent part, kneaded at 220 ° C., and pellets (POM-1) were produced with a pelletizer. The ester terminal amount in POM-1 was 5 μmol / g-POM as shown in Table 1. Moreover, the ratio of the oxyalkylene group having 2 or more carbon atoms in POM-1 was 0.5 mol as shown in Table 1. Furthermore, when MVR was measured about POM-1, as shown in Table 1, MVR was 14 cm < ³ > / 10min.

(Example 2)
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket whose temperature is set to 60 ° C., 1.3 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and boron trifluoride diethyl as a catalyst Etherate was continuously added as a benzene solution to 0.04 mmol with respect to 1 mol of all monomers (trioxane and 1,3-dioxolane), and methylal as a molecular weight regulator was added as a benzene solution to 500 ppm with respect to all monomers, Copolymerization of trioxane and 1,3-dioxolane was carried out so that the residence time was 15 minutes, and 1 mol of boron trifluoride diethyl etherate used as the benzene solution was used for the resulting copolymer. The catalyst is deactivated by adding 2 mol to the catalyst After it was then crushed and the resulting copolymer to obtain a crude polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. Part and 0.005 part by mass of a metal-containing compound were added at 60 kg / hour while being added as a stabilizer, the pressure was reduced to 20 kPa at the vent part, kneaded at 220 ° C., and pellets (POM-2) were produced with a pelletizer. The ester terminal amount in POM-2 was 12 μmol / g-POM as shown in Table 1. The ratio of oxyalkylene groups having 2 or more carbon atoms in POM-2 was 0.5 mol as shown in Table 1. Furthermore, when MVR was measured about POM-2, as shown in Table 1, MVR was 14 cm < ³ > / 10min.

(Example 3)
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket whose temperature is set to 60 ° C., 1.3 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and boron trifluoride diethyl as a catalyst Etherate was continuously added as a benzene solution to 0.055 mmol with respect to 1 mol of all monomers (trioxane and 1,3-dioxolane), and methylal as a molecular weight regulator was added as a benzene solution to 300 ppm with respect to all monomers, Copolymerization of trioxane and 1,3-dioxolane was carried out so that the residence time was 15 minutes, and 1 mol of boron trifluoride diethyl etherate used as the benzene solution was used for the resulting copolymer. The catalyst is lost by adding 2 mol to After and by pulverizing the resulting copolymer to obtain a crude polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. Part, 0.005 part by mass of a metal-containing compound was added as a stabilizer at 60 kg / hour, the pressure was reduced to 20 kPa at the vent part, kneaded at 220 ° C., and pellets (POM-3) were produced with a pelletizer. As shown in Table 1, the ester terminal amount in POM-3 was 18 μmol / g-POM. Moreover, the ratio of the oxyalkylene group having 2 or more carbon atoms in POM-3 was 0.5 mol as shown in Table 1. Furthermore, when MVR was measured about POM-3, MVR was 14 cm < ³ > / 10min as shown in Table 1. FIG.

Example 4
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket set at a temperature of 60 ° C., 3.5 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and diethyl boron trifluoride as a catalyst Etherate as a benzene solution was added in an amount of 0.055 mmol with respect to 1 mol of all monomers, and methylal as a molecular weight regulator was continuously added as a benzene solution to 200 ppm with respect to all monomers (trioxane and 1,3-dioxolane). Copolymerization of trioxane and 1,3-dioxolane was carried out so that the residence time was 15 minutes, and 1 mol of boron trifluoride diethyl etherate used as the benzene solution was used for the resulting copolymer. The catalyst is lost by adding 2 mol to After and by pulverizing the resulting copolymer to obtain a crude polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. Part and 0.005 part by mass of a metal-containing compound were added at 60 kg / hour while being added as a stabilizer, the pressure was reduced to 20 kPa at the vent part, kneaded at 220 ° C., and pellets (POM-4) were produced with a pelletizer. The ester terminal amount in POM-4 was 16 μmol / g-POM as shown in Table 1. Further, the ratio of the oxyalkylene group having 2 or more carbon atoms in POM-4 was 1.4 mol as shown in Table 1. Furthermore, when MVR was measured about POM-4, MVR was 9 cm < ³ > / 10min as shown in Table 1. FIG.

