JPH0687701A - Disinfectant for sterilizing antibiotic-resistant bacterium - Google Patents

Abstract

PURPOSE:To provide the sterilizing disinfectant excellent in its sterilization- disinfecting property against antibiotic-resistant bacteria and containing a vinylic copolymer containing structural units obtained from a non-cross-linking vinylic monomer and specific structural units as an active ingredient. CONSTITUTION:The antibiotic-resistant sterilizing disinfectant contains as an active ingredient a vinylic copolymer containing structural units obtained from a non-cross-linking vinylic monomer (e.g. styrene, ethyl acrylate, vinyl acetate) and structural units of formula I (R<1> is H, methyl; A is phenylene; R<2> is alkylene; B is a quaternary ammonium salt or a group containing a betaine type compound). B in the structural unit of formula I is a ground of formula II (in the bipyridine group bond positions between pyridine groups are 4,4'-, 2,2'-, 2,3'-, 2,4'-, 3,3'- or 3,4'-; X, Y are monovalent anion, etc.; R<3> is alkyl), a group of formula III (R<4> is alkylene; R<5> to R<8> are alkyl), etc. The sterilizing disinfectant is highly safe for target materials, etc., and can impart an excellent sterilizing property to the target materials over a long period.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disinfectant for antibiotic-resistant bacteria.

Infectious diseases are caused by various bacteria, and among them, infectious diseases caused by bacteria resistant to antibiotics have become a serious problem. For example, Staphylococcus aureus (MRSA) which shows resistance to methicillin is one of them.

Various methods have been studied as measures for reducing the occurrence of infectious diseases due to these, but it cannot be said that they are sufficiently effective.

Particularly in recent years, the problem of nosocomial infection has been emphasized,
Patients with impaired immune function, old people, newborns, premature infants, etc. have weak resistance to infection, and infection with these bacteria is easily established. Therefore, it is an obstacle to treatment or prevention.

Therefore, it has been desired to develop a safe drug that effectively sterilizes and disinfects antibiotic-resistant bacteria and has no harmful effects on the human body.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a germicidal disinfectant having excellent germicidal and disinfecting power against antibiotic resistant bacteria.

[0007]

The present invention provides an antibiotic-resistant bacterium containing as an active ingredient a vinyl copolymer containing a structural unit derived from a non-crosslinkable vinyl monomer and a structural unit represented by the general formula (I). Related to sterilizing agents.

[0008]

[Chemical 6]

[Wherein R ¹ represents a hydrogen atom or a methyl group,
Represents a phenylene group, R ² represents an alkylene group having 1 to ² carbon atoms, B represents a group containing a quaternary ammonium salt or a betaine compound, and A may contain a substituent. ]

In the vinyl copolymer, which is an active ingredient of the antibiotic-resistant bacterial bactericidal disinfectant of the present invention, the general formula (I)
Examples of B include groups represented by the following structural formulas (II) to (V).

[0011]

[Chemical 7]

[0012]

[Chemical 8]

[0013]

[Chemical 9]

[0014]

[Chemical 10]

[In the formula, bipyridine is 4,4'-, 2,2'-,
2,3'-, 2,4'-, 3,3'-, 3,4'-isomers are shown, and X,
Y is an anion which may be the same or different, and each of X and Y may be a monovalent anion or (X, Y) may be one divalent anion. R ³ is an alkyl group having 6 to 18 carbon atoms, R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ^{5 to} R ⁸ may be the same or different, and are an alkyl group having 1 to 3 carbon atoms, R ⁹ Represents an alkylene group having 1 to 3 carbon atoms, and each may contain a substituent. ]

In the general formula (I), the alkyl group represented by R ³ has a carbon number of 6 to 18, but from the viewpoint of antibacterial activity, 8, 10 and 12 are more preferable. The anion is not particularly limited, and Br ⁻ , Cl ⁻ , I ⁻ , NO ₃ ⁻ ,
CH ₃ COO ⁻ and SO ₄ ²⁻ are included.

The number average molecular weight Mn of the copolymer is 2,000 to 1,
, 000,000, preferably 5,000-100,000, Mw / Mn = 1.1-
2.0 (Mw is a weight average molecular weight) is desirable.

