JPH06347733A - Treatment to give antimicrobial property to frame of spectacles and parts of spectacles - Google Patents

Abstract

PURPOSE:To provide a treating method to give antimicrobial property to a frame of spectacles or parts of spectacles so that excellent antimicrobial property can be maintained for a long time without elusion of the antimicrobial agent and the intrinsic color tones of the frame or parts of spectacles can not be damaged, and the obtd. frame is excellent in safety. CONSTITUTION:Surfaces of the frame or parts of spectacles are coated with a polymer having antimicrobial property so that the frame or parts of spectacles have antimicrobial property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method for imparting antibacterial properties to eyeglass frames and eyeglass parts.

[0002]

2. Description of the Related Art Dirt from sweat or secretions attached to eyeglass frames, etc. not only cause discomfort and malodor, but also become a breeding source of various bacteria such as Staphylococcus aureus which is a skin-resident bacterium and adversely affects the human body. May affect

Therefore, various studies have been made as measures to prevent these problems. For example, a method of kneading a low-molecular compound antibacterial agent or the like with a resin and applying the kneaded resin to a spectacle frame (Japanese Patent Laid-Open No. 4-312058)
-194815, Actual Kaihei 3-71319, Actual Kaihei 4
No. 120922), a method for producing a spectacle frame by using a resin pellet with an antibacterial agent of a low molecular weight compound (Japanese Patent Laid-Open No. 3-2021).
249725), a method of supporting an antibacterial metal on an inorganic carrier and then kneading with a resin to produce an eyeglass frame (Actual No. 3-47513), or after supporting an antibacterial metal on an inorganic carrier. , A method of kneading with a resin and covering the spectacle frame (Jitsukaihei 3-69122).

However, in the method of using an antibacterial agent or the like of a low molecular weight compound, the antibacterial agent is gradually eluted during use of the spectacle frame, which may adversely affect the human body, and There are drawbacks such as the inability to maintain antibacterial activity. Further, in the method of using an antibacterial metal supported on an inorganic carrier, it is difficult to obtain a transparent color tone, and
There is a concern that the physical properties and strength of the spectacle frame may deteriorate.

[0005]

The object of the present invention is to prevent the antibacterial agent from eluting and to maintain the excellent antibacterial activity over a long period of time, and to impair the original color tone of the spectacle frame and spectacle parts. Another object of the present invention is to provide a treatment method for imparting antibacterial properties to eyeglass frames and eyeglass parts, which is excellent in safety.

[0006]

The present invention relates to a treatment method for imparting antibacterial properties to eyeglass frames and eyeglass parts, which is characterized in that the surface of the eyeglass frames and eyeglass parts is coated with a polymer having antibacterial properties. Pertain.

In the present invention, as the polymer having antibacterial properties, a vinyl-based copolymer containing a structural unit derived from a non-crosslinkable vinyl monomer and a structural unit represented by Chemical formula 6 can be preferably used.

[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 of the present invention, B in the general formula (1) is, for example, the following structural formulas (2) to (5).
The group represented by can be mentioned.

[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. ]

The compound (1) has a strong antibacterial spectrum over a wide range, is soluble in a solvent, has a large adhesive force, and easily forms an antibacterial film. When the surface of the spectacle frame and the spectacle part is coated with the compound (1), the antibacterial agent is not eluted and the excellent antibacterial activity can be maintained for a long period of time. Moreover, since the compound (1) is transparent, it does not impair the original color tone of the spectacle frame and spectacle parts.

Further, the compound (1) is acute oral toxicity in mice.
It is 5,000 mg / kg or more, has no irritation in the rabbit skin primary irritation test, and can be safely used for the human body.

As a method for coating the surface of the spectacle frame and the spectacle component of the present invention, known methods such as gun spray coating or coating with a brush are used. At that time, the compound (1) may be used as a single solution or as a mixture with an existing film-forming composition. It is also possible to use a mixture of the compound (1) and a commercially available antibacterial agent or the like.

In the present invention, the spectacle frame and spectacle parts capable of imparting antibacterial property are not particularly limited, but for example, so-called normal spectacles for spectacle frames, sports glasses, safety glasses and fashion glasses are also used. And the like, and the spectacle parts include a nose pad and a modern earpiece.