(Example 5)
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket set at a temperature of 60 ° C., 3.5 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and diethyl boron trifluoride as a catalyst Etherate was continuously added as a benzene solution to 0.055 mmol with respect to 1 mol of all monomers (trioxane and 1,3-dioxolane), and methylal as a molecular weight regulator was added continuously to 900 ppm with respect to all monomers as a benzene solution, Copolymerization of trioxane and 1,3-dioxolane was carried out so that the residence time was 15 minutes, and 1 mol of boron trifluoride diethyl etherate used as the benzene solution was used for the resulting copolymer. The catalyst is lost by adding 2 mol to After and by pulverizing the resulting copolymer to obtain a crude polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. In addition, 0.005 parts by mass of a metal-containing compound was added at 60 kg / hour while being added as a stabilizer, the pressure was reduced to 20 kPa at the vent, kneaded at 220 ° C., and pellets (POM-5) were produced with a pelletizer. The ester terminal amount in POM-5 was 18 μmol / g-POM as shown in Table 1. Moreover, the ratio of the oxyalkylene group having 2 or more carbon atoms in POM-5 was 1.4 mol as shown in Table 1. Furthermore, when MVR was measured about POM-5, as shown in Table 1, MVR was 27 cm < ³ > / 10min.

(Example 6)
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket set at a temperature of 60 ° C., 3.5 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and diethyl boron trifluoride as a catalyst Etherate was added as a benzene solution to 0.055 mmol per 1 mol of all monomers, and methylal as a molecular weight regulator was continuously added as a benzene solution to 1250 ppm with respect to all monomers, so that the residence time was 15 minutes. Copolymerization of trioxane and 1,3-dioxolane was performed, and triphenylphosphine was added to the resulting copolymer as a benzene solution so as to be 2 mol per 1 mol of boron trifluoride diethyl etherate used. After deactivating the catalyst, the resulting copolymer is pulverized To obtain a polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. Part and 0.005 part by mass of a metal-containing compound were added at 60 kg / hour while being added as a stabilizer, the pressure was reduced to 20 kPa at the vent part, kneaded at 220 ° C., and pellets (POM-6) were produced with a pelletizer. The ester terminal amount in POM-6 was 19 μmol / g-POM as shown in Table 1. Further, the ratio of oxyalkylene groups having 2 or more carbon atoms in POM-6 was 1.4 mol as shown in Table 1. Furthermore, when MVR was measured about POM-6, MVR was 45 cm < ³ > / 10min as shown in Table 1. FIG.

(Example 7)
Dimethyl distearyl as a catalyst for 1 kg of formaldehyde dissolved in hexane so as to be 0.01 w / v% in a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket set at a temperature of 60 ° C. Polymerization was performed such that 0.0018 mol of ammonium acetate and 0.014 mol of acetic anhydride as a molecular weight regulator were added, and the residence time was 15 minutes. The resulting polymerization slurry was subsequently reacted in a 1: 1 mixture of acetic anhydride and hexane at 140 ° C. for 2 hours to stabilize the ends. Thereafter, the pressure was reduced to 2 mmHg or less and dried for 4 hours with a vacuum dryer set at 90 ° C. to obtain a crude polyacetal resin. To 100 parts by mass of the obtained crude polyacetal resin, 0.3 parts by mass of a hindered phenol compound and 0.005 parts by mass of a metal-containing compound were added as stabilizers and mixed with a Henschel blender to obtain a mixture. Next, the obtained mixture was introduced into the same-direction twin screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) at 60 kg / hour, decompressed to 20 kPa at the vent and melted at 220 ° C. The mixture was kneaded and pellets (POM-7) were produced with a pelletizer. The ester terminal amount in POM-7 was 11 μmol / g-POM. Further, as shown in Table 1, the ratio of oxyalkylene groups having 2 or more carbon atoms in POM-7 was 0.0 mol. Furthermore, when MVR was measured about POM-7, as shown in Table 1, MVR was 10 cm < ³ > / 10min.