The proportion of the structural unit (I) contained in the copolymer is 0.1 to 90 mol%, preferably 1 to 50 mol%, and particularly preferably 10 to 30 mol%.

The copolymer is obtained by copolymerizing chloro (C _1-2 alkyl) styrenes with a non-crosslinkable vinyl monomer which can be copolymerized to form a copolymer, and then chloro (chlorine) of this chloroalkyl group. ) Atoms are replaced with the quaternary ammonium salt or betaine type compound described above.

As the chloro (C _1-2 alkyl) styrenes used in the present invention, p-chloromethylstyrene is preferable, but it is a chloro (C _1-2 alkyl) styrene derivative having another substituent. You can buy it.

Examples of non-crosslinkable vinyl monomers include:
Styrene-based monomers such as styrene and p-methylstyrene; acrylic ester-based monomers such as ethyl acrylate and lauryl acrylate; methacrylate-based monomers such as methyl methacrylate, ethyl methacrylate, lauryl methacrylate; vinyl acetate, butyric acid Vinyl ester monomers such as vinyl; N-methyl acrylamide, N
-N-alkyl-substituted (meth) acrylamides such as -ethylacrylamide, N-methylmethacrylamide, and N-ethylmethacrylamide; and nitrile-based monomers such as acrylonitrile and methacrylonitrile.
The monomer is not limited to the above monomers as long as it is a monomer copolymerizable with chloromethylstyrenes. These monomers are
It is possible to use alone or in combination of two or more.

In the copolymerization of chloroalkylstyrene and non-crosslinkable copolymerized vinyl monomer, the compounding molar ratio is 1
It is preferably about 50: 50-99.

As the copolymerization method, conventionally known bulk polymerization, solution polymerization, suspension polymerization and the like can be used.

Next, an example of a method for producing the copolymer is shown by a reaction formula.

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

In the above (1), the compound (P) is usually about 1.0 to 2.5 times mol, preferably about 1.
It is recommended to carry out a 1- to 2.1-fold molar reaction. The reaction is preferably carried out in an organic solvent, generally a reaction temperature of about 60 to 110 ° C. being suitable. The product (PQ) can be purified by methods such as concentration, distillation, extraction and recrystallization. The polymerization of (2) can be carried out by a usual method such as suspension polymerization, solution polymerization or bulk polymerization, and the obtained polymer (PCS) can be purified by a method such as reprecipitation or washing. In the reaction (3), the chloromethyl group 1 of the polymer (PCS)
The compound (PQ) is usually reacted in an amount of about 0.1 to 1.2 equivalents, preferably about 0.8 to 1.0 equivalents, based on the equivalent amount. The reaction is preferably carried out in an organic solvent, generally about 60-100 ° C.
The reaction temperature of is preferred. Product (BPQ) reprecipitated,
It can be purified by a method such as washing. (4) ~
Also for (9), it can be manufactured by almost the same method.

In the reaction of (10), the compound (PC
It is preferred to react about 0.8 to 1.5 moles of long chain alkyl amine with S).

In (11), it is generally preferable that the concentration of the NaOH solution is about 0.5 to 2.0N.

In (12), it is preferable to react monochloroacetic acid with the compound (PCS-AA) in a molar amount of about 1 to 2 times. The reaction is preferably carried out in an organic solvent, preferably at reflux for about 2-10 hours. Product (PCS-BT)
Can be purified by a method such as reprecipitation or washing.

The bipyridine used for producing the copolymer includes 2,2'-bipyridine, 2,3'-bipyridine, 2,4'-bipyridine, 3,3'-bipyridine, 3,4 '. -Bipyridine, 4,4'-bipyridine and mixtures thereof are used.

The alkyl halide has 6 to 18 carbon atoms.
Alkyl halides such as chlorine, bromine or iodine are used.