Next, the solvent for dissolving the compound (1) is not particularly limited as long as it can dissolve the compound (1), and examples thereof include methanol, ethanol, tetrahydrofuran, dimethylformamide, chloroform and methylene chloride. Or the like, or a mixed solvent thereof.

The coating film-forming composition which can be mixed with the compound (1) is not particularly limited as long as it is suitable for coating eyeglass frames and the like, and examples thereof include acrylic resin, amino resin, polyurethane resin and silicone. Resin, etc., or a mixture thereof can be mentioned.

Further, the commercially available antibacterial agent which can be used by mixing with the compound (1) is not particularly limited,
For example, benzalkonium chloride, alkyldiaminoethylglycine hydrochloride, 3- (trimethoxysilyl) -propyloctadecyldimethylammonium chloride, 2-
Examples thereof include (4′-thiazolyl) benzimidazole, 2- (carbomethoxyamino) benzimidazole and N- (fluorodichloromethylthio) phthalimide.

In the general formula (1), the alkyl group of R ³ has a carbon number in the range of 6 to 18, but is preferably 8 to 14 from the viewpoint of antibacterial activity. The anion is not particularly limited, and examples thereof include chlorine ion, bromine ion, iodine ion, perchlorate ion, acetate ion, methylsulfate ion, benzenesulfonate ion, chlorobenzenesulfonate ion, toluenesulfonate ion and the like. The monovalent anion, the sulfate ion, and the divalent anion such as methyl phosphate ion can be mentioned. The number average molecular weight Mn of the copolymer is 5,000 to 5,000,000, preferably 10,000.
0-2,000,000, Mw / Mn = 1.1-7.0 (Mw is a weight average molecular weight) is desirable.

The proportion of the structural unit (1) in the copolymer is 0.1 to 90 mol%, preferably 5 to 60 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 the chloroalkyl group. ) Atoms are replaced with the quaternary ammonium salt or betaine type compound described above. Alternatively, it can be produced by previously substituting the chlorine atom of chloroalkylstyrenes with a quaternary ammonium salt or a betaine-type compound and then copolymerizing with a copolymerizable non-crosslinkable vinyl monomer.

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.

As the non-crosslinkable vinyl monomer, for example,
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.

The molar ratio of the chloroalkyl styrene and the non-crosslinkable copolymerized vinyl monomer to be copolymerized is as follows:
1-60: 40-99 is preferable.

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.

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

In the above (1), the compound (DP) is usually about 1.0 to 10.0 times mol, preferably about about 10 times the compound RX.
It is better to carry out 1.1- 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 (Q) can be purified by a method such as 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 of (3),
The compound (Q) is usually used in an amount of about 0.1 to 2.0 equivalents, preferably about 0.8 to 1 equivalent of the chloromethyl group of the polymer (PCS).
React 1.2 equivalents. The reaction is preferably carried out in an organic solvent, generally a reaction temperature of about 60-100 ° C being suitable. The product (BPCQ) can be purified by a method such as reprecipitation and washing. Also (4) to (7) can be manufactured by substantially the same method.

In the reaction of (8), the compound (PC
It is preferred that the long-chain alkylamine is reacted in a molar amount of about 0.8 to 2.0 times that of S).

In (9), it is generally preferred that the concentration of the NaOH solution is about 0.5 to 2.0N.

In (10), 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 and 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.

Regarding the anion of the compound (1),
The desired type can be obtained according to known techniques. For example, at the stage of previously reacting chloroalkylstyrenes with a quaternary ammonium salt or a betaine-type compound, or at the stage of the copolymer as the final compound, after dissolving each compound in a soluble solvent, The anion can be exchanged by adding a salt containing a desired anion, concentrating, drying and purifying after the reaction.

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. In the present invention, the vinyl copolymer is easy to form a film and has a large adhesive force.