(Example 8)
Dimethyl distearyl as a catalyst for 1 kg of formaldehyde dissolved in hexane so as to be 0.01 w / v% in a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket set at a temperature of 60 ° C. Polymerization was performed such that 0.0018 mol of ammonium acetate and 0.03 mol of acetic anhydride as a molecular weight regulator were added, and the residence time was 15 minutes. The resulting polymerization slurry was subsequently reacted in a 1: 1 mixture of acetic anhydride and hexane at 140 ° C. for 2 hours to stabilize the ends. Thereafter, the pressure was reduced to 2 mmHg or less and dried for 4 hours with a vacuum dryer set at 90 ° C. to obtain a crude polyacetal resin. To 100 parts by mass of the obtained crude polyacetal resin, 0.3 parts by mass of a hindered phenol compound and 0.005 parts by mass of a metal-containing compound were added as stabilizers and mixed with a Henschel blender to obtain a mixture. Next, the obtained mixture was introduced into the same-direction twin screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) at 60 kg / hour, decompressed to 20 kPa at the vent and melted at 220 ° C. The mixture was kneaded and pellets (POM-8) were produced with a pelletizer. The ester terminal amount in POM-8 was 19 μmol / g-POM. Further, the proportion of oxyalkylene groups having 2 or more carbon atoms in POM-8 was 0.0 mol as shown in Table 1. Furthermore, when MVR was measured about POM-8, MVR was 34 cm < ³ > / 10min as shown in Table 1. FIG.

Example 9
The pellet (POM-4) obtained in Example 4 and the olefin-based a, which is an olefin-based lubricant, were mixed in a tumbler for 15 minutes in the blending amount (unit: parts by mass) shown in Table 1 to obtain a mixture. It was. Then, this mixture was melt-kneaded at a cylinder temperature of 190 ° C. and a discharge rate of 10 kg / hr using an extruder (manufactured by Ikekai Tekko Co., Ltd., model: PCM-30) to produce pellets.

(Example 10)
The pellets (POM-5) obtained in Example 5 and the olefin system a were mixed for 15 minutes with a tumbler in the blending amounts shown in Table 1 (unit: parts by mass) to obtain a mixture. Then, this mixture was melt-kneaded at a cylinder temperature of 190 ° C. and a discharge rate of 10 kg / hr using an extruder (manufactured by Ikekai Tekko Co., Ltd., model: PCM-30) to produce pellets.

(Examples 11 to 26)
The pellets (POM-6) obtained in Example 6 and the lubricant shown in Table 1 were mixed for 15 minutes with a tumbler in the blending amounts (units are parts by mass) shown in Table 1 to obtain a mixture. Then, this mixture was melt-kneaded at a cylinder temperature of 190 ° C. and a discharge rate of 10 kg / hr using an extruder (manufactured by Ikekai Tekko Co., Ltd., model: PCM-30) to produce pellets.

(Comparative Example 1)
A pellet of polyethylene resin product name “Novatec HD HJ360” manufactured by Nippon Polyethylene Co., Ltd. was prepared.

(Comparative Example 2)
In a biaxial continuous polymerization machine having a self-cleaning paddle having a jacket whose temperature is set to 60 ° C., 1.3 parts by mass of 1,3-dioxolane with respect to 100 parts by mass of trioxane, and boron trifluoride diethyl as a catalyst Etherate was continuously added as a benzene solution to 0.077 mmol with respect to 1 mol of all monomers (trioxane and 1,3-dioxolane), and methylal as a molecular weight regulator as a benzene solution to 500 ppm with respect to all monomers, Copolymerization of trioxane and 1,3-dioxolane was carried out so that the residence time was 15 minutes, and 1 mol of boron trifluoride diethyl etherate used as the benzene solution was used for the resulting copolymer. The catalyst is lost by adding 2 mol to After and by pulverizing the resulting copolymer to obtain a crude polyacetal resin. The crude polyacetal resin thus obtained was fed into a same-direction twin-screw extruder (Nippon Steel Works, inner diameter 47 mm, L / D = 59.5) with 0.3 mass of hindered phenol compound based on 100 mass parts of the crude polyacetal resin. Part, 0.005 parts by mass of a metal-containing compound was added as a stabilizer at 60 kg / hour, the pressure was reduced to 20 kPa at the vent part, kneaded at 220 ° C., and pellets were produced with a pelletizer (POM-9). . The ester terminal amount in POM-9 was 22 μmol / g-POM as shown in Table 1. Moreover, the ratio of the oxyalkylene group having 2 or more carbon atoms in POM-9 was 0.5 mol as shown in Table 1. Furthermore, when MVR was measured about POM-9, as shown in Table 1, MVR was 24 cm < ³ > / 10min.