As the alkyldiamine, for example, N, N,
N ', N'-tetramethylethylenediamine, N, N, N',
N'-tetramethyl-1,3-propanediamine, N, N,
N ', N'-tetramethyl-1,4-butanediamine, N, N,
N ', N'-tetramethyl-1,5-pentanediamine, N,
N, N ', N'-tetramethyl-1,6-hexanediamine,
N, N, N ', N'-tetraethylethylenediamine, N,
N, N ', N'-tetraethyl-1,3-propanediamine,
N, N, N ', N'-tetraethyl-1,4-butanediamine,
N, N, N ', N'-tetraethyl-1,5-pentanediamine, N, N, N', N'-tetraethyl-1,6-hexanediamine and the like are used.

Examples of amino alcohols include 2-aminoethanol, 3-amino-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 7-aminoheptanol, 8-aminooctanol and 2- ( Dimethylamino) ethanol, 2-
(Diethylamino) ethanol, 3- (dimethylamino) propanol, 3- (diethylamino) propanol and the like are used.

Examples of the secondary amine include N-methyloctylamine, N-methyldecylamine, N-methyldodecylamine, N-methylmyristylamine, N-methylcetylamine, N-methylstearylamine and N-ethyloctyl. Amine, N-ethyldecylamine, N-ethyldodecylamine and the like are used.

The obtained copolymer is subjected to ion exchange in accordance with a known method, and the counter anions are changed to Cl ⁻ , Br ⁻ ,
It can be I ⁻ , NO ₃ ⁻ , NO ₂ ⁻ , SO ₂ ²⁻ , CH ₃ COO ^−, or the like.

Since the copolymer uses a copolymer of chloroalkylstyrenes and a non-crosslinkable vinyl monomer as a raw material, it is excellent in the following points as compared with a homopolymer of chloroalkylstyrenes as a raw material.

That is, when a quaternary ammonium salt or a betaine type compound is introduced using the above copolymer,
Since the amount of unreacted chloroalkyl residues is smaller than that in the case of using the homopolymer, the stability of physical properties and the safety for human body are excellent. In addition, copolymerization using a non-crosslinkable vinyl monomer that is cheaper than chloroalkylstyrenes can reduce the production cost.

When the antibiotic-resistant bacterial bactericidal disinfectant of the present invention is used, one kind or a mixture of two or more kinds of the above-mentioned active ingredient polymers can be used.

The copolymer used as the active ingredient of the antibiotic-resistant bacterial bactericidal disinfectant of the present invention can be in the form of powder, granules, fibres, films or the like depending on the production method of the polymer. .

The antibiotic-resistant bacterial bactericidal disinfectant of the present invention is used in hospital walls, ceilings, corridors, floors, medical instruments, beds, sheets, clothes for medical workers, hand disinfection, and other food packaging materials.
It can be used across a wide range of tap water, cooling water, pools, building materials, clothing and household items.

In using the disinfectant of the present invention, known methods can be used. For example, when the surface of an object is subjected to antibacterial treatment, one or more of the above polymers may be dissolved in a suitable solvent and treated by a dipping method or a spray method. At that time, a known polymer may be mixed and used.

Specific examples of objects to which the sterilizing agent of the present invention can be used include synthetic polymers of all forms such as polypropylene, polyethylene, polystyrene, polyester, polyamide, polyacrylate, and the like.
Examples include natural polymers such as polyurethane and polyvinyl chloride, such as cotton, wool, feathers, hemp, silk, paper and rubber, as well as wood, glass, metal and ceramic products.

The shape of these objects may be a molded product or a raw material. For example, the antibacterial treatment can be carried out in a thread shape, a fiber shape, a film shape, a sheet shape, a granular shape, a powder shape, or the like.

Further, after dissolving the disinfectant of the present invention in an organic solvent such as alcohol, the fingers are dipped and dried,
A thin film is formed on the surface of the skin and acts as a simple glove.
If unnecessary, the sterilizing agent of the present invention can be removed by washing with a solvent capable of dissolving the sterilizing agent, for example, alcohol, and then washing with water.

The disinfectant of the present invention can impart high safety and excellent antibacterial property to the above-mentioned objects and the like for a long period of time.