[0053]

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

Example 1 300 ml of methyl alcohol was placed in a 1-liter four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a dropping funnel.
After charging l and 4,4'-bipyridyl 149.8g (0.96mol), lauryl bromide (abbreviated as LB) was added from a dropping funnel while introducing dry nitrogen and heating on an oil bath at 70 ° C.
29.9 g (0.12 mol) was added dropwise over 2 hours. After heating and stirring for 18 hours, the solvent was removed, and recrystallization from a methanol: acetone system was performed. The crystals were dried under reduced pressure by a vacuum pump at room temperature to obtain brown powder of N-lauryl bromide-4,
4'-pyridylpyridinium (hereinafter abbreviated as Q) 42.5 g (0.1
1 mol) was obtained. The yield of Q based on LB was 87.5%. The chemical structure of Q was confirmed by ¹ H-NMR, IR, CHN analysis, colloid titration, and quantification of total halogen by oxygen flask combustion method.

Then, by a conventional solution polymerization, a copolymerization reaction of 15.3 g (0.10 mol) of p-chloromethylstyrene (abbreviated as CMS) and 93.6 g (0.90 mol) of styrene (abbreviated as ST) was performed. A white polymer formed. After cooling the reaction mixed solution, the white polymer was taken out by decantation, and then reprecipitation was repeated three times with a tetrahydrofuran / methanol system to remove unreacted monomers and purify. The purified polymer was heated and dried under reduced pressure all day and night to give a white powdery polymer (abbreviated as PCS) 9
9.4 g (91.3% yield) was obtained. Regarding the PCS, ¹
When H-NMR, IR, CHN analysis, total halogen determination (oxygen flask combustion method) and GPC analysis (standard substance polystin) were carried out, the molecular weight was Mn = 150,000 and the polydispersity was Mw.
/Mn=1.6, CMS / ST molar ratio = 1/9.

Q 26.7 g (0.06) obtained as described above
6 mol) and PCS 65.3 g (CMS equivalent 0.060 equivalent)
When and were reacted in 850 ml of tetrahydrofuran at 65 ° C. for 64 hours, a yellow polymer was formed. After cooling the reaction mixture, it was added to 2 l of ethyl ether, and after stirring, the polymer was taken out by decantation. After washing with ethyl ether three times, the polymer was dissolved in a mixed solvent of methanol / tetrahydrofuran and added to water for reprecipitation. When the polymer thus purified was dried under reduced pressure with heating all day and night, a yellow powdery polymer (B
74.1 g (82.7% yield based on PCS) was obtained.

BPCQ was analyzed by using the same analysis method as for Q and PCS described above. As a result, the molecular weight was Mn = 17,000, the polydispersity was Mw / Mn = 1.8, and the degree of quaternization was 10.0%. The results are shown in Tables 1 and 2.

Example 2 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 6.1 g of ethanolamine (Wako Pure Chemical Industries, reagent grade 1, abbreviated as EA hereinafter). ) Was charged, 2.5 g (0.11 mol) of metallic sodium was gradually added with stirring. After addition, 5
The reaction was carried out at -10 ° C for 5 hours.

After the completion of the reaction, benzene was removed and Example 1 was used.
98.0 g of PCS obtained in step (0.090 equivalent to CMS)
And 100 ml of tetrahydrofuran were added, and the mixture was reacted under reflux for 24 hours. After the reaction, the obtained polymer (hereinafter, PC
S-EA) is re-precipitated with acetone / methanol,
Washed and dried. Yield 92.5g (Yield to EA 83.1g
%).

Next, to 92.5 g of PCS-EA (0.083 equivalent to CMS), 20 g of 40% formalin solution (0.27 mol to HCHO) and 20 g of formic acid (0.43 mol) were added, and the mixture was added to 60-
The reaction was carried out at 80 ° C for 8 hours. Obtained polymer (hereinafter PC
(Abbreviated as S-DA) is reprecipitated with an acetone / methanol system,
Washed and dried. Yield 87.7 g, 89.0% yield based on PCS-EA.

87.7 g of the PCS-DA (0.
074 equivalent), LB 21.2 g (0.085 mol) and 100 ml of ethyl alcohol were placed in a 500 ml eggplant-shaped flask and reacted at 90 ° C. for 24 hours to give a polymer (hereinafter abbreviated as PCS-TA) 93.1.
got g. Yield to PCS-DA 90.5%.

PCS-TA was analyzed in the same manner as in BPCQ of Example 1, and had a molecular weight Mn of 190,000 and a polydispersity Mw / Mn.
= 1.9, quaternization degree = 10.0%. The results are shown in Tables 1 and 2.