<Characteristic evaluation>
(Low microbial adhesion)
The pellets of Examples 1 to 26 and Comparative Examples 1 and 2 were evaluated for low microorganism adhesion as follows. That is, the number A of microorganisms attached per unit area to the pellets of Examples 1 to 26 and Comparative Examples 1 to 2 was determined, and the following formula:
Ratio of number of attached microorganisms = log ₁₀ [A / number of microorganisms attached to the surface of the pellet of Comparative Example 1 per unit area]
Based on the above, the attached microorganism ratios 1 and 2 were calculated. The results are shown in Table 1. The attached microorganism number ratio 1 is the attached microorganism number ratio when Staphylococcus aureus is used as the microorganism, and the attached microorganism number ratio 2 is the attached microorganism number ratio when Escherichia coli is used as the microorganism. Further, when the adhering microorganism ratios 1 and 2 were -1 or less, it was determined to be acceptable in terms of low microbial adhesion, and when it was greater than -1, it was determined to be unacceptable in terms of low microbial adhesion.

The number A of microorganisms attached per unit area to the pellets of Examples 1-26 and Comparative Examples 1-2 was determined according to the following procedures (1) to (8).
(1) First, the pellet was molded to obtain a molded piece having dimensions of 13 mm × 123 mm × 0.4 mmt. And the test piece cut about 13 mm square was obtained from this shaping | molding piece.
(2) After washing the cultured microorganisms, the microorganism concentration is adjusted to 1 × 10 ⁶ cells / ml in phosphate buffered saline (hereinafter referred to as “PBS”) to obtain a microorganism solution. It was.
(3) After putting three test pieces of each of Examples 1 to 26 and Comparative Examples 1 and 2 into the wells of a 24-well plate, the above microorganism solution was added to the well plate.
(4) After leaving still at 37 degreeC for 1 hour, the test piece was taken out from the well and it wash | cleaned 10 times lightly with PBS.
(5) The test piece was dried and gold was deposited on the surface.
(6) Using a tabletop scanning electron microscope (product name “Miniscope TM-1000”, manufactured by Hitachi, Ltd.), the surface of the test piece was observed at a magnification of 2000 times and randomly selected 10 fields of view. The image was captured.
(7) The number of adhering microorganisms in the visual field was measured using image analysis software (product name “Win Roof”, manufactured by Mitani Corporation).
(8) The total number of attached microorganisms in 10 fields of view was calculated, and this total was divided by the total area of 10 fields of view. Thus, the number A of attached microorganisms per square mm was calculated. The results are shown in Table 1.

  In addition, about Example 1-3 and Comparative Examples 1-2, for example, the observation image by the microscope of the surface of the test piece taken in by the said procedure (6) was shown to FIGS. FIGS. 1 to 3 are microscopic observation images of the surfaces of the test pieces of Examples 1 to 3 when S. aureus was attached as microorganisms, and FIGS. 4 and 5 were each attached to S. aureus as a microorganism. Observation images of the surface of the test pieces of Comparative Examples 1 and 2 with a microscope, FIGS. 6 to 8 are images of observation of the surface of the test pieces of Examples 1 to 3 with a microscope when E. coli is attached as microorganisms, respectively. Reference numerals 9 and 10 show images observed by a microscope on the surface of the test pieces of Comparative Examples 1 and 2 when Escherichia coli was attached as microorganisms, respectively.

  From the results shown in Table 1, it was found that all the pellets of Examples 1 to 26 satisfied the acceptance criteria in terms of low microbial adhesion. Also, from the results shown in FIGS. 1 to 10, it was found that the example had very little microorganisms attached and was extremely excellent in low microorganism adhesion as compared with the comparative example.