When the disinfectant of the present invention is used, it is generally methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, N, N-dimethylformamide, N, N-. It is preferably dissolved in dimethylacetamide, dimethylsulfoxide, or the like, or dissolved in a mixed solvent of these solvents and acetone, tetrahydrofuran, benzene, toluene, xylene, or the like for use. The concentration is 0.01 to 2.0% by weight, preferably 0.1 to 1.
Dissolve to 0% by weight. A substance to be imparted with antibacterial property is dipped in this solution, or the solution is applied to the surface by a method such as coating or spraying on the substance and then dried to remove the solvent. Drying temperature is 0-80
It is desirable to dry at 10 ° C, preferably 20 to 60 ° C in a drying chamber for 10 to 48 hours.

The known antibacterial agent that can be used in combination with the antibiotic-resistant bacterial bactericidal disinfectant of the present invention is not particularly limited, and examples include methicillin (DMPP).
C), Ampicillin (ABPC), Cefotiam (CT)
M), Cefzonam (CZON), Gentamicin (G
M), Arbekacin (ABK), Doxycycline (D
OXY), minocycline (MINO), fosfomycin (FOM), vancomycin (VCM), imipenem / cilastatin sodium (IPM / CS), ofloxacin (OFLX) and the like, and as a disinfectant, benzalkonium chloride (BAC), Examples thereof include chlorhexidine gluconate (CHG), alkyldiaminoethylglycine hydrochloride (TG), povidone iodine (PVP-I) and glutaraldehyde (GA).

Any known coating film-forming composition that can be used in combination with the germicidal disinfectant of the present invention may be used, for example, acrylic acid resin-based, phthalic acid resin-based, amino alkyd resin-based compositions, Examples thereof include synthetic resin emulsion type and ratker.

The antibiotic-resistant bacteria to which the present invention is directed covers a wide range, and includes, for example, methicillin-resistant Staphylococcus aureus (MRSA), various antibiotic-resistant Pseudomonas aeruginosa,
Examples include Escherichia coli, Bacillus subtilis, and Pneumococcus.

[0061]

EXAMPLES The present invention will now be described with reference to examples.

Example 1 300 ml of methyl alcohol was placed in a 1 l four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a dropping funnel.
l and 4,4'-bipyridyl 80.9 g (0.50 mol) were charged, and while introducing dry nitrogen, 22.3 g (0.25 mol) of lauryl bromide was added from a dropping funnel while heating on an oil bath at 70 ° C. It dripped over time. After heating and stirring for 18 hours,
The solvent was removed and recrystallized from a methanol: acetone system. 42.5 g of brown powdery N-lauryl-4,4'-pyridylpyridinium bromide (hereinafter abbreviated as PQ) was obtained. The same reaction was performed with other alkyl halides.

Then, a copolymer (hereinafter abbreviated as PCS) was produced by a copolymerization reaction of p-chloromethylstyrene (abbreviated as CS) and styrene (abbreviated as ST) by a conventional solution polymerization. The obtained PCS was reprecipitated with tetrahydrofuran / methanol to remove unreacted monomers.

Next, the total halogen quantitative analysis and elemental analysis were carried out on the PCS by the oxygen flask combustion method, and it was found that CS / ST in PCS was 3/7 (molar ratio).

The obtained PQ (53.3 g) and PCS (52.9 g) were reacted in 850 ml of tetrahydrofuran at 65 ° C. for 64 hours to obtain 94.8 g (yield 89.3%) of BPQ as a yellow powder.

Example 2 290 g of nitromethane (4. liter) was added to a 1 liter four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a dropping funnel.
80 mol) and 1,2'-bipyridyl 13.5 g (0.09 mol) were charged, and while introducing dry nitrogen, lauryl bromide 44.7 g from a dropping funnel while heating on an oil bath at 110 ° C.
(0.18 mol) was added dropwise over 2 hours.

After heating and stirring for 5 hours, the solvent was removed and the product was recrystallized from an ethanol: acetone system. 12 g of brown powdery N-lauryl-2,2'-pyridylpyridinium bromide (hereinafter abbreviated as PQ2) was obtained. The same reaction was performed with other alkyl halides.