Example 3 40.3 g of PCS obtained in Example 1 (0.03 with respect to CMS)
Tetrachloroethylene was added to
11.1 g (0.056 mol) of -methyl-N-dodecylamine was added dropwise, and after refluxing for 4 hours, the reaction mixture was put into a mixed solution of potassium hydroxide aqueous solution and methanol, and washed with methanol until no free amine was detected. The yield of the produced polymer (hereinafter abbreviated as PCS-AA) was 42.5 g, and the yield was 91.9% (vs. PCS).

Next, 42.5 g of the polymer PCS-AA (C
0.036 equivalents to MS) and methyl monochloroacetate 5.5g
(0.051 mol) was refluxed in a tetrachloroethylene solution for 4 hours with stirring. Next, 1-N N was added to this mixed solution.
After adding an aqueous solution of aOH to make the solution alkaline, it was filtered and washed with methanol. After heating under reduced pressure, 41.9 g of white powdery polymer (abbreviated as PCT-BT) (vs. PCS-AA)
Yield 94.1%) was obtained. PCS-BT is orange-
It was quantified by colorimetric determination by method II.

Further, by the same analysis as in Example 1, molecular weight Mn = 214,000, polydispersity Mw / Mn = 2.9, quaternization degree = 10.0.
It was in%. The results are shown in Tables 1 and 2.

Example 4 27.5 g (0.16 mol) of N, N, N ', N'-tetramethyl-1,6-diaminohexane (hereinafter abbreviated as TMH) was dissolved in 50 ml of acetonitrile, and LB was added thereto while stirring at room temperature. 10.0 g (0.0
4 mol) was added dropwise, followed by heating at 70 ° C. for 3 hours. Next, the reaction solution was cooled to room temperature, and the white precipitate formed was filtered to give 0.13 g of N, N, N ', N'-tetramethyl-1,6-diaminohexane-N, N'-dilauryl dibromide. (Vs L
B byproduct rate 1.0%) It was a byproduct. The filtrate was concentrated under reduced pressure to remove most of TMH, the resulting white paste-like residue was washed with 40 ml of hexane, and the hexane layer was separated by decantation to completely remove unreacted TMH and form a white wax. Material was obtained. When this was dried under reduced pressure with a vacuum pump, N, N, N ', N'-tetramethyl-1,6-diaminohexane-N-lauryl bromide (hereinafter TML
15.6 g was produced (abbreviated as C ₆ ).
%).

TML-C ₆ (15.6 g, 37 mmol) was dissolved in 200 ml of acetone, and 5.2 g (34 mmol) of 4-chloromethylstyrene was added dropwise thereto with stirring at room temperature. Then 50 ℃
After heating for 17 hours, white crystals started to precipitate. The reaction solution was cooled to room temperature, the resulting white crystals were isolated by filtration, washed with cold acetone and dried to give N, N, N ', N'-tetramethyl-N-lauryl-N'-(4-vinyl) benzyl. Hexamethylenediammonium bromide chloride (TML
17.2 g (abbreviated as S-C ₆ ) was produced (relative to CMS yield 88.2%).

5.7 g (10 mmol) of TMLS-C ₆ and 9.4 g (90 mmol) of styrene were dissolved in 10 ml of methanol, and 50 mg of AIBN (0.3 mmol) was dissolved in methanol.
A solution dissolved in 2 ml was added. The mixture became a viscous solution when stirred at 65 ° C. for 22 hours under nitrogen atmosphere. The reaction solution was poured into a large amount of water to stop the polymerization reaction, and a white polymer produced was filtered and isolated, and dried under reduced pressure to obtain a white polymer. After re-dissolving in methanol, the operation of charging in ethyl acetate was repeated twice, and purified and dried to obtain 14.3 g of white powdery polymer (abbreviated as OBAQ) (yield 9
4.8%) was obtained.

OBAQ was confirmed to be a copolymer of TMLS-C ₆ and styrene by TLC, IR, ¹ H-NMR and CHN analysis. From the results of GPC analysis, polystyrene was used as a standard substance and the molecular weight was Mn = 16,000,
The polydispersity was Mw / Mn = 3.1. The content of the quaternary ammonium salt was determined by colloid titration and total halogen determination (oxygen flask combustion method), and it was 11.5%. The results are shown in Tables 1 and 2.