  From the above, according to the antibacterial material of the present invention, it is confirmed that the microorganism can be easily removed with an aqueous solution even if microorganisms adhere by setting the ester terminal amount in the polyacetal resin to a specific value or less. It was done.

Claims (18)

Including a polyacetal resin (A) containing an ester end group represented by the following formula:
The antimicrobial material in which the ester end group is contained in 1 g of the polyacetal resin (A) at a ratio of 20 μmol or less.
RCOO-
(Wherein R represents a hydrogen atom or an alkyl group) The polyacetal resin (A) includes an oxymethylene group and an oxyalkylene group having 2 or more carbon atoms,
The antibacterial material according to claim 1, wherein the oxyalkylene group is contained at a ratio of greater than 0 mol to 10 mol or less per 100 mol of the oxymethylene group.   The antibacterial material according to claim 1 or 2, further comprising a lubricant (B).   The antibacterial material according to claim 3, wherein the lubricant (B) is blended at a ratio of 1 to 3 parts by mass with respect to 100 parts by mass of the polyacetal resin (A).   The antibacterial material according to claim 3 or 4, wherein the lubricant (B) is an olefin-based lubricant. The repellant material according to claim 5, wherein the density of the olefin-based lubricant is 950 to 1000 kg / m ³ .   The antibacterial material according to claim 5 or 6, wherein the olefin-based lubricant has a viscosity of 500 to 10,000 mPa · s.   The acid repellent material according to any one of claims 5 to 7, wherein the acid value of the olefin-based lubricant is greater than 0 mgKOH / g and not greater than 20 mgKOH / g. 190 ° C., repellent fungus material according to any one of claims 1 to 8 melt volume rate measured at 2.16kg is 2~50cm ^3/10 min of the polyacetal resin (A).   The antibacterial material according to any one of claims 1 to 9, further comprising a formaldehyde scavenger (C). The formaldehyde scavenger (C) is at least one dihydrazone compound (C1) selected from the group consisting of a dihydrazone compound represented by the following general formula (1) and a dihydrazone compound represented by the following general formula (2) Including
The antibacterial material according to claim 10, wherein the dihydrazone compound (C1) is blended at a ratio of 0.02 to 5 parts by mass with respect to 100 parts by mass of the polyacetal resin.
(In the above formula, R ¹ represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ² to R ⁵ each independently represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, at least one of R ² and R ³ represents an alkyl group having 1 or 2 carbon atoms, and among R ⁴ and R ⁵ At least one represents an alkyl group having 1 or 2 carbon atoms.)
(In the above formula, R ⁸ represents an aliphatic hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ⁶ and R < ⁷ > shows a C3-C12 alicyclic hydrocarbon group each independently.) In Formula (1), repellent fungus material according to claim 11 R ¹ is an aliphatic hydrocarbon group having 6 to 12 carbon atoms. In the general formula (1), when R ² and R ⁴ are ethyl groups, R ³ and R ⁵ are hydrogen atoms, and when R ² and R ⁴ are methyl groups, R ³ and The antibacterial material according to claim 11 or 12, wherein R ⁵ is a hydrogen atom or a methyl group.   The antibacterial material according to any one of claims 11 to 13, wherein 0.05 to 3 parts by mass of the dihydrazone compound (C1) is blended with respect to 100 parts by mass of the polyacetal resin (A). The formaldehyde scavenger (C) contains a hydrazide compound (C2),
The said hydrazide compound (C2) is mix | blended in the ratio of 0.01-1 mass part with respect to 100 mass parts of said polyacetal resins (A), The microbicidal material as described in any one of Claims 10-14. .   The antibacterial material according to claim 15, wherein the hydrazide compound (C2) is composed of at least one selected from the group consisting of a monohydrazide compound and a dihydrazide compound.   The antibacterial material according to claim 16, wherein the hydrazide compound (C2) comprises only a dihydrazide compound.   The dihydrazide compound is composed of adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,18-octadecanedicarbohydrazide, terephthalic acid dihydrazide, 1,8-naphthalenedicarbohydrate and 2,6-naphthalenedicarbohydrazide. The antimicrobial material of Claim 17 comprised by at least 1 sort (s) chosen from a group.