Then, PQ2 (10 g) and the polymer PCS (200 g) obtained in Example 1 were dissolved in tetrahydrofuran 80
As a result of reacting in 0 ml at 60 ° C for 50 hours, yellow powder B
2207 g (98.6%) of PQ were obtained.

Example 3 In a 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 50 ml of benzene and 6 ml (0.1 mol) of ethanolamine (Wako Pure Chemical Industries, Ltd., first grade reagent, hereinafter abbreviated as EA). 2.3 g (0.1 mol) of metallic sodium was gradually added with stirring. 5 to after addition
The reaction was carried out at 10 ° C for 5 hours.

After completion of the reaction, benzene was removed and
PCS (40.7g) and tetrahydrofuran 1 obtained in
00 ml was added, and the mixture was reacted under reflux for 24 hours. After the reaction, the obtained polymer (hereinafter, abbreviated as PCS-EA) was reprecipitated with acetone / methanol, washed, and dried. Yield 42.0
g.

Next, 40 g of PCS-EA was placed in a 300 ml eggplant-shaped flask, 20 ml of formaldehyde and 20 ml of formic acid were added, and the reaction was carried out at 60 to 80 ° C. for 8 hours. The obtained polymer (hereinafter abbreviated as PCS-DA) was reprecipitated with acetone / methanol, washed and dried. Yield 41.0g.

Next, 40 g of PCS-DA, 3 g (0.01 mol) of lauryl bromide and 100 ml of ethyl alcohol were added to 30 g.
Put in a 0 ml eggplant-shaped flask and react at 90 ° C for 24 hours.
41.2 g of a polymer (hereinafter abbreviated as PCS-TA) was obtained.

Example 4 N, N, N ′, N′-Tetramethyl-1,3-propanediamine (Tokyo Kasei Co., Ltd., reagent grade 1, hereinafter abbreviated as TMDA)
21.3 g (0.16 mol) and lauryl bromide 20.6 g (0.08 mol)
Mol) in a 200 ml four-necked flask at 77-80 ° C for 24 hours, and then the reaction mixture is centrifuged (Kokus).
an H-16) and separate at 3000 rpm. White paste N, N, N ', N'-tetramethyl-1,3-propanediamine-N-lauryl bromide (hereinafter abbreviated as TQ)
15.8 g (0.04 mol) was obtained.

10.2 g of PCS and TQ obtained in Example 1
After reacting 7.9 g with 150 ml of THF under stirring at 65 ° C for 12 hours, the solvent was removed and reprecipitation was carried out with methanol / acetone to obtain a white powdery polymer (hereinafter referred to as PCS-T).
Abbreviated as D) 16.2 g (yield 89.5%) was obtained.

Example 5 In Example 1, 56.2 g (0.25 mol) of decyl bromide was used in place of lauryl bromide, and 96 g (yield 90.4%) of yellow powder polymer (hereinafter abbreviated as BPQ-C10) was prepared in the same manner. Obtained.

Example 6 To 148 g of PCS obtained in Example 1 was added tetrachloroethylene, and N-methyl-N-decylamine 1 was added with stirring.
70 g (1 mol) was added dropwise, and the mixture was refluxed for 4 hours, and then the reaction mixture was put into a mixed solution of aqueous potassium hydroxide and methanol. Wash with methanol until no free amine is detected. Yield of produced polymer (hereinafter abbreviated as PCS-AH) 310
g, the yield was 96%.

Next, water was added to 310 g of the compound PCS-AH, and a caustic soda solution was added with stirring to make the concentration about 1 N. After refluxing for 30 minutes under stirring, the reaction product was filtered and washed with water. Chloride ions in the filtrate were titrated with silver nitrate to determine the reaction yield. The amount of the produced polymer (hereinafter abbreviated as PCS-AA) was 275 g, and the yield was 96%.

Finally, 275 g of the compound PCS-AA and 114 g (1.2 mol) of monochloroacetic acid were refluxed in a tetrachloroethylene solution for 4 hours with stirring. The produced polymer (hereinafter abbreviated as PCS-BT) was quantified by colorimetric determination by Orange II method. The yield was 322 g and the yield was 94%.