Example 5 15.1 g (10 meq) of the compound OBAQ obtained in Example 4 was dissolved in 2 l of a mixed solvent of methanol / water = 1/4, and 49.2 g (0.60 mol) of anhydrous sodium acetate was added. At room temperature
Stirring was continued for 24 hours. The solution was concentrated and then dried under reduced pressure at room temperature with a vacuum pump to obtain a white powdery mixture. Chloroform 300 was added to the white powder mixture.
After adding ml and filtering off the sodium salt, the chloroform solution was concentrated, and the precipitated white powder was dried under heating and reduced pressure for one day and night. As a result, a white powder polymer (abbreviated as OBAA) was obtained.
13.0 g (8.9 meq) was produced (89% yield of OBAA based on OBAQ). The results of performing the same analysis as in Example 4 are shown in Tables 1 and 2.

Comparative Examples 1-2 Commercially available antibacterial agent Benzalkonium chloride (abbreviated as BAC) was used as Comparative Example 1, commercial antibacterial agent silver-containing zeolite compound (Ag
Comparative Example 2 is abbreviated as -Z).

Example 6 Coating on spectacle frame Five beakers of 500 ml each were charged with 165 g of thinner (CS-50), and then the compounds BPCQ and PCS obtained in Examples 1, 2, 3, 4 and 5, respectively. -TA, PCS-B
After adding 1 g each of T, OBAQ and OBAA, they were dissolved by ultrasonic treatment for about 10 minutes to obtain a uniform solution. To this thinner solution, 99 g of AC970 clear resin (acrylic resin / amino resin varnish = 50/50 w / w) was added and dissolved by stirring at room temperature for about 1 hour. Then, this resin mixture was sprayed on a metal spectacle frame according to a conventional method, and dried at 45 ° C. for 60 minutes.

Instead of the compound used in Example 6 for comparison, the compounds BAC and Ag-Z of Comparative Examples 1 and 2 were used.
The same operations and post-treatments as in Example 6 were carried out except that 1 g each was used to obtain antibacterial eyeglass frames.

Comparative Example 3 Blank (Unantibacterial Treated Eyeglass Frame) The same operation and treatment as in Example 6 were carried out except that the compound BPCQ and the like were not used in Example 6 to obtain an unantibacterial treated eyeglass frame, which was blanked. And

Test Example 1 Eyeglass Frame Bath Wash Abuse Test Example 6 and Comparative Example 3 for the purpose of comparing the persistence of antibacterial activity.
Before the abuse, the eyeglass frames obtained in 1. were individually immersed in 1 liter of boiling water, and boiled for 15 minutes to be treated with hot water. After the main abuse, the frame was dried at 60 ° C. for about 24 hours, and used as eyeglass frames after bath-wash abuse.

Test Example 2 Antibacterial Test of Eyeglass Frame As the test eyeglass frame, the eyeglass frames before the abuse obtained in Example 6 and Comparative Example 3 and the eyeglass frames after the abuse in Test Example 1 were used, respectively. . Staphylo Staphylococcus aureus, which is a skin-resident bacterium, is used as the test bacterium.
Tested with coccus aureus IFO 12732. First, a bacterium that was shake-cultured for 18 hours in a nutrient broth (Difco. Lab.) Was diluted to 10 ⁴ cells / ml with sterile water to obtain a bacterium solution. Next, the sample eyeglass frame was placed in a polypropylene gas barrier bag (180 × 80 cm), 50 ml of the above-mentioned bacterial solution was placed therein, and heat sealed. The bag containing the spectacle frame was set in a constant temperature shaking culture device at 37 ° C., and a culture test was performed for 18 hours. After the culture test, the bacterial solution was collected, and the number of remaining viable bacteria was measured by the colony counting method according to a conventional method. The test results are shown in Tables 3-4.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

Initial number of bacteria (a): 62,000 cells / ml Bactericidal index = log [(b / a) × 100] Since the number of viable bacteria was 0 this time and the above equation was not satisfied, the number of viable bacteria was set to 1. The bactericidal index was calculated.

From Table 4, it is clear that even after the bath-washing abuse, the antibacterial effect of the compound of the present invention is superior to that of the commercially available antibacterial agent.