Example 7 The following experiment was conducted by changing the charged molar ratio of CS and ST in Example 1.

CS 62.8 g (0.41 mol) and ST 48 g (0.41 mol)
Mol) and using 300 g of AIBN as an initiator, 200 ml of THF
Solution polymerization was carried out in the medium at 67 ° C. for 19 hours, and purification was carried out in the same manner as in Example 1 to obtain 78.8 g (yield 71.1%) of PCS as a white powder. From the results of halogen determination and elemental analysis by the flask combustion method, CS / ST in PCS was 1/1. The number average molecular weight by GPC was 9,000.

Using this PCS, an antibacterial polymer compound (hereinafter abbreviated as BPQ-1 / 1) was prepared in the same manner as in Example 1.
5.1 g was obtained with a yield of 89.5%.

Examples 8 to 10 In Example 1, ethyl acrylate (EA), methyl methacrylate (MMA) and vinyl acetate (VA) were used in place of styrene to carry out a copolymerization reaction with CS. Copolymers PCE, PCM and PCV were obtained.

Then, the total halogen quantitative analysis and elemental analysis by the oxygen flask combustion method were carried out on these copolymers, and the molar ratio of the constituents was determined.

CS / EA in PCE = 3/7, CS / MMA in PCM = 3/7, CS / VA in PCV = 3 /
7

Then, using PCE, PCM and PCV in the same manner as in Example 1, in a tetrahydrofuran solvent, P was added.
When reacted with Q, each polymer compound BPQ-
EA, BPQ-MMA and BPQ-VA were obtained in the following yields. BPQ-EA ... 90.7 g (85.4%) ... Example 8 BPQ-MMA ... 89.5 g (84.3%) ... Example 9 BPQ-VA ... 82.0 g (77.2%) ... Example 10

Comparative Example 1 A homopolymer of CS (hereinafter referred to as P
CS-H) was produced by the polymerization reaction. PC obtained
S-H was washed with hot acetone to remove unreacted monomers.

53.0 g of PQ obtained in Example 1 and PCS-
As a result of reacting 53.0 g of H with 850 ml of a THF solvent at 65 ° C. for 64 hours, 95.0 g (yield 90.6%) of a yellow powder polymer (hereinafter abbreviated as BPQ-H) was obtained.

Test Example 1 (Acute skin irritation) OE was obtained using the BPQ of Example 1 and the BPQ-H of Comparative Example 1.
An acute skin irritation test was conducted in accordance with CD Chemicals Test Guideline 2 (Chemicals Inspection Association of Japan) 404.

A powder of the above compound was administered to a small part of the skin of a rabbit, fixed with a covering tape with a gauze patch, and after 4 hours, the patch was removed. The results of examining the skin after removal are shown in Table 1.

[0090]

[Table 1]

In Table 1, 0 ... no erythema 0 ... no edema 1 ... extremely light erythema 1 ... extremely light edema 2 ... attached erythema 2 ... light edema 3 ... medium to strong erythema 3 ... medium Edema 4 ... Intense erythema 4 ... Intense edema

Examples 11 to 20 Take 0.5 g each of the polymers obtained in Examples 1 to 10,
It was dissolved in 100 g of methanol. 1 high density polyethylene film (HDPE, thickness 80 μm) was added to this methanol solution.
A piece cut into a size of 4 cm × 50 cm was immersed for 30 seconds, then pulled up and dried at 25 ° C. for 1 hour. Further, it was dried in a dryer at 50 ° C. for 1 hour and given the following example numbers.
The polymers used in the above treatment are as follows. BPQ (Example 1) -Example 11 BPQ2 (Example 2) -Example 12 PCS-TA (Example 3) -Example 13 PCS-TD (Example 4) -Example 14 BPQ- C10 (Example 5) ... Example 15 PCS-BT (Example 6) ... Example 16 BPQ-1 / 1 (Example 7) ... Example 17 BPQ-EA (Example 8) ........ Example 18 BPQ-MMA (Example 9) ... Example 19 BPQ-VA (Example 10) ... Example 20 The amount of the above polymer adhering to the surface was 0.1 μmole / c.
It was m ² .

Comparative Examples 2 to 3 0.2 g of polyurethane resin, 30 g of methyl ethyl ketone, 70 g of toluene, and 0.2 g of benzalkonium chloride (manufactured by Nacalai Tesque, Inc.) were mixed and dissolved, and the same HDPE as in Example 11 was immersed therein. The same process was performed to obtain Comparative Example 2.

Comparative Example 3 was prepared by using 1,6-di (Np-chlorophenyl biguanide) hexane digluconate in place of the above-mentioned benzacornium chloride and treating in the same manner as in Example 11.

Test Example 2 (Adhesion to Film) The HDPE film pieces of Examples 11 to 20 and Comparative Examples 2 to 3 were each placed in a 2 liter beaker together with 1 liter of distilled water at 25 ° C. After vigorous stirring for 8 hours, a peel test was performed. After pulling up the film and drying it at 25 ° C for 1 hour, it is treated with bromophenol blue 10 ^-4 M (phosphate buffer pH 7.0) to make the surface develop a blue color to prevent the polymer compound film from peeling or falling off. The adhesion to the film before and after the peel test was compared. The results are shown in Table 2.

[0096]

[Table 2]

In Table 2, uniformly colored ones are indicated by ◯, and some uneven coloring is indicated by Δ.

Test Example 3 (Oxygen gas permeability and moisture permeability) Oxygen gas permeability and moisture permeability tests were conducted using the film pieces of Examples 11 to 20 and Comparative Examples 2 to 3. The former is GA
Using S TESTER TOYOSEIKI, ASTM
-D-1434-75-M.

The latter was carried out according to the method of JIS-Z-0208 using a TOYOSEIKI cup type moisture-permeable device. The results are shown in Tables 3 and 4.

[0100]

[Table 3]

[0101]

[Table 4]

Test Example 4 (Film Antibacterial Test) A part of the film pieces of Examples 11 to 20 and Comparative Examples 2 to 3 was subjected to a peeling test for 90 minutes with saturated steam at 90 ° C., and then at 25 ° C.
After being dried for 24 hours, the sample after the peeling test was used for the following test.

Bacteria shake-cultured in Nutrient broth (Difco. Lab.) For 18 hours were diluted with sterile water to 10 ⁴ cells / ml. Film pieces before and after the cut-off peeling test (Examples 11 to 20)
And Comparative Examples 2 to 3) were placed in a polypropylene gas barrier bag (180 × 80 cm), 50 ml of the above bacterial solution was placed therein, and heat sealed. The bag containing the film piece was set in a constant temperature shaking culture device at 37 ° C. and tested for 18 hours.

After the culture test, the bacterial solution was collected, and the number of remaining viable cells was measured by the colony counting method according to a conventional method.
The following 9 strains were used as test bacteria.

No. 1. Pseudomonas aeruginosa resistant isolate 2. Klebsiella pneumoniae resistant isolate 3. 3. Escherichia coli resistant isolate 4. Staphylococcus aureus resistant isolate a5. Staphylococcus aureus resistant isolate b6. Staphylococcus aureus resistant isolate c 7. Staphylococcus aureus resistant isolate d8. Staphylococcus aureus resistant isolate e9. Bacillus subtilis resistant isolates

After the measurement of the number of bacteria, the viable cell count of 10 ⁵ cells / ml or more was ×, 10 ³ to 10 ⁴ cells / ml was △, 10 to 10 ² cells / ml was ○,
Zero is represented by ⊚. The results are shown in Table 5. Specimen name and N
o. is as described above, and in Tables 5 to 7, only No. is shown.

[0107]

[Table 5]

Example 21 An acrylic resin plate having a size of 4 cm × 4 cm × 1 mm was subjected to the following treatment. 100 g of ethanol, 400 g of acrylic resin and BPQ obtained in Example 1 were mixed and spray-coated on the acrylic resin plate. Example 21 after drying at 45 ° C. for 60 minutes
And The BPQ content was adjusted to 0.1 μmole / cm ² .