Test Example 3 A primary skin irritation test was conducted by the following method. Test animals Young white rabbits of New Zealand White (island skin free) were obtained from Inoue Laboratory Animal Center. The age at the time of acquisition is 4 months, and the weight is 2.83-3.
It was 08 kg. The temperature of the breeding room is 22 ± 1 ℃, the humidity is 55-66%,
Ventilation rate 15 times / hour, lighting time 12 hours / day (7:00 am ~
It was 7pm). The animal is an aluminum cage (32 x
55 x 35 cm) were individually bred. The animals were allowed to freely ingest solid feed RC4 for experimental animals (Oriental Yeast Co., Ltd.). As for water, tap water was supplied to each cage by an automatic water supply system to allow free intake. The animals were acclimated to the above-mentioned breeding environment for 1 week or more before the start of the test.

Preparation of test substance The compounds of Examples 1 to 5 were preliminarily placed in a mortar to give 0.5 g of the test substance.
0.5 ml of distilled water for injection was added to form a paste, and the whole amount was collected and applied to a lint cloth. Exposure method The hair on the back of the animal during preliminary breeding was cut with an electric hair clipper (THRIVE A
NIMAL CLIPPER MODEL900, Natsume Seisakusho Co., Ltd.), lightly shaved the hair, and selected 3 animals with little island skin. Approximately 24 hours before the start of the test, the back hair of the animal was similarly shaved and hair was removed with a hair remover (Eva Claim, Tokyo Tanabe Seiyaku Co., Ltd.). As test sites, a total of 4 sites were provided for each animal, two on each side of the midline of the spine. The test substance was applied uniformly to 2.5 × 2.5 cm ² lint cloth (Nishio Sanitary Material Co., Ltd.) as described above (described in Preparation of test substance), and they were applied with a plaster (Dermicelle, Tokyo Hygiene Institute Co., Ltd.). It was used to occlude the skin at the test site. 0.5 ml as a control
Only the lint cloth coated with distilled water for injection was attached in the same manner. The application of lint cloth was randomly selected for each animal in consideration of the difference in sensitivity between test sites. Exposure time is 4 hours,
At the end of the exposure, the test substance remaining on the skin was removed by gently wiping it with absorbent cotton soaked in lukewarm water.

Observation Items The skin reaction at the test site after the exposure was evaluated according to the evaluation criteria for skin irritation of OECD [Table 5]. The observation time was 30 minutes after the end of the exposure and 1 day after the exposure until the skin reaction disappeared, and the observation was performed up to 14 days later. The results are shown in Table 6.
It was shown to.

[0086]

[Table 5] Erythema and crust formation No erythema ………………………………………………………………………… 0 Very mild erythema (barely distinguishable) Yes) ………………………………………… 1 is the erythema that was associated with …………………………………………………………………… 2 Moderate or not High-grade erythema ………………………………………………………… 3 From high-grade erythema (beet redness) to slight crust formation (deep damage) …… 4 Highest score 4 Edema formation No edema ………………………………………………………………………… 0 Very mild edema (barely distinguishable) …………… …………………… 1 Mild edema (a clear edge can be identified due to bulging bulge) ……………… 2 Moderate edema (bulge of about 1 mm) ………………………… ………………………………… 3 Advanced edema Beyond the bulging and exposure range of 1mm spread) .............................. 4 highest point 4

[0087]

[Table 6]

In Table 6, A indicates erythema and crust, and B indicates edema. From the results in Table 6, it can be seen that the compounds of the present invention have no skin irritation. Therefore, even if the spectacle frame is coated with the compound, it can be used with confidence.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masao Ikeda 2-7-5 Hanado Minami, Fukui City, Fukui Prefecture

Claims (3)

[Claims] 1. A treatment method for imparting antibacterial properties to an eyeglass frame and an eyeglass component, which comprises coating the surfaces of the eyeglass frame and the eyeglass component with an antibacterial polymer. 2. The antibacterial polymer is a polymer containing a vinyl copolymer containing a structural unit derived from a non-crosslinkable vinyl monomer and a structural unit represented by the general formula 1 as an active ingredient. Processing method. [Chemical 1] [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. ] 3. In the compound (1), B is represented by the general formula 2 to
The treatment method according to claim 2, which is a group represented by Chemical formula 5. [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [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. ]