Comparative Example 4 Comparative Example 4 was prepared by treating an acrylic resin plate in the same manner as in Example 21 except that benzalkonium chloride was used at the same concentration in place of BPQ in Example 21.

Test Example 5 (Acrylic Resin Plate Antibacterial Test) The acrylic resin plates of Example 21 and Comparative Example 4 were rinsed in warm water at 80 ° C. for 60 minutes with or without washing in Test Example 4
It was subjected to the same antibacterial test. The display mark of the viable cell count was also the same as in Test Example 4. The results are shown in Table 6.

[0111]

[Table 6]

Example 22 A 0.5% by weight methanol solution of BPQ obtained in Example 1 was treated with a cloth (cotton kanaquin: JIS standard cloth) by the exhaust method and subjected to an antibacterial test. The processing density for cloth is BPQ 5
It was prepared with μmole / g cloth.

Comparative Example 5 Benzalkonium chloride (BAC) was dissolved in an emulsion type resin in an amount of 0.5% by weight to prepare Example 2
It was attached to the same cloth as 2. After drying at 50 ° C. for 12 hours, it was subjected to an antibacterial test. The processing density on the cloth was BAC 5 μmole / g cloth.

Test Example 6 (Antibacterial Test of Cloth) Each of the cloths treated in Example 22 and Comparative Example 5 was subjected to a bacterial growth inhibition test without washing treatment or after washing treatment for a predetermined number of times. The sterilization rate was calculated by the method.

In each washing treatment, "Nitsusan Nonion NS-210" (manufactured by NOF CORPORATION) as a detergent was used.
Water is used at a ratio of 0.5g to 1 liter of water.
It was washed with a household electric washing machine for 5 minutes at a bath temperature of 1:30 at ℃, and then washed for 5 minutes while overflowing with water.

The above-mentioned bacterial growth inhibition test method was carried out based on the following method. As the test bacteria, the same 9 as in Test Example 4 was used.
A strain was used. 0.2 g of the above test cloth was put into a sterilization bile according to the JIS test method (currently under consideration, planned to be JIS in 1993) and sterilized by an autoclave at 121 ° C. for 15 minutes. The above bacteria were cultured in NB medium at 37 ° C for 18 hours with shaking to give 1/1
NB was adjusted to approximately 10 ⁶ cells / ml. Add the above bacterial solution to the bail
0.1 ml was inoculated and cultured at 37 ° C for 18 hours. After culturing, 10 ml of physiological saline containing 0.2% Tween 80 was added to the vial, the bacteria were washed out by shaking, and the viable cell count was performed by colony counting according to a conventional method. The test results are shown in the same manner as in Test Example 4.
The results are shown in Table 7.

[0117]

[Table 7]

[0118]

The bactericidal / disinfectant of the present invention is highly safe, has an excellent bactericidal effect against antibiotic-resistant bacteria, and can maintain the effect for a long period of time.

Claims (2)

[Claims] 1. A constitutional unit derived from a non-crosslinkable vinyl monomer and a general formula: [In the formula, R ¹ represents a hydrogen atom or a methyl group, A represents a phenylene group, R ² represents an alkylene group having 1 to ² carbon atoms, and B represents a fourth group.
A group containing a primary ammonium salt or a betaine compound is shown, and A may contain a substituent. ] An antibiotic-resistant bactericidal disinfectant containing a vinyl-based copolymer containing a structural unit represented by the following as an active ingredient. 2. In the compound (I), B is represented by the general formula: [Chemical 3] [Chemical 4] Or [In the formula, bipyridine is 4,4'-, 2,2'-, 2,3'-, 2,4 '
-, 3,3'-, 3,4'- isomers are shown, and X and Y may be the same or different anions, and X and Y are monovalent anions or (X, Y) respectively. It may be one divalent anion. R ³ is an alkyl group having 6 to 18 carbon atoms, R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ^{5 to} R ⁸ may be the same or different, and are an alkyl group having 1 to 3 carbon atoms, R ⁹ Represents an alkylene group having 1 to 3 carbon atoms, and each may contain a substituent. ] The antibiotic-resistant bacterial bactericidal disinfectant containing the vinyl copolymer according to claim 1 as the active ingredient.